Organic ammonium salt and hydrogen bonding material treating agent using the same

Abstract

The present invention provides a novel compound useful for various treatments of hydrogen-bonding materials such as biological samples and a hydrogen-bonding material treatment agent. The present invention is an organic ammonium salt and a hydrogen-bonding material treatment agent containing the organic ammonium salt. The organic ammonium salt is solid at 25°C and contains anions and ammonium cations represented by the following formula (I): N + R n H 4‑n (I) (In formula (I), R each independently represents a hydroxyalkyl group, etc., the hydroxyalkyl group has one or more hydroxyl groups, the alkyl portion is a straight chain or branched chain having 1 to 10 carbon atoms, and the alkyl portion may also contain an oxygen atom. n represents an integer of 0 to 4.)

Description

Technical Field

[0001] The present invention relates to an organic ammonium salt and a hydrogen-bonding material treating agent using the organic ammonium salt. Background Art

[0002] The three-dimensional structure of the molecules of biocatalysts such as enzymes and yeast, peptides, proteins, nucleic acids, or poorly soluble polysaccharides such as cellulose are easily destroyed due to the influence of temperature, pH, solvent, or electrostatic repulsion between molecules, thereby reducing their activity, that is, catalytic ability. Therefore, when they are used for the preservation of biocatalytic ability and biocatalytic reactions, or when preserving biological samples, it is necessary to maintain the three-dimensional structure of the active site and the three-dimensional structure of the amino acid residues.

[0003] As a method for long-term storage of biocatalysts and biological samples, freeze-drying in a powder state and cryopreservation in which the biocatalysts and biological samples are dissolved in a solution under low concentration and extremely low temperature conditions for storage are known.

[0004] Generally speaking, it is preferred to store the biocatalyst in a solution for ease of operation. However, in the case of cryopreservation, special equipment is required, and there is a problem that ice is generated during freezing, which destroys the three-dimensional structure of the biocatalyst, and when the frozen solution is dissolved for use, the structure of the biocatalyst changes, which leads to a decrease in activity. In addition, in the case of urease and catalase, for example, the storage concentration is usually low, about 1 to 3 mg / mL, which makes it difficult to store effectively.

[0005] In order to prevent the inactivation of such biocatalysts and maintain the activity of the enzyme, attempts have been made to add stabilizers. For example, a method of using polyols such as glycerol and sorbitol to preserve uricase (Patent Document 1) and a method of stabilizing cholesterol oxidase by adding bovine serum albumin and sugars to a solution containing cholesterol oxidase (Patent Document 2) have been proposed. However, these methods have the problem of reduced enzyme activity related to storage concentration, storage temperature and storage period.

[0006] In order to solve the above problems, the applicant has found that liquid ionic liquids can be used for the preservation of biocatalysts and biological samples at room temperature (Patent Documents 3 to 5). Although the room temperature liquid ionic liquids have excellent affinity with biological samples and excellent preservation, they are not suitable for uses that require solid substances at room temperature, for example, they are not suitable for clinical diagnostic reagents or biosensors, and further improvement is needed. In addition, when stored in a liquid state, it is difficult to preserve the biological sample under high concentration conditions from the perspective of the solubility of the biological sample in the liquid. Therefore, as a solid state, although freeze drying or frozen storage can be used, there is a problem of low long-term stability of the biological sample.

[0007] As an example of a solid enzyme stabilizer, there is disclosed an example of using a plant-derived polypeptide which is a hydrolyzate of soybean or the like (Patent Document 6), but the stabilization effect thereof is not sufficient.

[0008] In addition to such biological sample preservation materials, a treatment agent that can perform various treatments on hydrogen-bonding materials such as biological samples is also expected, for example, a treatment agent that has excellent solubility or dispersibility when water, solvents, etc. are added after the hydrogen-bonding material is made into a solid composition, and a novel compound that has good affinity with the hydrogen-bonding material to make this possible.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Laid-Open No. 06-70798

[0012] Patent Document 2: Japanese Patent Application Laid-Open No. 08-187095

[0013] Patent Document 3: Japanese Patent Application Publication No. 2014-131974

[0014] Patent Document 4: Japanese Patent Application Publication No. 2014-131975

[0015] Patent Document 5: International Publication No. 2015 / 156398

[0016] Patent Document 6: Japanese Patent Application Publication No. 2006-42757 Summary of the invention

[0017] Problem that the invention aims to solve

[0018] In view of the above circumstances, one of the objects of the present invention is to provide a novel compound useful for various treatments of hydrogen bonding materials.

[0019] Another object of the present invention is to provide a treatment agent useful for various treatments of hydrogen bonding materials.

[0020] Furthermore, another object of the present invention is to provide a treatment agent that is excellent in maintaining the three-dimensional structure of a biological sample even in a solid state, under high concentration, high temperature and long time conditions; and to provide a biological sample solution that is excellent in maintaining the three-dimensional structure of a biological sample even in a solution state such as an aqueous solution, under high concentration, high temperature and long time conditions.

[0021] Furthermore, another object of the present invention is to provide a treatment agent which has excellent solubility and dispersibility in an organic hydrogen-bonding material and an inorganic hydrogen-bonding material, and which has excellent solubility or dispersibility when water, a solvent, etc. are added after the obtained solution or dispersion is formed into a solid composition.

[0022] Technical means of solving problems

[0023] In order to solve the above problems, the organic ammonium salt of the present invention is characterized in that it is solid at 25° C. and contains an anion and an ammonium cation represented by the following formula (I):

[0024] N + R n H 4-n (I)

[0025] (In formula (I), R each independently represents: a hydroxyalkyl group having one or more hydroxyl groups, an alkyl group having 1 to 10 carbon atoms in a straight chain or branched chain, and the alkyl group may contain an oxygen atom; a carboxyalkyl group having one or more carboxyl groups, an alkyl group having 1 to 10 carbon atoms in a straight chain or branched chain, and the alkyl group may contain an oxygen atom; or a hydroxycarboxyalkyl group having one or more hydroxyl groups and one or more carboxyl groups, an alkyl group having 1 to 10 carbon atoms in a straight chain or branched chain, and the alkyl group may contain an oxygen atom, and n represents an integer from 0 to 4.)

[0026] The hydrogen-bonding material treating agent of the present invention contains the above-mentioned organic ammonium salt.

[0027] In a preferred example of the hydrogen-bonding material processing agent, the hydrogen-bonding material is a biological sample (hereinafter, in this case, also referred to as a biological sample processing agent).

[0028] The solid composition of the present invention includes the hydrogen-bonding material treating agent and the hydrogen-bonding material.

[0029] The biological sample solution of the present invention includes a hydrogen bonding material treating agent (biological sample treating agent), a biological sample, and a solvent.

[0030] Effects of the Invention

[0031] According to the present invention, a novel compound useful for various treatments of hydrogen bonding materials can be provided.

[0032] Furthermore, according to the present invention, it is possible to provide a treatment agent useful for various treatments of hydrogen-bonding materials such as biological samples.

[0033] According to the present invention, a treatment agent can be provided that is excellent in maintaining the three-dimensional structure of a biological sample even in a solid state, under high concentration, high temperature and long time conditions; and a biological sample solution can be provided that is excellent in maintaining the three-dimensional structure of a biological sample even in a solution state such as an aqueous solution, under high concentration, high temperature and long time conditions.

[0034] According to the present invention, there is provided a treatment agent which has excellent solubility and dispersibility in an organic hydrogen-bonding material or an inorganic hydrogen-bonding material, and which has excellent solubility or dispersibility when water, a solvent, or the like is added after the obtained solution or dispersion is formed into a solid composition. DETAILED DESCRIPTION

[0035] Hereinafter, the present invention will be described in detail.

[0036] (Organic ammonium salt)

[0037] In the cation of the organic ammonium salt of the present invention, R in formula (I) represents a hydroxyalkyl group, a carboxyalkyl group or a hydroxycarboxyalkyl group.

[0038] The hydroxyalkyl group has one or more hydroxyl groups, and the alkyl portion is preferably a linear or branched chain having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and the alkyl portion may contain an oxygen atom.

[0039] The carboxyalkyl group has one or more carboxyl groups, and the alkyl portion is preferably a linear or branched chain having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and the alkyl portion may contain an oxygen atom.

[0040] The hydroxycarboxyalkyl group has one or more hydroxyl groups and one or more carboxyl groups, and the alkyl portion is preferably a linear or branched chain having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and the alkyl portion may contain an oxygen atom.

[0041] Here, when the alkyl part contains an oxygen atom, the oxygen atom forms, for example, an ether bond, a carbonyl group, an ester bond, an amide bond, a urea bond or a urethane bond in the alkyl part. Therefore, in the present invention, "the alkyl part contains an oxygen atom" includes a case where the alkyl part is interrupted by a group containing a hetero atom such as a nitrogen atom as an atomic group containing an oxygen atom.

[0042] Examples of the hydroxyalkyl group include monohydroxyalkyl groups and polyhydroxyalkyl groups. Specific examples thereof include hydroxyalkyl groups not containing an oxygen atom at the alkyl portion, hydroxyalkoxyalkyl groups, alkoxyhydroxyalkyl groups, and hydroxypolyalkyleneoxyalkyl groups.

[0043] The monohydroxyalkyl group is not particularly limited. For example, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropane-1-yl, 2-hydroxypropane-1-yl, 3-hydroxypropane-1-yl, 1-hydroxypropane-2-yl, 2-hydroxypropane-2-yl, 1-hydroxybutane-1-yl, 2-hydroxybutane-1-yl, 3-hydroxybutane-1-yl, 4-hydroxybutane-1-yl, 1-hydroxy-2-methylpropane-1-yl, 2-hydroxy-2-methylpropane-2 ... The monohydroxyalkyl group is preferably a monohydroxyalkyl group having 1 to 10 carbon atoms, more preferably a monohydroxyalkyl group having 1 to 6 carbon atoms, and still more preferably a monohydroxyalkyl group having 1 to 3 carbon atoms.

[0044] The polyhydroxyalkyl group is not particularly limited, and examples thereof include dihydroxyalkyl, trihydroxyalkyl, tetrahydroxyalkyl, pentahydroxyalkyl, hexahydroxyalkyl, heptahydroxyalkyl, and octahydroxyalkyl. Specifically, examples thereof include dihydroxyethyl such as 1,2-dihydroxyethyl; dihydroxypropane-1-yl such as 1,2-dihydroxypropane-1-yl and 2,3-dihydroxypropane-1-yl; dihydroxypropane-2-yl such as 1,2-dihydroxypropane-2-yl and 1,3-dihydroxypropane-2-yl; trihydroxypropane-1-yl; trihydroxypropane-2-yl; dihydroxybutane-1-yl such as 1,2-dihydroxybutane-1-yl, 1,3-dihydroxybutane-1-yl, 1,4-dihydroxybutane-1-yl, 2,3-dihydroxybutane-1-yl, 2,4-dihydroxybutane-1-yl and 3,4-dihydroxybutane-1-yl. trihydroxybutane-1-yl, 1,2,3-trihydroxybutane-1-yl, 1,2,4-trihydroxybutane-1-yl, 1,3,4-trihydroxybutane-1-yl, 2,3,4-trihydroxybutane-1-yl, etc. trihydroxybutane-1-yl; tetrahydroxybutane-1-yl; dihydroxy-2-methylpropane-1-yl, 1,2-dihydroxy-2-methylpropane-1-yl, 1,3-dihydroxy-2-methylpropane-1-yl, 2,3-dihydroxy-2-methylpropane-1-yl, etc. trihydroxy-2-methylpropane-1-yl; tetrahydroxy-2-methylpropane-1-yl; 1,2-dihydroxybutane-2-yl, 1,3-dihydroxybutane- 1,4-dihydroxybutane-2-yl, 2,3-dihydroxybutane-2-yl, 2,4-dihydroxybutane-2-yl, 3,4-dihydroxybutane-2-yl and other dihydroxybutane-2-yl; 1,2,3-trihydroxybutane-2-yl, 1,2,4-trihydroxybutane-2-yl, 1,3,4-trihydroxybutane-2-yl, 2,3,4-trihydroxybutane-2-yl and other trihydroxybutane-2-yl; tetrahydroxybutane-2-yl; 1,3-dihydroxy-2-methylpropane-2-yl, 1,3-dihydroxy-2-ethylpropane-2-yl, 1,3-dihydroxy-2-hydroxymethylpropane-2-yl; dihydroxy The polyhydroxyalkyl group may be pentane-1-yl, trihydroxypentane-1-yl, tetrahydroxypentane-1-yl or pentahydroxypentane-1-yl; dihydroxyhexane-1-yl, trihydroxyhexane-1-yl, tetrahydroxyhexane-1-yl, pentahydroxyhexane-1-yl or hexahydroxyhexane-1-yl; dihydroxyheptane-1-yl, trihydroxyheptane-1-yl, tetrahydroxyheptane-1-yl, pentahydroxyheptane-1-yl, hexahydroxyheptane-1-yl or heptahydroxyheptane-1-yl; dihydroxyoctane-1-yl, trihydroxyoctane-1-yl, tetrahydroxyoctane-1-yl, pentahydroxyoctane-1-yl, hexahydroxyoctane-1-yl, heptahydroxyoctane-1-yl or octahydroxyoctane-1-yl, etc. The polyhydroxyalkyl group may be preferably a polyhydroxyalkyl group having 1 to 10 carbon atoms and having 2 to 6 hydroxyl groups, and more preferably a polyhydroxyalkyl group having 1 to 6 carbon atoms. In addition, a branched polyhydroxyalkyl group represented by the following formula (II) is exemplified as a preferred group.

[0045]

[0046] (In the formula, R 11 represents a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a linear monohydroxyalkyl group having 1 to 4 carbon atoms.

[0047] Among the above-mentioned polyhydroxyalkyl groups, preferred are 2,3-dihydroxypropane-1-yl, 1,3-dihydroxypropane-2-yl, 1,3-dihydroxy-2-ethylpropane-2-yl, 1,3-dihydroxy-2-hydroxymethylpropane-2-yl and pentahydroxyhexane-1-yl.

[0048] As the carboxyalkyl group, there can be listed a monocarboxyalkyl group and a polycarboxyalkyl group, and as specific examples thereof, there can be listed groups in which the hydroxyl group of the above-mentioned monohydroxyalkyl group, dihydroxyalkyl group, trihydroxyalkyl group, tetrahydroxyalkyl group, pentahydroxyalkyl group, hexahydroxyalkyl group, heptahydroxyalkyl group or octahydroxyalkyl group is replaced by a carboxyl group.

[0049] The monocarboxyalkyl group is not particularly limited, and examples thereof include carboxymethyl, 1-carboxyethyl, 2-carboxyethyl, 1-carboxypropane-1-yl, 2-carboxypropane-1-yl, 3-carboxypropane-1-yl, 1-carboxypropane-2-yl, 2-carboxypropane-2-yl, 1-carboxybutane-1-yl, 2-carboxybutane-1-yl, 3-carboxybutane-1-yl, 4-carboxybutane-1-yl, 1-carboxy-2-methylpropane-1-yl, 2-carboxy The carboxyalkyl group is preferably a carboxyalkyl group having 1 to 10 carbon atoms, more preferably a carboxyalkyl group having 1 to 6 carbon atoms.

[0050] The hydroxycarboxyalkyl group is not particularly limited, and examples thereof include groups in which a part of the hydroxyl groups of the dihydroxyalkyl, trihydroxyalkyl, tetrahydroxyalkyl, pentahydroxyalkyl, hexahydroxyalkyl, heptahydroxyalkyl or octahydroxyalkyl groups exemplified above are replaced with carboxyl groups.

[0051] In the organic ammonium salt of the present invention, n in formula (I) is an integer of 0 to 4, preferably an integer of 1 to 4. When R in formula (I) is a polyhydroxyalkyl group, n is preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, and particularly preferably 1.

[0052] The anion of the organic ammonium salt of the present invention is not particularly limited, and examples thereof include carboxylic acid anions, halide anions, sulfur anions, fluorine anions, boron anions, nitrogen oxide anions, phosphorus anions, and cyanide anions.

[0053] The carboxylate anion is an organic acid anion having at least one carboxylate anion (-COO-) in a molecule, and can include a functional group having heteroatoms such as an oxygen atom, a nitrogen atom, a sulphur atom. Although there is no particular limitation on it, as the carboxylate anion, for example, saturated aliphatic monocarboxylic acid anion, alicyclic carboxylic acid anion, unsaturated aliphatic monocarboxylic acid anion, saturated hydroxycarboxylic acid anion (saturated hydroxymonocarboxylic acid anion, saturated hydroxydicarboxylic acid anion or saturated hydroxytricarboxylic acid anion, etc.), saturated dicarboxylic acid anion, unsaturated dicarboxylic acid anion, aromatic carboxylic acid anion, saturated carbonyl carboxylic acid anion, alkyl ether carboxylic acid anion, halogenated carboxylic acid anion, etc. (the carbon number of the carboxylate anion listed below includes the carbon of the carboxyl group.).

[0054] The saturated aliphatic monocarboxylic acid anion is composed of a straight-chain or branched aliphatic saturated hydrocarbon group and a carboxylic acid anion, may contain a carboxyl group and a carboxylate group, and preferably has 1 to 22 carbon atoms. Specifically, for example, there can be mentioned anions from which protons are dissociated from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, arachidic acid, heneicosanoic acid, docosanoic acid, isobutyric acid, 2-methylbutyric acid, isovaleric acid, 2-ethylhexanoic acid, isononanoic acid, isopalmitic acid, isostearic acid, and the like.

[0055] When the anion of the organic ammonium salt is the saturated aliphatic monocarboxylic acid anion, one example of the compound of formula (I) is shown below.

[0056] R in the formula (I) is a linear monohydroxyalkyl group or a branched monohydroxyalkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 4.

[0057] In the formula (I), R is a linear monohydroxyalkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4.

[0058] In formula (I), R is 1-hydroxyethyl, and n=1.

[0059] In formula (I), R is 1-hydroxyethyl, and n=2.

[0060] In formula (I), R is 1-hydroxyethyl, and n=3.

[0061] R of formula (II) 11It is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a linear monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0062] R in formula (I) is 1,3-dihydroxypropane-2-yl, and n=1.

[0063] R of formula (II) 11 It is a straight-chain alkyl group having 1 to 4 carbon atoms, and n=1.

[0064] R in formula (I) is 1,3-dihydroxy-2-ethylpropane-2-yl, and n=1.

[0065] R of formula (II) 11 It is a straight-chain monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0066] R in formula (I) is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1.

[0067] In the formula (I), R is a linear polyhydroxyalkyl group or a branched polyhydroxyalkyl group having 1 to 10 carbon atoms and having two or more hydroxyl groups, and n is an integer of 1 to 4.

[0068] · R in formula (I) is pentahydroxyhexane-1-yl, and n=1.

[0069] R in formula (I) is 1-hydroxyethyl, and n = 3. The saturated aliphatic monocarboxylic acid anion is a formate anion.

[0070] R in formula (I) is 1,3-dihydroxy-2-ethylpropane-2-yl, and n=1; or R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1. The saturated aliphatic monocarboxylic acid anion is an acetic acid anion.

[0071] R in formula (I) is 1,3-dihydroxypropane-2-yl, and n=1; R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1; or R is pentahydroxyhexane-1-yl, and n=1. The saturated aliphatic monocarboxylic acid anion is a butyric acid anion.

[0072] In formula (I), R is 1-hydroxyethyl, and n=1; R is 1,3-dihydroxypropane-2-yl, and n=1; R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1; or R is pentahydroxyhexane-1-yl, and n=1. The saturated aliphatic monocarboxylic acid anion is a hexanoic acid anion.

[0073] In formula (I), R is 1-hydroxyethyl, and n=1; R is 1-hydroxyethyl, and n=3; R is 1,3-dihydroxypropane-2-yl, and n=1; R is 1,3-dihydroxypropane-2-yl, and n=1; R is 1,3-dihydroxy-2-ethylpropane-2-yl, and n=1; R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1; or R is pentahydroxyhexane-1-yl, and n=1. The saturated aliphatic monocarboxylic acid anion is an octanoic acid anion.

[0074] In formula (I), R is 1-hydroxyethyl, and n=1; R is 1-hydroxyethyl, and n=3; R is 1,3-dihydroxypropane-2-yl, and n=1; R is 1,3-dihydroxy-2-ethylpropane-2-yl, and n=1; R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1; or R is pentahydroxyhexane-1-yl, and n=1. The saturated aliphatic monocarboxylic acid anion is a decanoic acid anion.

[0075] In formula (I), R is 1-hydroxyethyl, and n=1; R is 1-hydroxyethyl, and n=2; R is 1-hydroxyethyl, and n=3; R is 1,3-dihydroxypropane-2-yl, and n=1; R is 1,3-dihydroxy-2-ethylpropane-2-yl, and n=1; R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1; or R is pentahydroxyhexane-1-yl, and n=1. The saturated aliphatic monocarboxylic acid anion is a lauric acid anion.

[0076] The alicyclic carboxylic acid anion is composed of a saturated or unsaturated carbon ring without aromatic properties and one or more carboxylic acid anions, and preferably has 6 to 20 carbon atoms. Among them, the alicyclic carboxylic acid anion having a cyclohexane ring skeleton is preferred, and specifically, for example, anions obtained by dissociating protons from cyclohexanecarboxylic acid and cyclohexanedicarboxylic acid can be cited.

[0077] When the anion of the organic ammonium salt is the alicyclic carboxylic acid anion, one example of the compound of formula (I) is shown below.

[0078] In the formula (I), R is a linear monohydroxyalkyl group or a branched monohydroxyalkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 4.

[0079] In the formula (I), R is a linear monohydroxyalkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4.

[0080] In formula (I), R is 1-hydroxyethyl, and n=1.

[0081] In formula (I), R is 1-hydroxyethyl, and n=2.

[0082] R of formula (II)11 It is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a linear monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0083] R in formula (I) is 1,3-dihydroxypropane-2-yl, and n=1.

[0084] In formula (I), R is 1-hydroxyethyl, and n=1; R is 1-hydroxyethyl, and n=3; or R is 1,3-dihydroxypropane-2-yl, and n=1. The alicyclic carboxylic acid anion is a cyclohexanecarboxylic acid anion.

[0085] The unsaturated fatty monocarboxylic acid anion is composed of a straight-chain aliphatic unsaturated hydrocarbon group or a branched aliphatic unsaturated hydrocarbon group and one or more carboxylic acid anions, may contain a carboxyl group or a carboxylate group, and preferably has 3 to 22 carbon atoms. Specifically, for example, anions from which protons are dissociated from acrylic acid, methacrylic acid, crotonic acid, palmitoleic acid, oleic acid, 11-octadecenoic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid, and the like can be cited.

[0086] When the anion of the organic ammonium salt is the unsaturated aliphatic monocarboxylic acid anion, one example of the compound of formula (I) is shown below.

[0087] In the formula (I), R is a linear monohydroxyalkyl group or a branched monohydroxyalkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 4.

[0088] In the formula (I), R is a linear monohydroxyalkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4.

[0089] In formula (I), R is 1-hydroxyethyl, and n=1.

[0090] In formula (II), R 11 It is a straight-chain alkyl group having 1 to 4 carbon atoms, and n=1.

[0091] R in formula (I) is 1,3-dihydroxy-2-ethylpropane-2-yl, and n=1.

[0092] R in formula (I) is 1-hydroxyethyl, and n = 1. The unsaturated aliphatic monocarboxylic acid anion is a crotonic acid anion.

[0093] R in formula (I) is 1,3-dihydroxy-2-ethylpropane-2-yl. The unsaturated aliphatic monocarboxylic acid anion is an oleic acid anion.

[0094] The saturated hydroxycarboxylic acid anion is composed of a straight-chain aliphatic saturated hydrocarbon group or a branched aliphatic saturated hydrocarbon group, one or more carboxylic acid anions and one or more hydroxyl groups, and may also contain a carboxyl group or a carboxylate group, and preferably has 2 to 24 carbon atoms. Among them, a saturated aliphatic hydroxycarboxylic acid anion having 2 to 7 carbon atoms and having 1 to 4 hydroxyl groups is preferred. Specifically, for example, anions from which protons are dissociated from glycolic acid, lactic acid, tartronic acid, glyceric acid, glycolic acid, hydroxybutyric acid, 2-hydroxydecanoic acid, 3-hydroxydecanoic acid, 12-hydroxystearic acid, dihydroxystearic acid, hydroxycerebral fatty acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, leucine, mevalonate, pantothenic acid, cinchona acid, etc. can be cited.

[0095] When the anion of the organic ammonium salt is a saturated aliphatic monohydroxycarboxylic acid anion among the saturated aliphatic hydroxycarboxylic acid anions, it preferably has 2 to 24 carbon atoms, and more preferably has 2 to 7 carbon atoms. The number of hydroxyl groups is preferably 1 to 4. An example of the compound of formula (I) is shown below.

[0096] In the formula (I), R is a linear monohydroxyalkyl group or a branched monohydroxyalkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 4.

[0097] In the formula (I), R is a linear monohydroxyalkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4.

[0098] In formula (I), R is 1-hydroxyethyl, and n=1.

[0099] In formula (I), R is 1-hydroxyethyl, and n=2.

[0100] In formula (I), R is 1-hydroxyethyl, and n=3.

[0101] In formula (II), R 11 It is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a linear monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0102] R in formula (I) is 1,3-dihydroxypropane-2-yl, and n=1.

[0103] R in formula (I) is 1,3-dihydroxy-2-ethylpropane-2-yl, and n=1.

[0104] In formula (II), R 11 It is a straight-chain monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0105] R in formula (I) is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1.

[0106] In the formula (I), R is a linear polyhydroxyalkyl group or a branched polyhydroxyalkyl group having 1 to 10 carbon atoms and having two or more hydroxyl groups, and n is an integer of 1 to 4.

[0107] · R in formula (I) is pentahydroxyhexane-1-yl, and n=1.

[0108] R in formula (I) is 1,3-dihydroxy-2-ethylpropane-2-yl, and n=1; or R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1. The saturated aliphatic monohydroxycarboxylic acid anion is a glycolic acid anion.

[0109] R of formula (I) is 1,3-dihydroxypropane-2-yl, and n=1; R is 1,3-dihydroxy-2-ethylpropane-2-yl, and n=1; R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1; or R is pentahydroxyhexane-1-yl, and n=1. The saturated aliphatic monohydroxycarboxylic acid anion is a 9,10-dihydroxystearic acid anion.

[0110] In formula (I), R is 1-hydroxyethyl, and n=1; R is 1-hydroxyethyl, and n=2; R is 1,3-dihydroxypropane-2-yl, and n=1; or R is 1,3-dihydroxy-2-ethylpropane-2-yl, and n=1. The saturated aliphatic monohydroxycarboxylic acid anion is a cinchona acid anion.

[0111] R in formula (I) is 1,3-dihydroxypropane-2-yl, and n = 1. The saturated aliphatic monohydroxycarboxylic acid anion is 12-hydroxystearic acid anion.

[0112] When the anion of the organic ammonium salt is a saturated aliphatic hydroxydicarboxylic acid anion or a saturated aliphatic hydroxytricarboxylic acid anion among the saturated aliphatic hydroxycarboxylic acid anions, the anion preferably has 4 to 24 carbon atoms. The number of hydroxyl groups is preferably 1 to 3. An example of the compound of formula (I) is shown below.

[0113] In the formula (I), R is a linear monohydroxyalkyl group or a branched monohydroxyalkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 4.

[0114] In the formula (I), R is a linear monohydroxyalkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4.

[0115] In formula (I), R is 1-hydroxyethyl, and n=1.

[0116] R in formula (I) is 1-hydroxyethyl, and n=1. The saturated aliphatic hydroxydicarboxylic acid anion or saturated aliphatic hydroxytricarboxylic acid anion is tartaric acid.

[0117] R in formula (I) is 1-hydroxyethyl, and n = 1. The saturated aliphatic hydroxydicarboxylic acid anion or saturated aliphatic hydroxytricarboxylic acid anion is a citrate anion.

[0118] The saturated dicarboxylic acid anion preferably has 2 to 24 carbon atoms, more preferably 2 to 10 carbon atoms. Specific examples include anions obtained by dissociating protons from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and the like.

[0119] When the anion of the organic ammonium salt is the saturated dicarboxylic acid anion, one example of the compound of formula (I) is shown below.

[0120] In the formula (I), R is a linear monohydroxyalkyl group or a branched monohydroxyalkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 4.

[0121] In the formula (I), R is a linear monohydroxyalkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4.

[0122] In formula (I), R is 1-hydroxyethyl, and n=1.

[0123] In formula (I), R is 1-hydroxyethyl, and n=3.

[0124] In formula (II), R 11 It is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a linear monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0125] R in formula (I) is 1,3-dihydroxypropane-2-yl, and n=1.

[0126] In formula (II), R 11 It is a straight-chain monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0127] R in formula (I) is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1.

[0128] R in formula (I) is 1,3-dihydroxypropane-2-yl, and n=1, and the saturated aliphatic monohydroxycarboxylic acid anion is an oxalate anion.

[0129] In formula (I), R is 1-hydroxyethyl, n=1; or R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, n=1, and the dicarboxylic acid anion is a succinic acid anion.

[0130] In formula (I), R is 1-hydroxyethyl, n=1; R is 1,3-dihydroxypropane-2-yl, n=1; or R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, n=1, and the saturated dicarboxylic acid anion is adipic acid anion.

[0131] R in formula (I) is 1,3-dihydroxypropane-2-yl, and the saturated dicarboxylic acid anion is a sebacic acid anion.

[0132] The unsaturated dicarboxylic acid anion preferably has 2 to 24 carbon atoms, more preferably 2 to 10 carbon atoms. Specific examples thereof include anions obtained by dissociating protons from maleic acid, fumaric acid, citraconic acid, mesaconic acid, 2-pentenoic acid, methylene succinic acid, allylmalonic acid, isopropylidene succinic acid, adipic acid, 2,4-hexadienedioic acid, and the like.

[0133] When the anion of the organic ammonium salt is the unsaturated dicarboxylic acid anion, one example of the compound of formula (I) is shown below.

[0134] In the formula (I), R is a linear monohydroxyalkyl group or a branched monohydroxyalkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 4.

[0135] In the formula (I), R is a linear monohydroxyalkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4.

[0136] R in formula (I) is 1,3-dihydroxypropane-2-yl, and n=1.

[0137] R in formula (I) is 1,3-dihydroxypropane-2-yl, n=1, and the dicarboxylic acid anion is a maleic acid anion.

[0138] The aromatic carboxylic acid anion includes a monocyclic or polycyclic carboxylic acid anion having aromatic characteristics and one or more carboxylic acid anions, and preferably has a carbon number of 6 to 20. Among them, aromatic carboxylic acid anions having a benzene ring skeleton are preferred, and specific examples thereof include anions obtained by dissociating protons from benzoic acid, cinnamic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like.

[0139] Among the aromatic carboxylic acid anions, the aromatic hydroxycarboxylic acid anions are composed of a monocyclic or polycyclic ring having aromatic characteristics, one or more carboxylic acid anions and one or more hydroxyl groups, and preferably have a carbon number of 6 to 20. Among them, aromatic carboxylic acid anions having a benzene ring skeleton having 1 to 3 hydroxyl groups are preferred, and specifically, for example, anions from which protons are dissociated from salicylic acid, hydroxybenzoic acid, dihydroxybenzoic acid, trihydroxybenzoic acid, hydroxymethylbenzoic acid, vanillic acid, syringic acid, protocatechuic acid, gentisic acid, orsuccinic acid, mandelic acid, benzilic acid, atrolactic acid, phloric acid, coumaric acid, umbelliferous acid, caffeic acid, ferulic acid, sinapinic acid, and the like can be cited.

[0140] When the anion of the organic ammonium salt is the aromatic carboxylic acid anion, one example of the compound of formula (I) is shown below.

[0141] In the formula (I), R is a linear monohydroxyalkyl group or a branched monohydroxyalkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 4.

[0142] In the formula (I), R is a linear monohydroxyalkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4.

[0143] In formula (I), R is 1-hydroxyethyl, and n=1.

[0144] In formula (I), R is 1-hydroxyethyl, and n=2.

[0145] In formula (I), R is 1-hydroxyethyl, and n=3.

[0146] In formula (II), R 11 It is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a linear monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0147] In the formula (I), R is 1,3-dihydroxypropane-2-yl, and n=1.

[0148] In formula (II), R 11 It is a straight-chain alkyl group having 1 to 4 carbon atoms, and n=1.

[0149] In the formula (I), R is 1,3-dihydroxy-2-ethylpropane-2-yl, and n=1.

[0150] In formula (II), R 11 It is a straight-chain monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0151] In the formula (I), R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1.

[0152] In the formula (I), R is a linear polyhydroxyalkyl group or a branched polyhydroxyalkyl group having 1 to 10 carbon atoms and having two or more hydroxyl groups, and n is an integer of 1 to 4.

[0153] In the formula (I), R is pentahydroxyhexane-1-yl, and n=1.

[0154] In formula (I), R is 1-hydroxyethyl, n=1; R is 1-hydroxyethyl, n=3; R is 1,3-dihydroxypropane-2-yl, n=1; R is 1,3-dihydroxy-2-ethylpropane-2-yl, n=1; R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, n=1; or R is pentahydroxyhexane-1-yl, n=1. The aromatic carboxylic acid anion is a benzoic acid anion.

[0155] In formula (I), R is 1-hydroxyethyl, n=1; R is 1-hydroxyethyl, n=2; R is 1-hydroxyethyl, n=3; or R is 1,3-dihydroxypropane-2-yl, n=1. The aromatic carboxylic acid anion is a terephthalic acid anion.

[0156] In formula (I), R is 1-hydroxyethyl, n=1; R is 1,3-dihydroxy-2-ethylpropane-2-yl, n=1; or R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, n=1. The aromatic carboxylic acid anion is a salicylic acid anion.

[0157] In formula (I), R is 1-hydroxyethyl, n=1; R is 1-hydroxyethyl, n=3; or R is 1,3-dihydroxypropane-2-yl, n=1. The aromatic carboxylic acid anion is a p-hydroxybenzoic acid anion.

[0158] R in formula (I) is 1-hydroxyethyl, and n=1. The aromatic carboxylic acid anion is a mandelic acid anion.

[0159] The saturated carbonyl carboxylic acid anion is a carboxylic acid anion having 3 to 22 carbon atoms in the molecule and having a carbonyl group, and preferably a saturated carbonyl carboxylic acid anion having 3 to 7 carbon atoms and having 1 to 2 carbonyl groups. p CO(CH2) q )COO - (p and q represent integers of 0 to 2.) The saturated carbonyl carboxylic acid anion represented by . Specifically, for example, an anion obtained by dissociating a proton from pyruvic acid or the like can be cited.

[0160] When the anion of the organic ammonium salt is the saturated carbonyl carboxylic acid anion, one example of the compound of formula (I) is shown below.

[0161] In the formula (I), R is a linear polyhydroxyalkyl group or a branched polyhydroxyalkyl group having 1 to 10 carbon atoms and having two or more hydroxyl groups, and n is an integer of 1 to 4.

[0162] In the formula (I), R is pentahydroxyhexane-1-yl, and n=1.

[0163] R in formula (I) is pentahydroxyhexane-1-yl, n=1, and the saturated carbonyl carboxylic acid anion is a pyruvic acid anion.

[0164] The alkyl ether carboxylic acid anion is a carboxylic acid anion having 2 to 22 carbon atoms and having an ether group in the molecule containing a polyoxyalkylene ether carboxylic acid anion, preferably an alkyl carboxylic acid anion having 2 to 12 carbon atoms and having 1 to 2 ether groups. r O(CH2) s COO - (r and s represent integers of 0 to 4.) Alkyl ether carboxylic acid anion represented by: polyoxyethylene alkyl ether carboxylic acid anion. Specific examples include anions obtained by dissociating protons from methoxyacetic acid, ethoxyacetic acid, methoxybutyric acid, ethoxybutyric acid, and the like.

[0165] When the anion of the organic ammonium salt is the alkyl ether carboxylate anion, one example of the compound of formula (I) is shown below.

[0166] In formula (II), R 11 It is a straight-chain alkyl group having 1 to 4 carbon atoms, and n=1.

[0167] In the formula (I), R is 1,3-dihydroxy-2-ethylpropane-2-yl, and n=1.

[0168] R in formula (I) is 1,3-dihydroxy-2-ethylpropane-2-yl, n=1, and the alkyl ether carboxylic acid anion is a methoxyacetic acid anion.

[0169] The halogenated carboxylic acid anion is preferably a halogenated carboxylic acid anion having a carbon number of 2 to 22. Specifically, for example, anions obtained by dissociating protons from halogenated carboxylic acids substituted with fluorine, such as trifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, pentafluoropropionic acid, pentachloropropionic acid, pentabromopropionic acid, perfluorononanoic acid, perchlorononanoic acid, and perbromononanoic acid, can be cited.

[0170] When the anion of the organic ammonium salt is the halogenated carboxylic acid anion, one example of the compound of formula (I) is shown below.

[0171] In the formula (I), R is a linear monohydroxyalkyl group or a branched monohydroxyalkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 4.

[0172] In the formula (I), R is a linear monohydroxyalkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4.

[0173] In formula (I), R is 1-hydroxyethyl, and n=1.

[0174] In formula (II), R 11 It is a straight-chain alkyl group having 1 to 4 carbon atoms, and n=1.

[0175] In the formula (I), R is 1,3-dihydroxy-2-ethylpropane-2-yl, and n=1.

[0176] In formula (II), R 11 It is a straight-chain monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0177] In the formula (I), R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1.

[0178] In formula (I), R is 1-hydroxyethyl, n=1; R is 1,3-dihydroxy-2-ethylpropane-2-yl, n=1; or R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, n=1. The halogenated carboxylic acid anion is a trifluoroacetic acid anion.

[0179] The halide anion is not particularly limited, and examples thereof include chloride ion, bromide ion, and iodide ion.

[0180] When the anion of the organic ammonium salt is the above-mentioned halide anion, one example of the compound of formula (I) is shown below.

[0181] In the formula (I), R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1.

[0182] In formula (I), R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, n=1, and the halide anion is a bromide ion.

[0183] In formula (I), R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, n=1, and the halide anion is a chloride ion.

[0184] Examples of the sulfur-based anions include sulfate anions, sulfite anions, sulfonate anions, hydrogensulfonate anions, alkylsulfonate anions (e.g., methylsulfonate, ethylsulfonate, butylsulfonate, benzenesulfonate, p-toluenesulfonate, 2,4,6-trimethylbenzenesulfonate, styrenesulfonate, 3-sulfopropylmethacrylate anion, 3-sulfopropylacrylate, etc.), sulfate anions, hydrogensulfate anions, alkylsulfate anions (e.g., methylsulfate anion, ethylsulfate anion, butylsulfate anion, octylsulfate anion, 2-(2-methoxyethoxy)ethylsulfate anion, etc.), and the like.

[0185] When the anion of the organic ammonium salt is the above-mentioned sulfur-based anion, one example of the compound of formula (I) is shown below.

[0186] In formula (II), R 11 It is a straight-chain monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0187] In the formula (I), R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1.

[0188] In the formula (I), R is a linear polyhydroxyalkyl group or a branched polyhydroxyalkyl group having 1 to 10 carbon atoms and having two or more hydroxyl groups, and n is an integer of 1 to 4.

[0189] In the formula (I), R is pentahydroxyhexane-1-yl, and n=1.

[0190] R in formula (I) is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, n=1; or R is pentahydroxyhexane-1-yl, n=1. The sulfur anion is a sulfate anion.

[0191] Examples of the fluorine-based anions include bis(fluorosulfonyl)imide anions, bis(perfluoroalkylsulfonyl)imide anions (e.g., bis(trifluoromethylsulfonyl)imide anions, bis(pentafluoroethylsulfonyl)imide, bis(heptafluoropropanesulfonyl)imide anions, bis(nonafluorobutylsulfonyl)imide, etc.), perfluoroalkylsulfonate anions (e.g., trifluoromethanesulfonate anions, pentafluoroethanesulfonate anions, heptafluoropropanesulfonate anions, perfluorobutylsulfonate anions, etc.), and bis(perfluoroalkylsulfonyl)imide anions.

[0063] The invention also includes an anion such as a fluorophosphate anion (e.g., a hexafluorophosphate anion, a tris(pentafluoroethyl)trifluorophosphate anion, etc.), a tris(perfluoroalkylsulfonyl)methide anion (e.g., a tris(trifluoromethanesulfonyl)methide anion, a tris(pentafluoroethanesulfonyl)methide anion, a tris(heptafluoropropanesulfonyl)methide anion, a tris(nonafluorobutanesulfonyl)methide anion, etc.), a hydrofluoride anion, etc.

[0192] When the anion of the organic ammonium salt is the fluorine-based anion, one example of the compound of formula (I) is shown below.

[0193] In formula (II), R 11 It is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a linear monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0194] In the formula (I), R is 1,3-dihydroxypropane-2-yl, and n=1.

[0195] R in formula (I) is 1,3-dihydroxypropane-2-yl, n=1, and the fluorine-based anion is a bis(trifluoromethylsulfonyl)imide anion.

[0196] The boron-based anions are not particularly limited, and examples thereof include tetraalkylborate anions such as tetrafluoroborate anion, dioxalatoborate anion, and tetraphenylborate anion.

[0197] The nitrogen oxide-based anions are not particularly limited, and examples thereof include nitrate anions and nitrite anions.

[0198] Examples of the phosphorus-based anions include phosphate anions, hydrogen phosphate anions, dihydrogen phosphate anions, phosphonate anions, hydrogen phosphonate anions, dihydrogen phosphonate anions, phosphinate anions, hydrogen phosphinate anions, alkyl phosphate anions (e.g., dimethyl phosphate anion, diethyl phosphate anion, dipropyl phosphate anion, dibutyl phosphate anion, etc.), alkyl phosphonate anions (e.g., methyl phosphonate anion, ethyl phosphonate anion, propyl phosphonate anion, butyl phosphonate anion, methyl methyl phosphonate anion, etc.), alkyl phosphinate anions, hexaalkyl phosphate anions, and the like.

[0199] When the anion of the organic ammonium salt is the phosphorus-based anion, one example of the compound of formula (I) is shown below.

[0200] In formula (II), R 11 It is a straight-chain monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0201] In the formula (I), R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1.

[0202] In the formula (I), R is a linear polyhydroxyalkyl group or a branched polyhydroxyalkyl group having 1 to 10 carbon atoms and having two or more hydroxyl groups, and n is an integer of 1 to 4.

[0203] In the formula (I), R is pentahydroxyhexane-1-yl, and n=1.

[0204] R in formula (I) is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, n=1; or R is pentahydroxyhexane-1-yl, n=1. The phosphorus-based anion is a dihydrogen phosphate anion.

[0205] The cyanide anion is not particularly limited, and examples thereof include tetracyanoborate anion, dicyanamide anion, thiocyanate anion, and isothiocyanate anion.

[0206] When the anion of the organic ammonium salt is the cyanide anion, one example of the compound of formula (I) is shown below.

[0207] In formula (II), R 11 It is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a linear monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0208] In the formula (I), R is 1,3-dihydroxypropane-2-yl, and n=1.

[0209] In formula (II), R 11 It is a straight-chain monohydroxyalkyl group having 1 to 4 carbon atoms, and n=1.

[0210] In the formula (I), R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, and n=1.

[0211] In the formula (I), R is a linear polyhydroxyalkyl group or a branched polyhydroxyalkyl group having 1 to 10 carbon atoms and having two or more hydroxyl groups, and n is an integer of 1 to 4.

[0212] In the formula (I), R is pentahydroxyhexane-1-yl, and n=1.

[0213] In formula (I), R is 1,3-dihydroxypropane-2-yl, n=1; R is 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, n=1; or R is pentahydroxyhexane-1-yl, n=1. The cyanide anion is a dicyanamide anion.

[0214] Among the anions of the organic ammonium salt of the present invention, preferred are the forms of carboxylic acid anions, halide anions, sulfur anions, fluorine anions, nitrogen oxide anions, phosphorus anions, and cyanide anions. From the viewpoint of safety, carboxylic acid anions are particularly preferred, and among them, preferred are the forms of saturated aliphatic monocarboxylic acid anions, alicyclic carboxylic acid anions, unsaturated aliphatic monocarboxylic acid anions, saturated hydroxycarboxylic acid anions, saturated dicarboxylic acid anions, unsaturated dicarboxylic acid anions, saturated hydroxydicarboxylic acid anions or saturated hydroxytricarboxylic acid anions, aromatic carboxylic acid anions, saturated carbonyl carboxylic acid anions, alkyl ether carboxylic acid anions, and halogenated carboxylic acid anions.

[0215] The organic ammonium salt of the present invention is not particularly limited and can be synthesized, for example, in the following manner.

[0216] The alkanolamine having one or more hydroxyl groups, the amino acid having one or more carboxyl groups, the aminohydroxyalkanoic acid having one or more hydroxyl groups and one or more carboxyl groups corresponding to R of formula (I) are reacted with an organic acid or inorganic acid corresponding to the anion in a solvent such as water or an organic solvent. Alternatively, the alkanolamine having one or more hydroxyl groups, the amino acid having one or more carboxyl groups, the aminohydroxyalkanoic acid having one or more hydroxyl groups and one or more carboxyl groups corresponding to R of formula (I) are reacted with an organic halogen compound such as an alkylene halohydrin, a monohalogenated alkylcarboxylic acid, and a monohalogenated hydroxyalkylcarboxylic acid in a solvent, and the obtained compound is reacted with an organic acid or inorganic acid corresponding to the anion of the target compound in a solvent such as water or an organic solvent.

[0217] Alkanolamines corresponding to the ammonium cation of formula (I) (e.g., monoalkanolamine, dialkanolamine, trialkanolamine, 2-amino-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, tris(hydroxymethyl)aminomethane, D-glucosamine, etc.) or amino acids consisting of carbonyl groups (e.g., glycine, aspartic acid, glutamic acid, etc.) or aminohydroxyalkanoic acids having one or more hydroxyl groups and one or more carboxyl groups (e.g., 3-amino-2-hydroxypropionic acid, etc.) and organic acids or inorganic acids corresponding to anions are reacted in polar solvents such as water or acetonitrile. The reaction temperature and reaction time depend on the type of raw materials, for example, the reaction can be carried out at room temperature for about 1 hour to 1 day. Then, the solvent is removed by distillation under reduced pressure, and the reaction is refined as needed, so that the target organic ammonium salt as a solid can be obtained. In addition, when the reaction is carried out under equimolar conditions and the reaction is completed, the refining process is not required, and the manufacturing process can be further simplified.

[0218] The compound in which R of the formula (I) is composed of a hydroxycarbonyl group, a hydroxyalkyl group or a carbonyl group and has no hydrogen atom (n is 4) can be synthesized, for example, as follows.

[0219] As the initial process, in order to correspond to the structure of the ammonium cation of formula (I), an aminohydroxyalkanoic acid (e.g., 3-amino-2-hydroxypropionic acid, etc.) having more than one hydroxyl group and one carboxyl group and a hydroxyalkyl halide having more than two hydroxyl groups or a halogenated alkyl carboxylic acid having more than two carboxyl groups are reacted in a polar solvent such as water or acetonitrile. The reaction temperature and reaction time depend on the type of raw materials, for example, the reaction can be carried out for about 1 day at room temperature. Then, the reactant is washed to obtain a compound consisting of the ammonium cation of formula (I) and the halide ion. In addition, when the target anion is formed from the halide ion, an anion exchange is performed. When an anion exchange is performed, for example, the obtained compound is reacted with an organic acid or an inorganic acid corresponding to the anion of the target compound in water. The reaction temperature and reaction time depend on the type of raw materials, for example, the reaction can be carried out for about 1 day at room temperature. Alternatively, the target organic ammonium salt can be obtained by using a strong basic ion exchange resin or the like, after anion exchange with a hydroxide anion, and then anion exchange with an organic acid or inorganic acid corresponding to the anion of the target compound.

[0220] The organic ammonium salt of the present invention is solid at 25°C. Here, the so-called solid state refers to a state that contains crystalline and non-crystalline substances and does not flow at 25°C. Due to the purity of the organic ammonium salt, the melting point (freezing point) sometimes changes, but considering the previous technical common sense, it also includes the solid substance at 25°C of the compound of formula (I) synthesized. Regarding the purity of the organic ammonium salt, although it varies according to its purification method and the molar ratio of anions and cations in the product, the melting point (freezing point) of the organic ammonium salt is high in purity as described in the examples of the present application, and the compounds further purified by IR spectrum and NMR spectrum, and have a melting point clearly determined by the compound itself, so the results of the examples of the present invention can be referred to. The organic ammonium salt of the present invention can be in an anhydrous state (anhydrous substance) or a hydrate that absorbs moisture in the air. The so-called hydrate refers to a compound that absorbs water when the compound is placed in the air at 25°C, and its water content reaches a saturated state. A compound that does not absorb water when left in the air at 25°C does not have a hydrate and is an anhydrous compound.

[0221] The organic ammonium salt of the present invention is solid at 25°C by selecting the functional group, characteristic group and anion of the ammonium cation, and broadly includes ionic liquids as organic salts having a melting point of 100°C or less. When reacting in a high temperature region, since the ionic liquid is non-volatile due to its structural characteristics and has a high decomposition temperature, for example, the reaction can be carried out even at a temperature of 100°C or more, which is higher than that of water as a solvent, and the applicable range of the reaction temperature can be expanded. In addition, the flammability and combustibility are very low, so the convenience is high.

[0222] The organic ammonium salt of the present invention has a high affinity for hydrogen-bonding materials having hydrogen-bonding functional groups or hydrogen-bonding accepting elements, and the hydrogen-bonding functional groups or hydrogen-bonding accepting elements interact with the hydroxyl group of the cation, the carboxyl group of the cation, and the hydrogen atom bonded to nitrogen. Therefore, the organic ammonium salt of the present invention can be used in various applications that require affinity with hydrogen-bonding materials that can form hydrogen bonds, coordination bonds, and ionic bonds.

[0223] The hydrogen of the hydroxyl group, the hydrogen of the carboxyl group, and the hydrogen bonded to nitrogen of the organic ammonium salt of the present invention form hydrogen bonds with the target compound or material, for example, elements having lone pairs of electrons in groups 15 to 17, which are not particularly limited, or π-electron compounds; or, the oxygen atom of the hydroxyl group and the oxygen atom of the carboxyl group of the organic ammonium salt of the present invention form hydrogen bonds with the hydrogen atom of the target compound or material. Therefore, the organic ammonium salt of the present invention has excellent affinity with compounds and materials having hydrogen-bonding functional groups.

[0224] In addition, since the organic ammonium salt of the present invention is an organic salt having a hydroxyl group and / or a carboxyl group, it has excellent affinity with metals or ionic compounds or materials through coordination interaction or electrostatic interaction. As the metal, there is no particular limitation, and for example, elements of the 2nd to 14th families can be cited.

[0225] Examples of the hydrogen bonding functional group include a carbon-carbon unsaturated bond group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, and a hydrogen atom directly bonded to nitrogen.

[0226] The carbon-carbon unsaturated bond group is not particularly limited, and examples thereof include a vinyl group, a vinylene group, an ethynyl group, and an unsaturated cyclic hydrocarbon group.

[0227] The oxygen-containing group is not particularly limited, and examples thereof include hydroxyl group, carbonyl group, ether group, ester group, aldehyde group, carboxyl group, carboxylate group, urea group, carbamate group, amide group, oxazole group, morpholine group, carbamate group, and carbamate group.

[0228] The nitrogen-containing group is not particularly limited, and examples thereof include an amino group and a nitro group.

[0229] The sulfur-containing group is not particularly limited, and examples thereof include a sulfate group (—OS(═O)2O—), a sulfonyl group (—S(═O)2O—), a sulfonic acid group (—S(═O)2—), a mercapto group (—SH), a thioether group (—S—), a thiocarbonyl group (—C(═S)—), a thiourea group (—NC(═S)-N—), a thiocarboxyl group (—C(═S)OH), a thiocarboxylate group (—C(═S)O—), a dithiocarboxyl group (—C(═S)SH), and a dithiocarboxylate group (—C(═S)S—).

[0230] There are no particular limitations on the phosphorus-containing group, and examples thereof include a phosphate group (-OP(=O)(-O-)-O-), a phosphonic acid group (-P(=O)(-O-)-O-), a phosphinate group (-P(=O)-O-), a phosphite group (-OP(-O-)-O-), a phosphite group (-P(-O-)-O-), a trivalent phosphonic acid group (-PO-), and a pyrophosphate group [(-OP(=O)(-O-))2-O-].

[0231] Examples of hydrogen-bonding materials having hydrogen-bond-accepting elements include materials containing compounds of hydrogen-bond-accepting elements or their oxides as constituent elements of molecules or functional groups, and materials surface-modified with functional groups containing these elements or their oxides.

[0232] The organic ammonium salt of the present invention has any one of a hydroxyl group, a carboxyl group, and a hydrogen atom bonded to a nitrogen atom as a hydrogen bonding functional group in the cation, and therefore has excellent affinity with hydrogen bonding materials. Furthermore, if the anion of the organic ammonium salt also has a hydrogen bonding functional group, the affinity with the hydrogen bonding material is even more excellent.

[0233] The hydrogen bonding material is not particularly limited, and examples thereof include biological samples, organic compounds, and inorganic compounds.

[0234] Examples of biological samples include biocatalysts such as enzymes, peptides, proteins, nucleic acids, poorly soluble polysaccharides such as cellulose, cells, cell tissue fluid, cell membranes, blood, biological tissues, antibodies / antigens, and the like.

[0235] As the material of organic compound, there is no particular limitation, and the above-mentioned compounds with hydrogen bonding functional groups can be listed. For example, organic resins, organic pigments, organic dyes, organic fluorescent pigments, etc. can be listed. As organic resins, for example, thermoplastic resins, thermosetting resins, etc. can be listed. As organic pigments, there is no particular limitation, and for example, azo systems, diazo systems, condensed azo systems, thioindigo systems, indanthrone systems, quinacridone systems, anthraquinone systems, benzimidazolone systems, perylene systems, phthalocyanine systems, anthrapyridine systems and dioxazine systems, etc. can be listed. As organic fluorescent pigments, there is no particular limitation, and for example, rhodamine pigments, squarylium pigments, cyanine pigments, aromatic hydrocarbon pigments, oxazine pigments, carbopyronine systems, methylene pyrrole systems, etc. can be listed. As organic dyes, for example, organic solvent-soluble dyes classified as solvent dyes in the colorimetric index, etc. can be listed. Specific examples of solvent dyes include ValiFast Black 3806, Vali Fast Black 3807, Vali Fast Black 3830, Alcohol Black SB, Spilon Black GMH, Vali Fast Red 1320, Vali Fast Red 1308, Vali Fast Yellow AUM, Spilon Yellow C2GH, Spilon Violet CRH, Vali Fast Violet 1701, Spilon Red CGH, Spilon Pink BH, Nigrosine Base EX, Oil Blue 613, Neozapon Blue 808, and Vali Fast Blue 1621.

[0236] The material of the inorganic compound is not particularly limited, and for example, metals, metal oxides, rare earth metal oxides, hydroxides, carbonates, sulfates, silicates, nitrides, titanate compounds, carbons, etc. are listed. The metal is not particularly limited, and for example, elements of Groups 2 to 14 are listed, that is, for example, iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver, gold, platinum, etc. are listed. In order to form a hydrogen bond well with the organic ammonium salt of the present invention, metal oxides can be preferably used. The metal oxide is not particularly limited, and examples thereof include silicon dioxide, aluminum oxide (alumina), zirconium oxide, titanium oxide, magnesium oxide, indium tin oxide (ITO), cobalt blue (CoO·Al2O3), antimony oxide, zinc oxide, cesium oxide, zirconium oxide, yttrium oxide, tungsten oxide, vanadium oxide, cadmium oxide, tantalum oxide, niobium oxide, tin oxide, bismuth oxide, cerium oxide, copper oxide, iron oxide, indium oxide, boron oxide, calcium oxide, barium oxide, thorium oxide, indium tin oxide, ferrite, etc. Examples of rare earth metal oxides include dysprosium oxide, erbium oxide, europium oxide, gadolinium oxide, holmium oxide, lanthanum oxide, lutetium oxide, neodymium oxide, praseodymium oxide, samarium oxide, scandium oxide, terbium oxide, thulium oxide, ytterbium oxide, etc. Examples of hydroxides include calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, iron hydroxide, etc. As carbonates, for example, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, etc. can be listed. As sulfates, for example, calcium sulfate, barium sulfate, aluminum sulfate, etc. can be listed. As silicates, for example, calcium silicate, wollastonite, xonotlite, kaolin, talc, clay, mica, montmorillonite, bentonite, dolomite, hydrotalcite, calcium silicate, aluminum silicate, magnesium silicate, zirconium silicate, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica balls, etc. can be listed. As nitrides, for example, aluminum nitride, boron nitride, silicon nitride, etc. can be listed. As titanate compounds, for example, barium titanate, barium zirconate titanate, calcium titanate, strontium titanate, etc. can be listed. Examples of carbon include carbon black, graphite, carbon fiber, carbon spheres, activated carbon, bamboo charcoal, charcoal, single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanohorns, and fullerene.

[0237] (Hydrogen bonding material treatment agent)

[0238] The organic ammonium salt of the present invention can be used as an organic hydrogen-bonding material treatment agent and an inorganic hydrogen-bonding material treatment agent. It is expected to be used in, for example, biological sample treatment agents such as hydrogen-bonding material dispersion media, biological sample preservation materials, and protein refolding reagents; moisture regulators such as antifogging agents and humidifying agents; surface treatment agents such as dispersants for inorganic and organic materials; electronic materials such as electrolyte materials, conductive materials, and fuel cells; resin additives such as antistatic agents; life science materials such as pharmaceuticals, cosmetics, fragrances, antibacterial agents, deodorants, and deodorants; industrial materials such as reaction aids, heat media, adhesives, antifogging agents, adsorbents, thermal insulation agents, and polymer substrates; agricultural materials such as agricultural sustained-release agents, etc.

[0239] The hydrogen bonding material treatment agent of the present invention contains the organic ammonium salt of the present invention described above. Here, the so-called "containing" refers to the material consisting of the organic ammonium salt of the present invention as the main object. In addition, it can also be a material mixed with other allowable arbitrary components according to the purpose of use. As other arbitrary components, there is no particular limitation, and solvents such as water, organic solvents, and dispersion media can be listed, and they can be used in the form of solutions and dispersions. Among the solvents and dispersion media, water, alcohol, etc. with high affinity to the organic ammonium salt of the present invention can be preferably used.

[0240] The organic ammonium salt of the present invention can stably store and disperse the hydrogen bonding material as a solution or dispersion obtained by mixing the hydrogen bonding material with water or a solvent. It can also stably store, dissolve and disperse the hydrogen bonding material when the water or solvent is removed from the solution or dispersion to form a solid composition and then the solvent is added again to form a solution or dispersion.

[0241] If the hydrogen-bonding material treatment agent containing the organic ammonium salt of the present invention is mixed with the hydrogen-bonding material and a solvent to form a solution or a dispersion, and then the solvent is removed, a solid composition in which the hydrogen-bonding material is uniformly mixed in the hydrogen-bonding treatment agent can be obtained. This is useful when the hydrogen-bonding material is stored in a solid form. Furthermore, if a solvent is added to the solid composition, a solution or a dispersion in which the hydrogen-bonding material is uniformly dissolved or dispersed again is obtained, which is useful as a method for uniformly dissolving or dispersing it again after forming it into a solid state.

[0242] (Biological sample treatment agent)

[0243] The biological sample treatment agent is a treatment agent for treating a biological sample among the above-mentioned hydrogen bonding material treatment agents, and as mentioned above, examples thereof include biological sample preservation materials, protein refolding reagents, biosensor stabilizers, biological sample surface treatment agents, biological sample modifiers, hair treatment agents, skin care agents, and the like.

[0244] In the following, the hydrogen bonding material treatment agent, in particular the biological sample treatment agent, is mainly described, but the description of the hydrogen bonding material treatment agent is also included. For details of the biological sample and the effects of the organic ammonium salt of the present invention on various treatment agents based on the affinity with the target hydrogen bonding material and the interaction with the hydrogen bonding functional group, please refer to the following description.

[0245] The hydrogen-bonding material treatment agent of the present invention can be used as a biological sample treatment agent, for example, it can be used to maintain the three-dimensional structure of the biological sample, activate the biological sample, maintain the activity of the biological sample, and store it for a long time in a state of maintaining the activity. Therefore, it is useful for protein renaturation, enzyme activity maintenance, and storage in a state of maintaining the three-dimensional structure of the biological sample.

[0246] The biological sample processing agent of the present invention contains the organic ammonium salt of the present invention described above. Here, "containing" means that the material composed of the organic ammonium salt of the present invention is the main object, and other arbitrary components that are allowed when performing biological sample processing may also be mixed.

[0247] Examples of biological samples include biocatalysts such as enzymes, peptides, proteins, nucleic acids, poorly soluble polysaccharides such as cellulose, cells, cell tissue fluid, cell membranes, blood, biological tissues, antibodies / antigens, etc. Among them, biocatalysts, proteins, and nucleic acids are preferred.

[0248] In biological samples, the biocatalyst is a catalyst for biochemical reactions; the biocatalysts in the present invention include microorganisms, animal and plant cells, animal and plant tissues and enzymes derived from these organisms, and further include artificial compounds with enzyme functions, natural enzymes, artificial enzymes that artificially change biological molecules to give them new properties, etc.

[0249] The primary structure of an enzyme is formed by one-dimensional bonding of amino acids, but the arrangement and number of amino acids determine the structure in two dimensions or more. These structures determine the unique properties of each enzyme.

[0250] The primary structure is a one-dimensional arrangement of 20 kinds of amino acids through peptide bonds. Most enzymes are composed of 100 to 300 amino acids, and the order of amino acid arrangement is a piece of information that determines the characteristics of the enzyme. The secondary structure is a one-dimensional arrangement of parts (multiple) of the whole with advanced regular structures such as α helix, β fold, β-turn, etc. The tertiary structure is a three-dimensional structure formed by the primary structure and the secondary structure. This three-dimensional structure determines the site of the enzyme as a reaction catalyst, that is, the active center, and the three-dimensional structure of the amino acid residues composed of the hydrophilic part / hydrophobic part, etc., and expresses chemical reactions with substrate specificity and reaction specificity that are unique to biocatalysts such as enzymes and are not found in general proteins (structural proteins, transport proteins, storage proteins, contractile proteins, defense proteins, hormone proteins). The quaternary structure is an association composed of multiple molecules of enzymes that form a three-dimensional structure. That is, biocatalysts such as enzymes have reaction specificity through primary to quaternary structures in addition to substrate specificity possessed by proteins. Therefore, in order to maintain activity in catalytic reactions, it is important to maintain not only the primary and secondary structures but also the tertiary and quaternary structures.

[0251] Examples of enzymes that can be used in the present invention include oxidoreductase, transferase, hydrolase, lyase, isomerase, and ligase.

[0252] Examples of the oxidoreductase include glucose oxidase, alcohol oxidase, glucose dehydrogenase, alcohol dehydrogenase, fructose dehydrogenase, gluconate dehydrogenase, aldehyde dehydrogenase, amine dehydrogenase, succinate dehydrogenase, p-cresol methyl hydroxylase, histamine dehydrogenase, fumarate reductase, nitrate reductase, arsenate reductase, sulfite reductase, catalase, peroxidase, and cytochrome P450.

[0253] Examples of the transferase include citrate synthase, methyltransferase, phosphotransferase, glycine hydroxymethyltransferase, transketolase, aspartate aminotransferase, hexokinase, glycerol kinase, creatine kinase, aminotransferase, and transacylase.

[0254] Examples of the hydrolase include carboxylesterase, acetyl-CoA hydrolase, alkaline phosphatase, phospholipase, arylsulfatase, amylase, glucoamylase, cellulase, DNA glycosylase, trypsin, chymotrypsin, pepsin, urease, serine protease, and lipase.

[0255] Examples of the lyase include alginate lyase, pyruvate decarboxylase, phosphoketase, citrate lyase, phosphopyruvate hydratase, tryptophan synthase, pectin lyase, aspartate ammonia lyase, cysteine ​​lyase, adenylate cyclase, and ferrochelatase.

[0256] Examples of the isomerase include amino acid racemase, tartrate epimerase, glucose-6-phosphate 1-epimerase, maleate isomerase, phenylpyruvate tautomerase, phosphoglucose isomerase, phosphomannose mutase, and tyrosine-2,3-aminomutase.

[0257] Examples of the synthetase include tyrosine tRNA ligase, acetyl-CoA synthetase, asparagine synthetase, GMP synthetase, pyruvate carboxylase, and DNA ligase.

[0258] Examples of microorganisms applicable to the present invention include prokaryotes (bacteria, actinomycetes, archaea), eukaryotes (molds, yeasts, mushrooms, algae, protozoa), etc. Examples of animal and plant cells include animal cells, plant cells, animal cultured cells, plant cultured cells, etc.

[0259] Examples of tissues derived from animals and plants include animal tissues and plant tissues.

[0260] Biocatalysts such as enzymes and yeasts are often easily destroyed in their molecular 3D structures due to the influence of temperature, pH, solvents, or electrostatic repulsion between molecules, which reduces their activity, i.e., catalytic ability. Therefore, as long-term storage methods for biocatalysts, freeze-drying in a powder state or cryopreservation in which the biocatalyst is dissolved in a solution under low concentration and extremely low temperature conditions is known. However, in the case of the cryopreservation method, special equipment is required, and when the frozen solution is dissolved for use, the structure of the biocatalyst is often changed, resulting in a reduction in activity. In addition, the low storage concentration makes it difficult to effectively store the biocatalyst.

[0261] In order to improve the affinity of the enzyme, various factors need to be considered. For example, by adding salts, the repulsion (Coulomb interaction) generated by the charge of the enzyme molecules is suppressed, and the interaction between the enzyme molecules is caused, so that more enzyme molecules are present in a unit volume; in addition, it is also important to improve the affinity of amino acid residues such as hydroxyl groups, carbonyl groups, and amino groups that are mostly present on the surface of the enzyme with the storage material.

[0262] The organic ammonium that is constituted by the salt structure of anion and cation, though can suppress the intermolecular interaction of enzyme each other, can expect to improve the affinity of enzyme, but the organic ammonium salt of known imidazolium system, tetraalkylammonium system in the past has low affinity with enzyme surface.On the other hand, the compound of polyol system such as glycerine, propylene glycol, glucose, trehalose etc. that has the hydroxyl group of affinity with the amino-acid residues such as hydroxyl group, carbonyl, amino group on enzyme surface, suppresses the effect of intermolecular interaction of enzyme low, and is low to the affinity of enzyme.And, owing to the organic ammonium salt of the imidazolium system with hydroxyl group has rigid ring structure, so is low to the affinity of enzyme.

[0263] In contrast, since the organic ammonium salt used in the biological sample treatment agent of the present invention is an organic ammonium salt having a hydrogen bonding functional group in the cation or in both the cation and the anion, it is possible to inhibit the intermolecular interaction of the enzyme. In addition, the cation has a hydrogen bonding functional group (hydroxyl group, carboxyl group, ether group, hydrogen bonded to a nitrogen atom), and has a high affinity with amino residues such as hydroxyl group, carbonyl group, and amino group on the enzyme surface, and has a small molecular size and a flexible structure, and can obtain high affinity. In addition, by having a hydrogen bonding functional group in the anion, the affinity can be further improved.

[0264] The preservation of enzyme activity requires the maintenance of the three-dimensional structure of the enzyme. In general, enzymes have substrate specificity and reaction specificity expressed by amino acid residues, and play a role as reaction catalysts. Substrate specificity refers to the structure of the substrate to be identified and selected for bonding by the three-dimensional structure of the reaction site and the amino acid residues of the reaction site, and only specific substrates react. Reaction specificity refers to that the enzyme only catalyzes a specific chemical reaction, which is related to the three-dimensional structure of the reaction site and the amino acid residues of the reaction site and the metal ions possessed by part enzymes. For example, metal ions present in enzymes such as oxidoreductases form complexes with amino acid residues three-dimensionally and express catalysis. That is, the inactivation of substrate specificity, reaction specificity, metal ions, etc., is the main reason for the disintegration of the three-dimensional structure of amino acid residues. Therefore, protecting amino residues such as hydroxyl groups, carbonyl groups, and amino groups that express the hydrophilicity of the enzyme surface and protecting the hydrophilic amino acid residues such as hydroxyl groups, carbonyl groups, and amino groups inside the enzyme of the active site and protecting the amino acid residues with hydrophobic functional groups are particularly important for maintaining the three-dimensional structure of the enzyme.

[0265] In the past, the water / buffer used as the solvent of the enzyme, although the affinity with the hydrophilic part of the enzyme surface is high, it is impossible to protect the three-dimensional structure of the hydrophobic part of the enzyme inside that is important in terms of expression substrate specificity and reaction specificity, and the catalytic activity cannot be maintained. Although the aqueous solution of bovine serum albumin as protein is sometimes used as a stabilizer, there is a worry about infectious diseases such as BSE, and it is difficult to use it in the medical field. Using the aqueous solution of polyol stabilizers such as glycerol, propylene glycol, glucose, trehalose, although there is affinity between the hydrophilic part of the enzyme surface and the hydroxyl group of these polyols, there is affinity between the hydrophilic part of the enzyme inside the active point and the hydroxyl group of the polyol, and there is affinity between the hydrophobic part of the enzyme inside the active point and the hydrophobic alkyl chain in the polyol, and the three-dimensional structure of the enzyme can be maintained, but its storage stability effect is low. Surfactant (amino acid) aqueous solution such as glycine and lysine, the hydrophobic part of its surfactant is bonded to the hydrophobic amino acid residue in the hydrophobic region inside the enzyme, and this hydrophobic region becomes hydrophilic by generating electric charge, moves to the hydrophilic surface, and therefore causes the three-dimensional structure of the enzyme to disintegrate and inactivate. And then, as organic ammonium salt, the organic ammonium salt such as imidazolium system and tetraalkylammonium system that are not known to have hydrogen bonding functional group in the past, because can not protect the hydrophilic amino residue on the enzyme surface and the hydrophilic amino residue inside the enzyme, so the affinity to the enzyme is low.

[0266] In contrast, the organic ammonium salt used in the biological sample processing agent of the present invention has hydrogen bonding functional groups in the cations and anions constituting the salts to protect the hydroxyl, carbonyl, amino, and other amino acid residues on the surface and inside the enzyme. In addition, by simultaneously protecting the internal amino acid residues having hydrophobic functional groups at the hydrophobic sites of the alkyl chains in the organic ammonium salts, the three-dimensional structure of the enzyme can be maintained even under conditions of long periods of time and high concentrations, and the catalytic activity can be maintained.

[0267] In addition, the organic ammonium salt used in the biological sample processing agent of the present invention is composed of a combination of cations and anions having hydrogen-bonding functional groups (hydroxyl group, carboxyl group, ether group, hydrogen bonded to a nitrogen atom), and due to their electrostatic interaction, it has a high retention of the enzyme's three-dimensional structure and a high retention of the enzyme's activity compared to non-ionic compounds having hydrogen-bonding functional groups.

[0268] In addition, since the organic ammonium salt used in the biological sample processing agent of the present invention has a small molecular size and a flexible structure, even if the organic ammonium salt contains a hydroxyl group, the organic ammonium salt of the present invention can more effectively enter the interior of a complex three-dimensional structure than an imidazolium organic ammonium salt with a cyclic rigid structure, thereby protecting the amino acid residues from three-dimensional distortion and maintaining high enzyme activity.

[0269] Oxidoreductases are enzymes that express catalytic action by transferring hydrogen atoms, electrons, or oxygen atoms from a substrate. Most of them express catalytic action by a change in valence caused by electron transfer of metal ions in the enzyme.

[0270] Transferase is an enzyme that catalyzes a reaction that transfers an atomic group (functional group) from one substrate to another substrate. Since the transfer reaction is performed only on the functional group present in the substrate to be reacted, it is particularly important to maintain a steric structure that can adapt to the substrate.

[0271] A hydrolase is an enzyme that cleaves (hydrolyzes) a specific bond in a substrate by reacting a substrate with water, a hydroxyl group in an amino acid residue of the enzyme, or the like.

[0272] Lyases are enzymes that cleave carbon-carbon, carbon-oxygen, etc. bonds in substrates without oxidizing or hydrolyzing the substrate molecules. Most of them cleave bonds in substrate molecules by reacting metal ions with the substrate to form intermediates.

[0273] Isomerase is an enzyme that converts a substrate into stereoisomers having different spatial arrangements. Therefore, the three-dimensional structure of the amino acid residues in the enzyme that bind the substrate becomes important.

[0274] Ligase is an enzyme that can bond two substrates by hydrolyzing ATP. The reaction is to generate the target product by reacting two substrates via an intermediate formed by bonding ATP and a specific amino acid residue in the enzyme.

[0275] That is, in any enzyme, the amino acid residues, the three-dimensional structure of the amino acid residues or the metal ions that form a three-dimensional complex with the amino acid residues are important, and they express the activity of the enzyme. The biocatalyst solvent of the present invention can protect the amino acid residues or the metal ions that form a complex according to its structural characteristics, and can maintain the activity of the biocatalyst.

[0276] In addition, the biological sample processing agent of the present invention can suppress denaturation caused by heat even in the presence of various denaturing factors such as heat (temperature) and pH. Although heat cuts hydrogen bonds between amino acid residues, disintegrates the three-dimensional structure, and causes enzyme denaturation, the biological sample processing agent of the present invention can more firmly maintain the three-dimensional structure and suppress thermal denaturation by forming a hydrogen bond network between the amino acid residues inside the enzyme and the hydrogen-bonding functional groups in the organic ammonium salt. That is, the biological sample processing agent of the present invention can maintain activity for a long time at a high enzyme concentration and can be stored for a long time even at room temperature (25°C) higher than the general enzyme storage condition of -20 to 5°C and at 40°C, which promotes enzyme inactivation.

[0277] In biological samples, there is no particular limitation on the proteins. For example, from the perspective of solution properties, there can be listed acidic proteins that contain a large amount of amino acids having carboxyl groups (aspartic acid, glutamic acid, etc.), alkaline proteins that contain a large amount of amino acids having amino groups (lysine, alginate, histidine, etc.), and neutral proteins that are balanced by amino acids having carboxyl groups and amino acids having amino groups.

[0278] As its constituent elements, simple proteins composed only of amino acids and complex proteins composed of components other than amino acids can be listed. Among simple proteins, there are albumin, casein, collagen, keratin, protamine, and histone; among complex proteins, there are glycoproteins (luteinizing hormone, follicle-stimulating hormone, thyroid-stimulating hormone, human chorionic gonadotropin, avidin, cadherin, proteoglycan, mucin, etc.); lipoproteins (chylomicrons, LDL, HDL, etc.); nuclear proteins (proteomes of histones or telomerase, protamine, etc.); pigment proteins (chlorophyll, etc.); metal proteins (hemoglobin, cytochrome C, etc.); phosphoproteins (casein in milk, yolk phosvitin in egg yolk, etc.), etc. All enzymes are proteins of any of these proteins.

[0279] In addition, according to the shape of the molecule, it can be divided into fibrous proteins (keratin, collagen, etc.) and globular proteins (hemoglobin, etc.). According to its function, it can be divided into enzyme proteins (enzymes), structural proteins (collagen, keratin, etc.), transport proteins (hemoglobin, albumin, apolipoprotein, etc.), storage proteins (ovalbumin, ferritin, hemosiderin, etc. in egg white), contractile proteins (actin, myosin, etc.), defense proteins (globulin, etc.), and regulatory proteins (calmodulin, etc.).

[0280] Based on the molecular and intermolecular structures, proteins with primary structure (amino acid arrangement), secondary structure (α-helix and β-structure or random coil), tertiary structure (specific spatial arrangement), and quaternary structure (hemoglobin, DNA polymerase, ion channels, etc.) can be listed.

[0281] The molecular weight of the protein is not particularly limited, but is considered to be 4,000 to 300,000.

[0282] In biological samples, examples of nucleic acids include DNA and RNA. It is known that these nucleic acids are easily hydrolyzed by degrading enzymes in water, and when water is used as a solvent, they need to be dissolved in water from which the degrading enzymes have been removed when they are stored. However, by using the biological sample processing agent of the present invention for the storage of nucleic acids and storing them in a state of a solution containing nucleic acids, nucleic acids can be stored in an environment where the nucleic acid degrading enzymes are inactivated, and since they are non-volatile and have high thermal stability, nucleic acids can be stored simply and stably for a long period of time.

[0283] From the above viewpoints, when the organic ammonium salt of the present invention is used in a biological sample processing agent, it is preferred that the organic ammonium salt has a hydrogen bonding functional group in the anion, that is, it is particularly preferred that the organic ammonium salt has a hydrogen bonding functional group in both the cation and the anion. The functional group of the anion includes oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, phosphorus-containing groups and other groups capable of hydrogen bonding, and the above-mentioned carboxylic acid anions, sulfur-based anions, phosphorus-based anions, cyanide-based anions, and nitrogen oxide-based anions are preferred.

[0284] The hydrogen bonding functional group in the anion is preferably a hydroxyl group, a carbonyl group, a carboxyl group, a carboxylate group, a sulfonyl group, a sulfate group, a phosphoric acid group, or a phosphate group, and more preferably a hydroxyl group, a carboxyl group, a carboxylate group, a sulfonyl group, or a phosphoric acid group.

[0285] As described above, the organic ammonium salt used in the biological sample processing agent of the present invention is solid at 25°C, and has a hydrogen bonding functional group in the cation or in both the cation and the anion, so it has high affinity with the biological sample and excellent preservation of the biological sample. When the biological sample is dissolved, dispersed and stored in the liquid organic ammonium salt at 25°C, it is limited by the solubility of the biological sample and the uniform dispersion stability. However, if it is solid at 25°C, the biological sample can be mixed at a higher concentration and can be stored at a high concentration. Furthermore, the biological sample processing agent of the present invention can store the biological sample for a long time even in a high temperature environment, for example, it can be stored for a long time under high temperature conditions in a state where the structure of proteins, nucleic acids, and enzymes is maintained, and the activity of the enzyme can be maintained.

[0286] The hydrogen-bonding material treatment agent of the present invention, for example, can form hydrogen bonds between hydrogen-bond accepting functional groups of biological samples such as enzymes, peptides, proteins, nucleic acids or poorly soluble polysaccharides such as cellulose having carbonyl or ether groups, and the organic ammonium salt enters the complex intertwined structure of the biological sample to unravel the biological molecular structure and reduce the interaction between biological polymers. Therefore, it can convert inactive denatured proteins into active states and is useful as a protein refolding reagent.

[0287] Protein renaturation refers to the restoration of an insoluble protein or a protein that has lost its higher structure to a protein of a higher structure in its native state (activated state). For example, as needed, a denaturant is directly added to a protein renaturation solution containing the organic ammonium salt of the present invention, thereby solubilizing or renaturing the insoluble protein or the protein that has lost its higher structure. Alternatively, by adding a denaturant as needed and solubilizing the insoluble protein or the protein that has lost its higher structure with a general protein solubilizing agent, and dissolving the solubilizing agent in a renaturation solution containing the organic ammonium salt of the present invention, the protein is restored to its higher structure, thereby obtaining an active protein.

[0288] The biological sample solution of the present invention comprises the biological sample treatment agent of the present invention, the biological sample and a solvent. As the biological sample, preferably a biocatalyst, a protein or a nucleic acid. When used as a biological sample solution, the organic ammonium salt of the present invention has a high hydrophilicity due to its structural characteristics and a high affinity for the biological sample. Therefore, in addition to using the organic ammonium salt of the present invention alone as a solid state, it can also be mixed with other solvent components such as water or a polar solvent and used as a solution or a dispersion as described above. In addition, additives can also be added for use.

[0289] The biological sample solution includes, for example, a solution containing an activated biological sample and a solution stored while maintaining the biological sample in an activated state.

[0290] The storage period of the biocatalyst as the activated biological sample depends on the type of the biocatalyst, and may be, for example, 30 days or longer, or 60 days or longer.

[0291] Regarding the storage temperature of the biocatalyst, the biocatalyst solution of the present invention can be stored under harsh conditions such as high temperature and high humidity, for example, within a range of 40° C. or less, and the biocatalyst can be stored in a liquid state while maintaining its activity for a long period of time.

[0292] Example

[0293] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0294] The compounds of Examples 1 to 108 shown in Tables 1 to 6 were synthesized in the following manner.

[0295] <Example 1> Synthesis of Compound 1

[0296] The compound represented by the following formula was synthesized.

[0297]

[0298] Triethanolamine (19.11 g, 0.128 mol) and formic acid (5.89 g, 0.128 mmol) were reacted in 100 mL of water at room temperature for 3 hours, and then water was distilled off under reduced pressure to obtain a pale yellow solid. The obtained solid was washed to obtain compound 1 (triethanolamine formate) as a white solid.

[0299] FT-IR(KBr):3360cm -1 :OH stretching vibration 2950cm -1 :CH stretching vibration 1558cm -1 :COO - Stretching vibration

[0300] 1 H-NMR (D2O 400MHz): δ3.31(t, 6H, N + C H2 CH2OH), δ3.85(t, 6H, N + CH2C H2 OH), δ8.36(s,1H, H COO - ).

[0301] 13 C-NMR (D2O 100MHz): δ55.4 (N + C H 2 CH2OH), δ55.6(N + CH2 C H2OH), δ171.0(H C OO - ).

[0302] <Examples 2 to 87>

[0303] Compounds 2 to 87 of Examples 2 to 87 shown in Tables 1 to 5 were synthesized by the same synthesis method as in Example 1 and in accordance with the blending molar ratios described in Tables 7 to 9. The physical property values ​​are shown below.

[0304] <Example 2> Synthesis of Compound 2

[0305]

[0306] FT-IR(KBr):3388cm -1 :OH stretching vibration 2922cm -1 :CH stretching vibration 1543cm-1:COO - Stretching vibration

[0307] 1H-NMR (D2O 400MHz): δ0.73-0.77(m, 3H, NH3 + C(CH2OH)2CH2C H3 ), δ1.50-1.56 (m, 2H, NH3 + C(CH2OH)2C H2 CH3), δ1.84(s, 3H, C H3 COO - ), δ3.49-3.50 (m, 4H, NH3 + C(C H2 OH)2CH2CH3).

[0308] 13 C-NMR (D2O100MHz):δ6.3(NH3 + C(CH2OH)2CH2 C H3),δ23.2(NH3 + C(CH2OH)2 C H2CH3),δ23.3( C H3CO - ),δ60.5(NH3 + C (CH2OH)2CH2CH3),δ63.3(NH3 + C( C H2OH)2CH2CH3),δ181.4(CH3 C OO - ).

[0309]

[0310] FT-IR(KBr):3145cm -1 :O-H stretching vibration 2946cm -1 :C-H stretching vibration 1572cm -1 :COO - Stretching vibration

[0311] 1 H-NMR(D2O 400MHz): δ1.84(s,3H,C H3 COO － ),δ3.57(s,6H,NH3 + C(C H2 OH)3).

[0312] 13 C-NMR (D2O 100MHz): δ23.3( C H3COO －),δ59.2(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3),δ181.4(CH3 C OO － ).

[0313] <Example 4> Synthesis of Compound 4

[0314]

[0315] FT-IR(KBr):3375cm -1 :O-H stretching vibration 2955cm -1 :C-H stretching vibration 1576cm -1 :COO - Stretching vibration

[0316] 1 H-NMR(D2O 400MHz): δ0.80(t,3H,C H3 CH2),δ1.44(m,2H,CH3C H2 ),δ2.06(t,2H,C H2 COO － ),δ3.32-3.38(m,1H,HOCH2C H (N + H3)CH2OH),δ3.61-3.77(m,4H,HOC H2 CH(N + H3)C H2 OH).

[0317] 13 C-NMR (D2O 100MHz):δ13.2( C H3CH2),δ19.3(CH3 C H2),δ39.6( C H2CO - ),δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ184.1(CH2 C OO - ).

[0318] <Example 5> Synthesis of Compound 5

[0319]

[0320] FT-IR(KBr):3145cm -1 :O-H stretching vibration 2946cm -1 :C-H stretching vibration 1572cm -1 :COO - Stretching vibration

[0321] 1 H-NMR(D2O 400MHz): δ0.80(t,3H,C H3 CH2),δ1.44(m,2H,CH3C H2 ),δ2.06(t,2H,C H2 COO － ),δ3.57(s,6H,NH3 + C(C H2 OH)3).

[0322] 13 C-NMR (D2O 100MHz):δ13.2( C H3CH2),δ19.3(CH3 C H2),δ39.6( C H2COO - ),δ59.2(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3),δ184.1(CH2 C OO - ).

[0323] <Example 6> Synthesis of Compound 6

[0324]

[0325] FT-IR(KBr):3167cm -1 :O-H stretching vibration 2920cm -1 :C-H stretching vibration 1573cm -1 :COO - Stretching vibration

[0326] 1 H-NMR(D2O 400MHz): δ0.80(t,3H,C H3 CH2),δ1.44(m,2H,CH3C H2 ),δ2.06(t,2H,C H2 COO -),δ2.94-3.13(m,2H,HOCH2(CH(OH))3CH(OH)C H2 NH3 + ),δ3.51-3.72(m,5H,HOC H2 (C H (OH))3CH(OH)CH2NH3 + ),δ3.89-3.96(m,1H,HOCH2(CH(OH))3C H (OH)CH2NH3 + ).

[0327] 13 C-NMR (D2O100MHz):δ13.2( C H3CH2),δ19.3(CH3 C H2),δ39.6( C H2COO - ),δ41.7(HOCH2(CH(OH))3CH(OH) C H2NH3 + ),δ62.6(HO C H2(CH(OH))3CH(OH)CH2NH3 + ),δ68.9-70.9(HOCH2( C H(OH))3 C H(OH)CH2NH3 + ),δ184.1(CH2 C OO － ).

[0328] <Example 7> Synthesis of Compound 7

[0329]

[0330] FT-IR(KBr):3177cm -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1563cm -1 :COO - Stretching vibration

[0331] 1 H-NMR(D2O 400MHz): δ0.80(t,3H,C H3 CH2),δ1.17(m,4H,CH3C H2 C H2 ),δ1.44(m,2H,C H2 CH2COO - ),δ2.10(t,2H,CH2 COO - ),δ3.04(m,2H,N + C H2 CH2OH),δ3.77(m,2H,N + CH2C H2 OH).

[0332] 13 C-NMR (D2O 100MHz):δ13.3( C H3CH2),δ21.8(CH3 C H2),δ25.5(CH3CH2 C H2),δ31.0( C H2CH2COO - ),δ37.5( C H2COO - ),δ41.2(N + C H2CH2OH),δ57.6(N + CH2 C H2OH),δ184.2(CH2 C OO - ).

[0333] <Example 8> Synthesis of Compound 8

[0334]

[0335] FT-IR(KBr):3375cm -1 :O-H stretching vibration 2955cm -1 :C-H stretching vibration 1576cm -1 :COO - Stretching vibration

[0336] 1 H-NMR(D2O 400MHz): δ0.80(t,3H,C H3 CH2),δ1.17(m,4H,CH3C H2 C H2 ),δ1.44(m,2H,C H2 CH2COO - ),δ2.10(t,2H,C H2 COO - ), δ3.32-3.38(m, 1H, HOCH2C H (N + H3)CH2OH), δ3.61-3.77(m, 4H, HOC H2 CH(N +H3)C H2 OH).

[0337] 13 C-NMR (D2O100MHz): 13.3( C H3CH2),δ21.8(CH3 C H2),δ25.5(CH3CH2 C H2),δ31.0( C H2CH2COO - ),δ37.5( C H2COO - ),δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ184.2(CH2 C OO - ).

[0338] <Example 9> Synthesis of Compound 9

[0339]

[0340] FT-IR(KBr):3145cm -1 :O-H stretching vibration 2946cm -1 :C-H stretching vibration 1572cm -1 :COO - Stretching vibration

[0341] 1 H-NMR(D2O 400MHz): δ0.80(t,3H,C H3 CH2),δ1.17(m,4H,CH3C H2 C H2 ),δ1.44(m,2H,C H2 CH2COO - ),δ2.10(t,2H,C H2 COO - ),δ3.57(s,6H,NH3 + C(C H2 OH)3).

[0342] 13 C-NMR (D2O 100MHz):δ13.3( C H3CH2),δ21.8(CH3 C H2),δ25.5(CH3CH2 CH2),δ31.0( C H2CH2COO - ),δ37.5( C H2COO - ),δ59.2(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3),δ184.2(CH2 C OO － ).

[0343] <Example 10> Synthesis of Compound 10

[0344]

[0345] FT-IR(KBr):3167cm -1 :O-H stretching vibration 2920cm -1 :C-H stretching vibration 1573cm -1 :COO - Stretching vibration

[0346] 1 H-NMR(D2O400MHz): δ0.80(t,3H,C H3 CH2),δ1.17(m,4H,CH3C H2 C H2 ),δ1.44(m,2H,C H2 CH2COO - ),δ2.10(t,2H,C H2 COO - ),δ2.94-3.13(m,2H,HOCH2(CH(OH))3CH(OH)C H2 NH3 + ),δ3.51-3.72(m,5H,HOC H2 (C H (OH))3CH(OH)CH2NH3 + ),δ3.89-3.96(m,1H,HOCH2(CH(OH))3C H (OH)CH2NH3 + ).

[0347] 13 C-NMR (D2O100MHz):δ13.3( C H3CH2),δ21.8(CH3 C H2),δ25.5(CH3CH2 CH2),δ31.0( C H2CH2COO - ),δ37.5( C H2COO - ),δ41.7(HOCH2(CH(OH))3CH(OH) C H2NH3 + ),δ62.6(HO C H2(CH(OH))3CH(OH)CH2NH3 + ),δ68.9-70.9(HOCH2( C H(OH))3 C H(OH)CH2NH3 + ),δ184.2(CH2 C OO － ).

[0348] <Example 11> Synthesis of Compound 11

[0349]

[0350] FT-IR(KBr):3177cm -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1563cm -1 :COO - Stretching vibration

[0351] 1 H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,8H,CH3(C H2 )4),δ1.48(m,2H,C H2 CH2COO － ),δ2.09(m,2H,C H2 COO － ),δ3.04(m,2H,N + C H2 CH2OH),δ3.77(m,2H,N + CH2C H2 OH).

[0352] 13 C-NMR (D2O 100MHz):δ13.4( C H3CH2),δ22.0(CH3 C H2CH2),δ25.9(CH3CH2 C H2),δ28.3(CH3CH2CH2 CH2),δ28.7( C H2CH2CH2COO － ),δ31.0( C H2CH2COO － ),δ37.7( C H2COO － ),δ41.2(N + C H2CH2OH),δ57.6(N + CH2 C H2OH),δ184.3(CH2 C OO － ).

[0353] <Example 12> Synthesis of Compound 12

[0354]

[0355] FT-IR(KBr):3360cm -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1558cm -1 :COO - Stretching vibration

[0356] 1 H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,8H,CH3(C H2 )4),δ1.48(m,2H,C H2 CH2COO - ),δ2.09(m,2H,C H2 COO - ),δ3.31(t,6H,N + C H2 CH2OH),δ3.85(t,6H,N + CH2C H2 OH).

[0357] 13 C-NMR (D2O 100MHz):δ13.4( C H3CH2),δ22.0(CH3 C H2CH2),δ25.9(CH3CH2 C H2),δ28.3(CH3CH2CH2 C H2),δ28.7( C H2CH2CH2COO － ),δ31.0( CH2CH2COO - ),δ37.7( C H2COO - ),δ55.4(N + C H2CH2OH),δ55.6(N + CH2 C H2OH),δ184.3(CH2 C OO － ).

[0358] <Example 13> Synthesis of Compound 13

[0359]

[0360] FT-IR(KBr):3375cm -1 :O-H stretching vibration 2955cm -1 :C-H stretching vibration 1576cm -1 :COO - Stretching vibration

[0361] 1 H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,8H,CH3(C H2 )4),δ1.48(m,2H,C H2 CH2COO － ),δ2.09(m,2H,C H2 COO － ),δ3.32-3.38(m,1H,HOCH2C H (N + H3)CH2OH),δ3.61-3.77(m,4H,HOC H2 CH(N + H3)C H2 OH).

[0362] 13 C-NMR (D2O 100MHz):δ13.4( C H3CH2),δ22.0(CH3 C H2CH2),δ25.9(CH3CH2 C H2),δ28.3(CH3CH2CH2 C H2),δ28.7( C H2CH2CH2COO - ),δ31.0( C H2CH2COO -),δ37.7( C H2COO - ),δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ184.3(CH2 C OO - ).

[0363] <Example 14> Synthesis of Compound 14

[0364]

[0365] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1543cm -1 :COO - Stretching vibration

[0366] 1 H-NMR (D2O 400MHz): δ0.73-0.77(m,3H,NH3 + C(CH2OH)2CH2C H3 ),δ0.79(t,3H,C H3 CH2),δ1.21(m,8H,CH3(C H2 )4),δ1.50-1.56(m,2H,NH3 + C(CH2OH)2C H2 CH3),δ1.48(m,2H,C H2 CH2COO - ),δ2.09(m,2H,C H2 COO - ),δ3.49-3.50(m,4H,NH3 + C(C H2 OH)2CH2CH3).

[0367] 13 C-NMR (D2O 100MHz):δ6.3(NH3 + C(CH2OH)2CH2 C H3),δ13.4( C H3CH2),δ22.0(CH3 C H2CH2),δ23.2(NH3 + C(CH2OH)2 CH2CH3),δ25.9(CH3CH2 C H2),δ28.3(CH3CH2CH2 C H2),δ28.7( C H2CH2CH2COO － ),δ31.0( C H2CH2COO － ),δ37.7( C H2COO － ),δ60.5(NH3 + C (CH2OH)2CH2CH3),δ63.3(NH3 + C( C H2OH)2CH2CH3),δ184.3(CH2 C OO － ).

[0368] <Example 15> Synthesis of Compound 15

[0369]

[0370] FT-IR(KBr):3145cm- 1 :O-H stretching vibration 2946cm -1 :C-H stretching vibration 1572cm -1 :COO - Stretching vibration

[0371] 1 H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,8H,CH3(C H2 )4),δ1.48(m,2H,C H2 CH2COO － ),δ2.09(m,2H,C H2 COO － ),δ3.57(s,6H,NH3 + C(C H2 OH)3).

[0372] 13 C-NMR (D2O 100MHz):δ13.4( C H3CH2),δ22.0(CH3 C H2CH2),δ25.9(CH3CH2 C H2),δ28.3(CH3CH2CH2 C H2),δ28.7( CH2CH2CH2COO － ),δ31.0( C H2CH2COO - ),δ37.7( C H2COO - ),δ59.2(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3),δ184.3(CH2 C OO - ).

[0373] <Example 16> Synthesis of Compound 16

[0374]

[0375] FT-IR(KBr):3167cm -1 :O-H stretching vibration 2920cm -1 :C-H stretching vibration 1573cm -1 :COO - Stretching vibration

[0376] 1 H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,8H,CH3(C H2 )4),δ1.48(m,2H,C H2 CH2COO － ),δ2.09(m,2H,C H2 COO － ),δ2.94-3.13(m,2H,HOCH2(CH(OH))3CH(OH)C H2 NH3 + ),δ3.51-3.72(m,5H,HOC H2 (C H (OH))3CH(OH)CH2NH3 + ),δ3.89-3.96(m,1H,HOCH2(CH(OH))3C H (OH)CH2NH3 + ).

[0377] 13 C-NMR (D2O100MHz):δ13.4( C H3CH2),δ22.0(CH3 C H2CH2),δ25.9(CH3CH2C H2),δ28.3(CH3CH2CH2 C H2),δ28.7( C H2CH2CH2COO - ),δ31.0( C H2CH2COO - ),δ37.7( C H2COO - ),δ41.7(HOCH2(CH(OH))3CH(OH) C H2NH3 + ),δ62.6(HO C H2(CH(OH))3CH(OH)CH2NH3 + ),δ68.9-70.9(HOCH2( C H(OH))3 C H(OH)CH2NH3 + ),δ184.3(CH2 C OO - ).

[0378] <Example 17> Synthesis of Compound 17

[0379]

[0380] FT-IR(KBr):3177cm -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1563cm -1 :COO - Stretching vibration

[0381] 1 H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,12H,CH3(C H2 )6),δ1.47(m,2H,C H2 CH2COO - ),δ2.10(t,2H,C H2 COO - ),δ3.04(m,2H,N + C H2 CH2OH),δ3.77(m,2H,N + CH2C H2 OH).

[0382] 13 C-NMR (D2O 100MHz):δ13.5( CH3CH2),δ22.2(CH3 C H2CH2),δ26.0(CH3CH2 C H2),δ28.7(CH3CH2CH2 C H2),δ28.8(CH3CH2CH2CH2 C H2),δ29.0(( C H2)2CH2CH2COO - ),δ31.4( C H2CH2COO - ),δ37.5( C H2COO - ),δ41.2(N + C H2CH2OH),δ57.6(N + CH2 C H2OH),δ183.6(CH2 C OO - ).

[0383] <Example 18> Synthesis of Compound 18

[0384]

[0385] FT-IR(KBr):3360cm -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1558cm -1 :COO - Stretching vibration

[0386] 1 H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,12H,CH3(C H2 )6),δ1.47(m,2H,C H2 CH2COO - ),δ2.10(t,2H,C H2 COO - ),δ3.31(t,6H,N + C H2 CH2OH),δ3.85(t,6H,N + CH2C H2 OH).

[0387] 13 C-NMR (D2O 100MHz):δ13.5( C H3CH2),δ22.2(CH3 CH2CH2),δ26.0(CH3CH2 C H2),δ28.7(CH3CH2CH2 C H2),δ28.8(CH3CH2CH2CH2 C H2),δ29.0(( C H2)2CH2CH2COO － ),δ31.4( C H2CH2COO － ),δ37.5( C H2COO － ),δ55.4(N + C H2CH2OH),δ55.6(N + CH2 C H2OH),δ183.6(CH2 C OO － ).

[0388] <Example 19> Synthesis of Compound 19

[0389]

[0390] FT-IR(KBr):3375cm -1 :O-H stretching vibration 2955cm -1 :C-H stretching vibration 1576cm -1 :COO - Stretching vibration

[0391] 1 H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,12H,CH3(C H2 )6),δ1.47(m,2H,C H2 CH2COO - ),δ2.10(t,2H,C H2 COO - ),δ3.32-3.38(m,1H,HOCH2C H (N + H3)CH2OH),δ3.61-3.77(m,4H,HOC H2 CH(N + H3)C H2 OH).

[0392] 13 C-NMR (D2O 100MHz):δ13.5( C H3CH2),δ22.2(CH3C H2CH2),δ26.0(CH3CH2 C H2),δ28.7(CH3CH2CH2 C H2),δ28.8(CH3CH2CH2CH2 C H2),δ29.0(( C H2)2CH2CH2COO － ),δ31.4( C H2CH2COO － ),δ37.5( C H2COO － ),δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ183.6(CH2 C OO － ).

[0393] <Example 20> Synthesis of Compound 20

[0394]

[0395] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1543cm -1 :COO - Stretching vibration

[0396] 1 H-NMR (D2O 400MHz): δ0.73-0.77(m,3H,NH3 + C(CH2OH)2CH2C H3 ),δ0.79(t,3H,C H3 CH2),δ1.21(m,12H,CH3(C H2 )6),δ1.47(m,2H,C H2 CH2COO - ),δ1.50-1.56(m,2H,NH3 + C(CH2OH)2C H2 CH3),δ2.10(t,2H,C H2 COO － ),δ3.49-3.50(m,4H,NH3 + C(C H2 OH)2CH2CH3).

[0397] 13 C-NMR (D2O 100MHz):δ6.3(NH3 + C(CH2OH)2CH2 C H3),δ13.5( C H3CH2),δ22.2(CH3 C H2CH2),δ23.2(NH3 + C(CH2OH)2 C H2CH3),δ26.0(CH3CH2 C H2),δ28.7(CH3CH2CH2 C H2),δ28.8(CH3CH2CH2CH2CH2),δ29.0(( C H2)2CH2CH2COO － ),δ31.4( C H2CH2COO － ),δ37.5( C H2COO － ),δ60.5(NH3 + C (CH2OH)2CH2CH3),δ63.3(NH3 + C( C H2OH)2CH2CH3),δ183.6(CH2 C OO － ).

[0398] <Example 21> Synthesis of Compound 21

[0399]

[0400] FT-IR(KBr):3145cm -1 :O-H stretching vibration 2946cm -1 :C-H stretching vibration 1572cm -1 :COO - Stretching vibration

[0401] 1 H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,12H,CH3(C H2 )6),δ1.47(m,2H,C H2 CH2COO - ),δ2.10(t,2H,C H2 COO - ),δ3.57(s,6H,NH3+ C(C H2 OH)3).

[0402] 13 C-NMR (D2O 100MHz):δ13.5( C H3CH2),δ22.2(CH3 C H2CH2),δ26.0(CH3CH2 C H2),δ28.7(CH3CH2CH2 C H2),δ28.8(CH3CH2CH2CH2 C H2),δ29.0(( C H2)2CH2CH2COO - ),δ31.4( C H2CH2COO - ),δ37.5( C H2COO - ),δ59.2(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3),δ183.6(CH2 C OO － ).

[0403] <Example 22> Synthesis of Compound 22

[0404]

[0405] FT-IR(KBr):3167cm -1 :O-H stretching vibration 2920cm -1 :C-H stretching vibration 1573cm -1 :COO - Stretching vibration

[0406] 1 H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,12H,CH3(C H2 )6),δ1.47(m,2H,C H2 CH2COO － ),δ2.10(t,2H,C H2 COO - ),δ2.94-3.13(m,2H,HOCH2(CH(OH))3CH(OH)C H2 NH3 +),δ3.51-3.72(m,5H,HOC H2 (C H (OH))3CH(OH)CH2NH3 + ),δ3.89-3.96(m,1H,HOCH2(CH(OH))3C H (OH)CH2NH3 + ).

[0407] 13 C-NMR (D2O 100MHz):δ13.5( C H3CH2),δ22.2(CH3 C H2CH2),δ26.0(CH3CH2 C H2),δ28.7(CH3CH2CH2 C H2),δ28.8(CH3CH2CH2CH2 C H2),δ29.0(( C H2)2CH2CH2COO - ),δ31.4( C H2CH2COO - ),δ37.5( C H2COO - ),δ41.7(HOCH2(CH(OH))3CH(OH) C H2NH3 + ),δ62.6(HO C H2(CH(OH))3CH(OH)CH2NH3 + ),δ68.9-70.9(HOCH2( C H(OH))3 C H(OH)CH2NH3 + ),δ183.6(CH2 C OO - ).

[0408] <Example 23> Synthesis of Compound 23

[0409]

[0410] FT-IR(KBr):3177cm -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1563cm -1 :COO - Stretching vibration

[0411] 1H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,16H,CH3(C H2 )8),δ1.47(m,2H,C H2 CH2COO － ),δ2.10(t,2H,C H2 COO － ),δ3.04(m,2H,N + C H2 CH2OH),δ3.77(m,2H,N + CH2C H2 OH).

[0412] 13 C-NMR (D2O 100MHz):δ13.5( C H3CH2),δ22.2(CH3 C H2CH2),δ26.0(CH3CH2 C H2),δ28.7(CH3CH2CH2 C H2),δ28.8(CH3CH2CH2CH2 C H2),δ29.0(( C H2)4CH2CH2COO － ),δ31.4( C H2CH2COO － ),δ37.5( C H2COO － ),δ41.2(N + C H2CH2OH),δ57.6(N + CH2 C H2OH),δ183.6(CH2 C OO － ).

[0413] <Example 24> Synthesis of Compound 24

[0414]

[0415] FT-IR(KBr):3306cm －1 :O-H stretching vibration 2923cm －1 :C-H stretching vibration 1559cm －1 :COO － Stretching vibration

[0416] 1H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,16H,CH3(C H2 )8),δ1.47(m,2H,C H2 CH2COO － ),δ2.10(t,2H,C H2 COO － ),δ3.15(t,4H,N + C H2 CH2OH),δ3.79(t,4H,N + CH2C H2 OH).

[0417] 13 C-NMR (D2O 100MHz):δ13.5( C H3CH2),δ22.2(CH3 C H2CH2),δ26.0(CH3CH2 C H2),δ28.7(CH3CH2CH2 C H2),δ28.8(CH3CH2CH2CH2 C H2),δ29.0(( C H2)4CH2CH2COO - ),δ31.4( C H2CH2COO - ),δ37.5( C H2COO - ),δ48.9(N + C H2CH2OH),δ56.6(N + CH2 C H2OH),δ183.6(CH2 C OO - ).

[0418] <Example 25> Synthesis of Compound 25

[0419]

[0420] FT-IR(KBr):3360cm -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1558cm -1 :COO - Stretching vibration

[0421] 1H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,16H,CH3(C H2 )8),δ1.47(m,2H,C H2 CH2COO - ),δ2.10(t,2H,C H2 COO - ),δ3.31(t,6H,N + C H2 CH2OH),δ3.85(t,6H,N + CH2C H2 OH).

[0422] 13 C-NMR (D2O 100MHz):δ13.5( C H3CH2),δ22.2(CH3 C H2CH2),δ26.0(CH3CH2 C H2),δ28.7(CH3CH2CH2 C H2),δ28.8(CH3CH2CH2CH2 C H2),δ29.0(( C H2)4CH2CH2COO - ),δ31.4( C H2CH2COO - ),δ37.5( C H2COO - ),δ55.4(N + C H2CH2OH),δ55.6(N + CH2 C H2OH),δ183.6(CH2 C OO - ).

[0423] <Example 26> Synthesis of Compound 26

[0424]

[0425] FT-IR(KBr):3375cm -1 :O-H stretching vibration 2955cm -1 :C-H stretching vibration 1576cm -1 :COO - Stretching vibration

[0426] 1H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,16H,CH3(C H2 )8),δ1.47(m,2H,C H2 CH2COO - ),δ2.10(t,2H,C H2 COO - ),δ3.32-3.38(m,1H,HOCH2C H (N + H3)CH2OH),δ3.61-3.77(m,4H,HOC H2 CH(N + H3)C H2 OH).

[0427] 13 C-NMR (D2O 100MHz):δ13.5( C H3CH2),δ22.2(CH3 C H2CH2),δ26.0(CH3CH2 C H2),δ28.7(CH3CH2CH2 C H2),δ28.8(CH3CH2CH2CH2 C H2),δ29.0(( C H2)4CH2CH2COO - ),δ31.4( C H2CH2COO - ),δ37.5( C H2COO - ),δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ183.6(CH2 C OO - ).

[0428] <Example 27> Synthesis of Compound 27

[0429]

[0430] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1543cm -1 :COO - Stretching vibration

[0431] 1 H-NMR(D2O 400MHz):δ0.73-0.77(m,3H,NH3 + C(CH2OH)2CH2C H3 ),δ0.79(t,3H,C H3 CH2),δ1.21(m,16H,CH3(C H2 )8),δ1.47(m,2H,C H2 CH2COO - ),δ1.50-1.56(m,2H,NH3 + C(CH2OH)2C H2 CH3),δ3.49-3.50(m,4H,NH3 + C(C H2 OH)2CH2CH3),δ2.10(t,2H,C H2 COO - ).

[0432] 13 C-NMR(D2O 100MHz):δ6.3(NH3 + C(CH2OH)2CH2 C H3),δ13.5( C H3CH2),δ22.2(CH3 C H2CH2),δ23.2(NH3 + C(CH2OH)2 C H2CH3),δ26.0(CH3CH2 C H2),δ28.7(CH3CH2CH2 C H2),δ28.8(CH3CH2CH2CH2 C H2),δ29.0(( C H2)4CH2CH2COO - ),δ31.4( C H2CH2COO - ),δ37.5( C H2COO - ),δ60.5(NH3 + C (CH2OH)2CH2CH3),δ63.3(NH3 + C( C H2OH)2CH2CH3),δ183.6(CH2 C OO - ).

[0433] <Example 28> Synthesis of Compound 28

[0434]

[0435] FT-IR(KBr):3145cm -1 :O-H stretching vibration 2946cm -1 :C-H stretching vibration 1572cm -1 :COO - Stretching vibration

[0436] 1 H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,16H,CH3(C H2 )8),δ1.47(m,2H,C H2 CH2COO - ),δ2.10(t,2H,C H2 COO - ),δ3.57(s,6H,NH3 + C(C H2 OH)3).

[0437] 13 C-NMR (D2O 100MHz):δ13.5( C H3CH2),δ22.2(CH3 C H2CH2),δ26.0(CH3CH2 C H2),δ28.7(CH3CH2CH2 C H2),δ28.8(CH3CH2CH2CH2 C H2),δ29.0(( C H2)4CH2CH2COO - ),δ31.4( C H2CH2COO - ),δ37.5( C H2COO - ),δ59.2(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3),δ183.6(CH2 C OO - ).

[0438] <Example 29> Synthesis of Compound 29

[0439]

[0440] FT-IR(KBr):3167cm -1 :O-H stretching vibration 2920cm -1 :C-H stretching vibration 1573cm -1 :COO - Stretching vibration

[0441] 1 H-NMR(D2O 400MHz): δ0.79(t,3H,C H3 CH2),δ1.21(m,16H,CH3(C H2 )8),δ1.47(m,2H,C H2 CH2COO － ),δ2.10(t,2H,C H2 COO － ),δ2.94-3.13(m,2H,HOCH2(CH(OH))3CH(OH)C H2 NH3 + ),δ3.51-3.72(m,5H,HOC H2 (C H (OH))3CH(OH)CH2NH3 + ),δ3.89-3.96(m,1H,HOCH2(CH(OH))3C H (OH)CH2NH3 + ).

[0442] 13 C-NMR (D2O 100MHz):δ13.5( C H3CH2),δ22.2(CH3 C H2CH2),δ26.0(CH3CH2 C H2),δ28.7(CH3CH2CH2 C H2),δ28.8(CH3CH2CH2CH2 C H2),δ29.0(( C H2)4CH2CH2COO - ),δ31.4( C H2CH2COO - ),δ37.5( C H2COO - ),δ41.7(HOCH2(CH(OH))3CH(OH) C H2NH3 + ),δ62.6(HO C H2(CH(OH))3CH(OH)CH2NH3+ ),δ68.9-70.9(HOCH2( C H(OH))3 C H(OH)CH2NH3 + ),δ183.6(CH2 C OO － ).

[0443] <Example 30> Synthesis of Compound 30

[0444]

[0445] FT-IR(KBr):3177cm -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1563cm -1 :COO - Stretching vibration

[0446] 1 H-NMR (D2O 400MHz): δ1.13(m,6H,CHCH2(C H2 )3),δ1.55(m,4H,CHC H2 ),δ2.03(m,1H,C H COO － ),δ3.04(m,2H,N + C H2 CH2OH),δ3.77(m,2H,N + CH2C H2 OH).

[0447] 13 C-NMR (D2O 100MHz): δ25.5( C H2CH2CHCOO - ),δ25.7( C H2CHCOO - ),δ29.9( C H2CH2CH2CHCOO - ),δ41.2(N + C H2CH2OH),δ47.1( C HCOO - ),δ57.6(N + CH2 C H2OH),δ186.8(CH C OO - ).

[0448] <Example 31> Synthesis of Compound 31

[0449]

[0450] FT-IR(KBr):3360cm -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1558cm -1 :COO - Stretching vibration

[0451] 1 H-NMR (D2O 400MHz): δ1.13(m,6H,CHCH2(C H2 )3),δ1.55(m,4H,CHC H2 ),δ2.03(m,1H,C H COO － ),δ3.31(t,6H,N + C H2 CH2OH),δ3.85(t,6H,N + CH2C H2 OH).

[0452] 13 C-NMR (D2O 100MHz): δ25.5( C H2CH2CHCOO - ),δ25.7( C H2CHCOO - ),δ29.9( C H2CH2CH2CHCOO - ),δ47.1( C HCOO - ),δ55.4(N + C H2CH2OH),δ55.6(N + CH2 C H2OH),δ186.8(CH C OO - ).

[0453] <Example 32> Synthesis of Compound 32

[0454]

[0455] FT-IR(KBr):3375cm -1 :O-H stretching vibration 2955cm -1 :C-H stretching vibration 1576cm -1 :COO - Stretching vibration

[0456] 1 H-NMR (D2O 400MHz): δ1.13(m,6H,CHCH2(C H2 )3),δ1.55(m,4H,CHC H2 ),δ2.03(m,1H,C H COO - ),δ3.32-3.38(m,1H,HOCH2C H (N + H3)CH2OH),δ3.61-3.77(m,4H,HOC H2 CH(N + H3)C H2 OH).

[0457] 13 C-NMR (D2O 100MHz): δ25.5( C H2CH2CHCOO - ),δ25.7( C H2CHCOO - ),δ29.9( C H2CH2CH2CHCOO － ),δ47.1( C HCOO - ),δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ186.8(CH C OO - ).

[0458] <Example 33> Synthesis of Compound 33

[0459]

[0460] FT-IR(KBr):3177cm -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1563cm -1 :COO - Stretching vibration

[0461] 1 H-NMR(D2O 400MHz): δ1.68-1.70(m,3H,C H3 CHCHCOO - ),δ3.04(m,2H,N + C H2CH2OH),δ3.77(m,2H,N + CH2C H2 OH),δ5.69-5.75(m,1H,CH3CHC H COO - ),δ6.49-6.53(m,1H,CH3C H CHCOO - ).

[0462] 13 C-NMR (D2O 100MHz):δ16.9( C H3CHCHCOO - ),δ41.2(N + C H2CH2OH),δ57.6(N + CH2 C H2OH),δ127.2(CH3CH C HCOO - ),δ141.2(CH3 C HCHCOO - ),δ175.9(CH3CHCH C OO - ).

[0463] <Example 34> Synthesis of Compound 34

[0464]

[0465] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1543cm -1 :COO - Stretching vibration

[0466] 1 H-NMR (D2O 400MHz): δ0.73-0.77(m,3H,NH3 + C(CH2OH)2CH2C H3 ),δ0.89(t,3H,C H3 CH2),δ1.27(m,20H,CH3(C H2 )6CH2,(C H2 )4CH2CH2COO - ),δ1.50-1.56(m,2H,NH3 + C(CH2OH)2C H2 CH3),δ1.53(m,2H,C H2 CH2COO- ),δ2.00(m,4H,C H2 CH=CHC H2 ),δ2.14(t,2H,CH2C H2 COO - ),δ2.99(t,2H,N + C H2 CH2OH),δ3.49-3.50(m,4H,NH3 + C(C H2 OH)2CH2CH3),δ3.76(t,2H,N + CH2C H2 OH),δ5.32(m,2H,C H =C H ).

[0467] 13 C-NMR(D2O 100MHz):δ6.3(NH3 + C(CH2OH)2CH2 C H3),δ14.0( C H3CH2),δ22.6(CH3 C H2),δ23.2(NH3 + C(CH2OH)2 C H2CH3),δ26.4( C H2CH2COO － ),δ27.2( C H2CH=CH C H2),δ29.3(CH3CH2CH2( C H2)4,( C H2)4CH2CH2COO － ),δ31.9(CH3CH2 C H2),δ37.8( C H2CH2COO － ),δ41.9(N + C H2CH2OH),δ58.6(N + CH2 C H2OH),δ60.5(NH3 + C (CH2OH)2CH2CH3),δ63.3(NH3 + C( C H2OH)2CH2CH3),δ129.7( C H= C H),δ181.7( C OO －).

[0468] <Example 35> Synthesis of Compound 35

[0469]

[0470] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1543cm -1 :COO - Stretching vibration

[0471] 1 H-NMR (D2O 400MHz): δ0.73-0.77(m,3H,NH3 + C(CH2OH)2CH2C H3 ),δ1.50-1.56(m,2H,NH3 + C(CH2OH)2C H2 CH3),δ3.49-3.50(m,4H,NH3 + C(C H2 OH)2CH2CH3),δ3.87(s,2H,HOC H2 COO － ).

[0472] 13 C-NMR (D2O 100MHz):δ6.3(NH3 + C(CH2OH)2CH2 C H3),δ23.2(NH3 + C(CH2OH)2 C H2CH3),δ60.5(NH3 + C (CH2OH)2CH2CH3),δ61.3(HO C H2COO - ),δ63.3(NH3 + C( C H2OH)2CH2CH3),δ179.9(HOCH2 C OO - ).

[0473] <Example 36> Synthesis of Compound 36

[0474]

[0475] FT-IR(KBr):3145cm -1 :O-H stretching vibration 2946cm -1:C-H stretching vibration 1572cm -1 :COO - Stretching vibration

[0476] 1 H-NMR(D2O 400MHz): δ3.57(s,6H,NH3 + C(C H2 OH)3),δ3.87(s,2H,HOC H2 COO - ).

[0477] 13 C-NMR(D2O 100MHz): δ59.2(NH3 + C (CH2OH)3),δ61.3(HO C H2COO - ),δ61.4(NH3 + C( C H2OH)3),δ179.9(HOCH2 C OO - ).

[0478] <Example 37> Synthesis of Compound 37

[0479]

[0480] FT-IR(KBr):3375cm -1 :O-H stretching vibration 2955cm -1 :C-H stretching vibration 1576cm -1 :COO - Stretching vibration

[0481] 1 H-NMR(D2O 400MHz): δ0.89(t,3H,C H3 CH2),δ1.27(m,20H,CH3(C H2 )6CH2,(C H2 )4CH2CH2COO - ),δ1.53(m,2H,C H2 CH2COO - ),δ1.54(m,4H,C H2 CH(OH)CH(OH)C H2 ),δ2.14(t,2H,CH2C H2 COO - ),δ3.29(m,2H,C H (OH)C H(OH)),δ3.32-3.38(m,1H,HOCH2C H (N + H3)CH2OH),δ3.61-3.77(m,4H,HOC H2 CH(N + H3)C H2 OH).

[0482] 13 C-NMR (D2O 100MHz):δ14.0( C H3CH2),δ22.6(CH3 C H2),δ26.4( C H2CH2COO － ),δ29.3(CH3CH2CH2( C H2)4,( C H2)4CH2CH2COO - ),δ31.7( C H2CH(OH)CH(OH) C H2),δ31.9(CH3CH2 C H2),δ37.8( C H2CH2COO - ),δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ77.2( C H(OH) C H(OH)),δ181.7( C OO - ).

[0483] <Example 38> Synthesis of Compound 38

[0484]

[0485] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1543cm -1 :COO - Stretching vibration

[0486] 1 H-NMR (D2O 400MHz): δ0.73-0.77(m,3H,NH3 + C(CH2OH)2CH2C H3),δ0.89(t,3H,C H3 CH2),δ1.27(m,20H,CH3(C H2 )6CH2,(C H2 )4CH2CH2COO - ),δ1.50-1.56(m,2H,NH3 + C(CH2OH)2C H2 CH3),δ1.53(m,2H,C H2 CH2COO - ),δ1.54(m,4H,C H2 CH(OH)CH(OH)C H2 ),δ2.14(t,2H,CH2C H2 COO - ),δ3.29(m,2H,C H (OH)C H (OH)),δ3.49-3.50(m,4H,NH3 + C(C H2 OH)2CH2CH3).

[0487] 13 C-NMR(D2O 100MHz):δ6.3(NH3 + C(CH2OH)2CH2 C H3),δ14.0( C H3CH2),δ22.6(CH3 C H2),δ23.2(NH3 + C(CH2OH)2 C H2CH3),δ26.4( C H2CH2COO - ),δ29.3(CH3CH2CH2( C H2)4,( C H2)4CH2CH2COO - ),δ31.7( C H2CH(OH)CH(OH) C H2),δ31.9(CH3CH2 C H2),δ37.8( C H2CH2COO - ),δ60.5(NH3 + C (CH2OH)2CH2CH3),δ63.3(NH3 + C( C H2OH)2CH2CH3),δ77.2( C H(OH)C H(OH)),δ181.7( C OO - ).

[0488] <Example 39> Synthesis of Compound 39

[0489]

[0490] FT-IR(KBr):3145cm -1 :O-H stretching vibration 2946cm -1 :C-H stretching vibration 1572cm -1 :COO - Stretching vibration

[0491] 1 H-NMR(D2O 400MHz): δ0.89(t,3H,C H3 CH2),δ1.27(m,20H,CH3(C H2 )6CH2,(C H2 )4CH2CH2COO - ),δ1.53(m,2H,C H2 CH2COO - ),δ1.54(m,4H,C H2 CH(OH)CH(OH)C H2 ),δ2.14(t,2H,CH2C H2 COO - ),δ3.29(m,2H,C H (OH)C H (OH)),δ3.57(s,6H,NH3 + C(C H2 OH)3).

[0492] 13 C-NMR (D2O 100MHz):δ14.0( C H3CH2),δ22.6(CH3 C H2),δ26.4( C H2CH2COO - ),δ29.3(CH3CH2CH2( C H2)4,( C H2)4CH2CH2COO - ),δ31.7( C H2CH(OH)CH(OH) C H2),δ31.9(CH3CH2 C H2),δ37.8( CH2CH2COO - ),δ59.2(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3),δ77.2( C H(OH) C H(OH)),δ181.7( C OO - ).

[0493] <Example 40> Synthesis of Compound 40

[0494]

[0495] FT-IR(KBr):3167cm -1 :O-H stretching vibration 2920cm -1 :C-H stretching vibration 1573cm -1 :COO － Stretching vibration

[0496] 1 H-NMR(D2O 400MHz): δ0.89(t,3H,C H3 CH2),δ1.27(m,20H,CH3(C H2 )6CH2,(C H2 )4CH2CH2COO － ),δ1.53(m,2H,C H2 CH2COO - ),δ1.54(m,4H,C H2 CH(OH)CH(OH)C H2 ),δ2.14(t,2H,CH2C H2 COO - ),δ2.94-3.13(m,2H,HOCH2(CH(OH))3CH(OH)CH 2 NH3 + ),δ3.29(m,2H,C H (OH)C H (OH)),δ3.51-3.72(m,5H,HOC H2 (C H (OH))3CH(OH)CH2NH3 + ),δ3.89-3.96(m,1H,HOCH2(CH(OH))3C H (OH)CH2NH3 + ).

[0497] 13 C-NMR (D2O100MHz):δ14.0( C H3CH2),δ22.6(CH3 C H2),δ26.4( C H2CH2COO - ),δ29.3(CH3CH2CH2( C H2)4,( C H2)4CH2CH2COO - ),δ31.7( C H2CH(OH)CH(OH) C H2),δ31.9(CH3CH2 C H2),δ37.8( C H2CH2COO - ),δ41.7(HOCH2(CH(OH))3CH(OH) C H2NH3 + ),δ62.6(HO C H2(CH(OH))3CH(OH)CH2NH3 + ),δ68.9-70.9(HOCH2( C H(OH))3 C H(OH)CH2NH3 + ),δ77.2( C H(OH) C H(OH)),δ181.7( C OO - ).

[0498] <Example 41> Synthesis of Compound 41

[0499]

[0500] FT-IR(KBr):3177cm -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1563cm -1 :COO - Stretching vibration

[0501] 1 H-NMR(D2O 400MHz): δ1.66-1.89(m,4H,C H2 C(OH)(COO - )),δ3.04(m,2H,N + C H2 CH2OH),δ3.35(m,1H,CH(OH)CH (OH)CH(OH)),δ3.77(m,2H,N + CH2C H2 OH),δ3.79-3.95(m,2H,CH2C H (OH)CH(OH)).

[0502] 13 C-NMR (D2O 100MHz): δ25.5( C H2CH2CHCOO - ),δ25.7( C H2CHCOO - ),δ29.9( C H2CH2CH2CHCOO - ),δ37.3( C H2C(OH)(COO - )),δ40.6( C H2C(OH)(COO - )),δ41.2(N + C H2CH2OH),δ47.1( C HCOO - ),δ57.6(N + CH2 C H2OH),δ66.9(CH2 C H(OH)CH(OH)),δ70.3(CH2 C H(OH)CH(OH)),δ75.1(CH(OH) C H(OH)CH(OH)),δ76.9(CH2 C (OH)(COO - )),δ181.3(CH2C(OH)( C OO - )).

[0503] <Example 42> Synthesis of Compound 42

[0504]

[0505] FT-IR(KBr):3306cm -1 :O-H stretching vibration 2923cm -1 :C-H stretching vibration 1559cm -1 :COO - Stretching vibration

[0506] 1H-NMR(D2O 400MHz): δ1.66-1.89(m,4H,C H2 C(OH)(COO - )),δ3.15(t,4H,N + C H2 CH2OH),δ3.35(m,1H,CH(OH)C H (OH)CH(OH)),δ3.79(t,4H,N + CH2C H2 OH),δ3.79-3.95(m,2H,CH2C H (OH)CH(OH)).

[0507] 13 C-NMR (D2O 100MHz): δ37.3( C H2C(OH)(COO - )),δ40.6( C H2C(OH)(COO - )),δ48.9(N + C H2CH2OH),δ56.6(N + CH2 C H2OH),δ66.9(CH2 C H(OH)CH(OH)),δ70.3(CH2 C H(OH)CH(OH)),δ75.1(CH(OH) C H(OH)CH(OH)),δ76.9(CH2 C (OH)(COO - )),δ181.3(CH2C(OH)( C OO - )).

[0508] <Example 43> Synthesis of Compound 43

[0509]

[0510] FT-IR(KBr):3375cm -1 :O-H stretching vibration 2955cm -1 :C-H stretching vibration 1576cm -1 :COO - Stretching vibration

[0511] 1 H-NMR(D2O 400MHz): δ1.66-1.89(m,4H,C H2 C(OH)(COO- )),δ3.32-3.38(m,1H,HOCH2C H (N + H3)CH2OH),δ3.35(m,1H,CH(OH)C H (OH)CH(OH)),δ3.61-3.77(m,4H,HOC H2 CH(N + H3)C H2 OH),δ3.79-3.95(m,2H,CH2C H (OH)CH(OH)).

[0512] 13 C-NMR (D2O 100MHz): δ37.3( C H2C(OH)(COO - )),δ40.6( C H2C(OH)(COO - )),δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ66.9(CH2 C H(OH)CH(OH)),δ70.3(CH2 C H(OH)CH(OH)),δ75.1(CH(OH) C H(OH)CH(OH)),δ76.9(CH2 C (OH)(COO - )),δ181.3(CH2C(OH)( C OO - )).

[0513] <Example 44> Synthesis of Compound 44

[0514]

[0515] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1543cm -1 :COO - Stretching vibration

[0516] 1 H-NMR (D2O 400MHz): δ0.73-0.77(m,3H,NH3 +C(CH2OH)2CH2C H3 ), δ 1.50-1.56 (m, 2H, NH3 + C(CH2OH)2C H2 CH3), δ 1.66-1.89 (m, 4H, C H2 C(OH)(COO - ), δ 3.35 (m, 1H, CH(OH)C H (OH)CH(OH)), δ 3.49-3.50 (m, 4H, NH3 + C(C H2 OH)2CH2CH3), δ 3.79-3.95 (m, 2H, CH2C H (OH)CH(OH)).

[0517] 13 C-NMR (D2O 100MHz): δ 6.3 (NH3 + C(CH2OH)2CH2 C H3), δ 23.2 (NH3 + C(CH2OH)2 C H2CH3), δ 37.3 ( C H2C(OH)(COO - ), δ 40.6 ( C H2C(OH)(COO - ), δ 60.5 (NH3 + C (CH2OH)2CH2CH3), δ 63.3 (NH3 + C( C H2OH)2CH2CH3), δ 66.9 (CH2 C H(OH)CH(OH)), δ 70.3 (CH2 C H(OH)CH(OH)), δ 75.1 (CH(OH) C H(OH)CH(OH)), δ 76.9 (CH2 C (OH)(COO - ), δ 181.3 (CH2C(OH)( C OO - ).

[0518] <Example 45> Synthesis of Compound 45

[0519]

[0520] FT-IR (KBr): 3375 cm -1 : O-H stretching vibration 2955 cm-1 : C-H stretching vibration at 1576 cm -1 : COO - Stretching vibration

[0521] 1 H-NMR (D2O 400 MHz): δ 0.89 (t, 3H, C H3 CH2), δ 1.27 (m, 22H, CH3(C H2 )9CH2, (C H2 )2CH2CH2COO - , δ 1.53 (m, 2H, C H2 CH2COO - ), δ 1.54 (m, 4H, C H2 CH(OH)C H2 ), δ 2.14 (t, 2H, CH2C H2 COO - ), δ 3.29 (m, 1H, C H (OH)), δ 3.32 - 3.38 (m, 1H, HOCH2C H (N + H3)CH2OH), δ 3.61 - 3.77 (m, 4H, HOC H2 CH(N + H3)C H2 OH).

[0522] 13 C-NMR (D2O 100 MHz): δ 14.0( C H3CH2), δ 22.6 (CH3 C H2), δ 26.4( C H2CH2COO - ), δ 29.3 (CH3CH2CH2( C H2)7, ( C H2)2CH2CH2COO - ), δ 31.7( C H2CH(OH) C H2), δ 31.9 (CH3CH2 C H2), δ 37.8( C H2COO - ), δ 54.1 (HOCH2 C H(N + H3)CH2OH), δ 58.6 (HO C H2CH(N + H3) C H2OH), δ 77.2( CH(OH)),δ181.7( C OO - ).

[0523] <Example 46> Synthesis of Compound 46

[0524]

[0525] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2958cm -1 :C-H stretching vibration 1714cm -1 :COOH stretching vibration 1558cm -1 :COO - Stretching vibration

[0526] 1 H-NMR (D2O 400MHz): δ3.29-3.35(m,1H,HOCH2C H (N + H3)CH2OH), δ3.58-3.74(m,4H,HOC H2 CH(N + H3)C H2 OH).

[0527] 13 C-NMR(D2O 100MHz): δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ179.7(HOO CC OO - ).

[0528] <Example 47> Synthesis of Compound 47

[0529]

[0530] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1715cm -1 :COOH stretching vibration 1578cm -1 :COO - Stretching vibration

[0531] 1 H-NMR(D2O 400MHz): δ2.51(s,4H,HOOCC H2C H2 COO - ),δ3.08(t,2H,N + C H2 CH2OH),δ3.76(t,2H,N + CH2C H2 OH).

[0532] 13 C-NMR (D2O 100MHz): δ31.4 (HOOC C H2 C H2COO - ),δ41.3(N + C H2CH2OH),δ57.6(N + CH2 C H2OH),δ179.7( C OOH, C OO - ).

[0533] <Example 48> Synthesis of Compound 48

[0534]

[0535] FT-IR(KBr):3145cm -1 :O-H stretching vibration 2946cm -1 :C-H stretching vibration 1711cm -1 :COOH stretching vibration 1572cm -1 :COO - Stretching vibration

[0536] 1 H-NMR(D2O 400MHz): δ2.51(s,4H,HOOCC H2 C H2 COO － ),δ3.57(s,6H,NH3 + C(C H2 OH)3).

[0537] 13 C-NMR (D2O 100MHz): δ31.4 (HOOC C H2 C H2COO - ),δ59.2(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3),δ179.7(C OOH, C OO - ).

[0538] <Example 49> Synthesis of Compound 49

[0539]

[0540] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1715cm -1 :COOH stretching vibration 1578cm -1 :COO - Stretching vibration

[0541] 1 H-NMR(D2O 400MHz): δ1.56(t,4H,HOOCCH2C H2 C H2 CH2COO - ),δ2.27(t,4H,HOOCC H2 CH2CH2C H2 COO - ),δ3.08(t,2H,N + C H2 CH2OH),δ3.76(t,2H,N + CH2C H2 OH).

[0542] 13 C-NMR (D2O 100MHz): δ24.8 (HOOCCH2 C H2 C H2CH2COO - ),δ35.5(HOOC C H2CH2CH2 C H2COO - ),δ41.3(N + C H2CH2OH),δ57.6(N + CH2 C H2OH),δ179.7( C OOH, C OO - ).

[0543] <Example 50> Synthesis of Compound 50

[0544]

[0545] FT-IR(KBr):3312m -1 :O-H stretching vibration 2939cm -1 :C-H stretching vibration 1719cm -1 :COOH stretching vibration 1588cm -1 :COO - Stretching vibration

[0546] 1 H-NMR(D2O 400MHz): δ1.56(t,4H,HOOCCH2C H2 C H2 CH2COO - ),δ2.27(t,4H,HOOCC H2 CH2CH2C H2 COO - ),δ3.31(t,6H,N + C H2 CH2OH),δ3.85(t,6H,N + CH2C H2 OH).

[0547] 13 C-NMR (D2O 100MHz): δ24.8 (HOOCCH2 C H2 C H2CH2COO - ),δ35.5(HOOC C H2CH2CH2 C H2COO - ),δ55.4(N + C H2CH2OH),δ55.6(N + CH2 C H2OH),δ179.7( C OOH, C OO - ).

[0548] <Example 51> Synthesis of Compound 51

[0549]

[0550] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2958cm -1 :C-H stretching vibration 1714cm -1 :COOH stretching vibration 1558cm -1 :COO - Stretching vibration

[0551] 1 H-NMR(D2O 400MHz): δ1.56(t,4H,HOOCCH2C H2 C H2 CH2COO - ),δ2.27(t,4H,HOOCC H2 CH2CH2C H2 COO - ),δ3.29-3.35(m,1H,HOCH2C H (N + H3)CH2OH), δ3.58-3.74(m,4H,HOC H2 CH(N + H3)C H2 OH).

[0552] 13 C-NMR (D2O 100MHz): δ24.8 (HOOCCH2 C H2 C H2CH2COO － ),δ35.5(HOOC C H2CH2CH2 C H2COO - ),δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ179.7( C OOH, C OO - ).

[0553] <Example 52> Synthesis of Compound 52

[0554]

[0555] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2958cm -1 :C-H stretching vibration 1714cm -1 :COOH stretching vibration 1558cm -1 :COO - Stretching vibration

[0556] 1 H-NMR(D2O 400MHz): δ1.29(t,8H,HOOCCH2CH2(C H 2) 4CH2CH2COO -),δ1.56(t,4H,HOOCCH2C H2 (C H 2) 4C H2 CH2COO - ),δ2.27(t,4H,HOOCC H2 CH2(C H 2) 4CH2C H2 COO - ),δ3.29-3.35(m,1H,HOCH2C H (N + H3)CH2OH), δ3.58-3.74(m,4H,HOC H2 CH(N + H3)C H2 OH).

[0557] 13 C-NMR(D2O 100MHz): δ24.8(HOOCCH2 C H2(C H 2)4 C H2CH2COO - ),δ29.7(HOOCCH2CH2( C H2)4CH2CH2COO - ),δ35.5(HOOC C H2CH2(C H 2) 4CH2 C H2COO - ),δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ179.7( C OOH, C OO - ).

[0558] <Example 53> Synthesis of Compound 53

[0559]

[0560] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2958cm -1 :C-H stretching vibration 1714cm -1 :COOH stretching vibration 1558cm -1 :COO - Stretching vibration

[0561] 1 H-NMR (D2O 400MHz): δ3.29-3.35(m,1H,HOCH2C H (N + H3)CH2OH), δ3.58-3.74(m,4H,HOC H2 CH(N + H3)C H2 OH),δ7.03(t,4H,HOOC H =C H COO － ).

[0562] 13 C-NMR(D2O 100MHz): δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ137.7(HOOCC H =C H COO － ),δ179.7( C OOH, C OO - ).

[0563] <Example 54> Synthesis of Compound 54

[0564]

[0565] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1715cm -1 :COOH stretching vibration 1578cm -1 :COO － Stretching vibration

[0566] 1 H-NMR(D2O 400MHz): δ2.27(t,4H,HOOCC H2 CH2CH2C H2 COO - ),δ3.08(t,2H,N + C H2 CH2OH),δ3.76(t,2H,N + CH2C H2 OH),δ4.49(s,2H,HOOC H(OH)C H (OH)COO - ).

[0567] 13 C-NMR (D2O 100MHz): δ41.3 (N + C H2CH2OH),δ57.6(N + CH2 C H2OH),δ72.8(HOOC C H(OH) C H(OH)COO - ),δ176.3(HOO C CH(OH)CH(OH) C OO - ).

[0568] <Example 55> Synthesis of Compound 55

[0569]

[0570] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1715cm -1 :COOH stretching vibration 1578cm -1 :COO - Stretching vibration

[0571] 1 H-NMR(D2O 400MHz): δ2.65(m,4H,HOOCC H2 C(OH)(COOH)C H2 COO - ),δ3.08(t,2H,N + C H2 CH2OH),δ3.76(t,2H,N + CH2C H2 OH).

[0572] 13 C-NMR (D2O100MHz):δ41.3(N + C H2CH2OH),δ43.7(HOOC C H2C(OH)(COOH) C H2COO - ),δ57.6(N + CH2 C H2OH),δ73.9(HOOCCH2C (OH)(COOH)CH2COO - ),δ174.8(HOO C CH2C(OH)(COOH)CH2 C OO - ),δ178.7(HOOCCH2C(OH)( C OOH)CH2COO - ).

[0573] <Example 56> Synthesis of Compound 56

[0574]

[0575] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1578cm -1 :COO - Stretching vibration

[0576] 1 H-NMR(D2O 400MHz): δ3.08(t,2H,N + C H2 CH2OH),δ3.76(t,2H,N + CH2C H2 OH),δ7.40-7.50(m,3H,C H C H C H CHCCOO - ),δ7.51-7.80(m,2H,C H CCOOH).

[0577] 13 C-NMR (D2O 100MHz): δ41.3 (N + C H2CH2OH),δ57.6(N + CH2 C H2OH),δ128.3(CH C HCHCCOO - ),δ128.8(CH C HCCOO － ),δ131.2( C COO - ),δ136.3( C HCHCHCCOO - ),δ175.7( C OO - ).

[0578] <Example 57> Synthesis of Compound 57

[0579]

[0580] FT-IR(KBr):3360cm -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1558cm -1 :COO - Stretching vibration

[0581] 1 H-NMR (D2O 400MHz): δ3.31(t,6H,N + C H2 CH2OH),δ3.85(t,6H,N + CH2C H2 OH),δ7.40-7.50(m,3H,C H C H C H CHCCOO － ),δ7.51-7.80(m,2H,C H CCOOH).

[0582] 13 C-NMR (D2O 100MHz): δ25.5( C H2CH2CHCOO - ),δ55.4(N + C H2CH2OH),δ55.6(N + CH2 C H2OH),δ128.3(CH C HCHCCOO - ),δ128.8(CH C HCCOO - ),δ131.2( C COO - ),δ136.3( C HCHCHCCOO - ),δ175.7( C OO - ).

[0583] <Example 58> Synthesis of Compound 58

[0584]

[0585] FT-IR(KBr):3388cm -1:O-H stretching vibration 2958cm -1 :C-H stretching vibration 1558cm -1 :COO - Stretching vibration

[0586] 1 H-NMR (D2O 400MHz): δ3.29-3.35(m,1H,HOCH2C H (N + H3)CH2OH), δ3.58-3.74(m,4H,HOC H 2CH(N + H3)C H 2OH),δ7.40-7.50(m,3H,C H C H C H CHCCOO - ),δ7.51-7.80(m,2H,C H CCOOH).

[0587] 13 C-NMR(D2O 100MHz): δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ128.3(CH C HCHCCOO - ),δ128.8(CH C HCCOO - ),δ131.2( C COO - ),δ136.3( C HCHCHCCOO - ),δ175.7( C OO - ).

[0588] <Example 59> Synthesis of Compound 59

[0589]

[0590] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1543cm -1 :COO - Stretching vibration

[0591] 1 H-NMR (D2O 400MHz): δ0.73-0.77(m,3H,NH3 + C(CH2OH)2CH2C H3 ),δ1.50-1.56(m,2H,NH3 + C(CH2OH)2C H2 CH3),δ3.49-3.50(m,4H,NH3 + C(C H2 OH)2CH2CH3),δ7.40-7.50(m,3H,C H C H C H CHCCOO - ),δ7.51-7.80(m,2H,C H CCOOH).

[0592] 13 C-NMR (D2O 100MHz):δ6.3(NH3 + C(CH2OH)2CH2 C H3),δ23.2(NH3 + C(CH2OH)2 C H2CH3),δ60.5(NH3 + C (CH2OH)2CH2CH3),δ63.3(NH3 + C( C H2OH)2CH2CH3),δ128.3(CH C HCHCCOO - ),δ128.8(CH C HCCOO - ),δ131.2( C COO - ),δ136.3( C HCHCHCCOO - ),δ175.7( C OO - ).

[0593] <Example 60> Synthesis of Compound 60

[0594]

[0595] FT-IR(KBr):3145cm -1 :O-H stretching vibration 2946cm -1 :C-H stretching vibration 1572cm -1 :COO - Stretching vibration

[0596] 1 H-NMR(D2O 400MHz): δ3.57(s,6H,NH3 + C(C H2 OH)3),δ7.40-7.50(m,3H,C H C H C H CHCCOO - ),δ7.51-7.80(m,2H,C H CCOOH).

[0597] 13 C-NMR(D2O 100MHz): δ59.2(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3),δ128.3(CH C HCHCCOO - ),δ128.8(CH C HCCOO - ),δ131.2( C COO - ),δ136.3( C HCHCHCCOO - ),δ175.7( C OO - ).

[0598] <Example 61> Synthesis of Compound 61

[0599]

[0600] FT-IR(KBr):3167cm -1 :O-H stretching vibration 2920cm -1 :C-H stretching vibration 1573cm -1 :COO - Stretching vibration

[0601] 1 H-NMR (D2O 400MHz): δ2.94-3.13(m,2H,HOCH2(CH(OH))3CH(OH)C H2 NH3 + ),δ3.51-3.72(m,5H,HOC H2 (C H (OH))3CH(OH)CH2NH3 +),δ3.89-3.96(m,1H,HOCH2(CH(OH))3C H (OH)CH2NH3 + ),δ7.40-7.50(m,3H,C H C H C H CHCCOO - ),δ7.51-7.80(m,2H,C H CCOOH).

[0602] 13 C-NMR(D2O 100MHz): δ41.7(HOCH2(CH(OH))3CH(OH) C H2NH3 + ),δ62.6(HO C H2(CH(OH))3CH(OH)CH2NH3 + ),δ68.9-70.9(HOCH2( C H(OH))3 C H(OH)CH2NH3 + ),δ128.3(CH C HCHCCOO - ),δ128.8(CH C HCCOO - ),δ131.2( C COO - ),δ136.3( C HCHCHCCOO - ),δ175.7( C OO - ).

[0603] <Example 62> Synthesis of Compound 62

[0604]

[0605] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1715cm -1 :COOH stretching vibration 1578cm -1 :COO - Stretching vibration

[0606] 1 H-NMR(D2O 400MHz): δ3.08(t,2H,N + C H2 CH2OH),δ3.76(t,2H,N+ CH2C H2 OH),δ8.34(m,4H,C H CCOO - ).

[0607] 13 C-NMR (D2O 100MHz): δ41.3 (N + C H2CH2OH),δ57.6(N + CH2 C H2OH),δ128.8(CH C HCCOO - ),δ131.2( C COO - ),δ175.7( C OO - ).

[0608] <Example 63> Synthesis of Compound 63

[0609]

[0610] FT-IR(KBr):3306cm -1 :O-H stretching vibration 2923cm -1 :C-H stretching vibration 1715cm -1 :COOH stretching vibration 1559cm -1 :COO - Stretching vibration

[0611] 1 H-NMR (D2O 400MHz): δ3.15(t,4H,N + C H2 CH2OH),δ3.79(t,4H,N + CH2C H2 OH),δ8.34(m,4H,C H CCOO - ).

[0612] 13 C-NMR (D2O 100MHz): δ48.9 (N + C H2CH2OH),δ56.6(N + CH2 C H2OH),δ128.8(CH C HCCOO - ),δ131.2( C COO - ),δ175.7(C OO - ).

[0613] <Example 64> Synthesis of Compound 64

[0614]

[0615] FT-IR(KBr):3360cm -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1715cm -1 :COOH stretching vibration 1558cm -1 :COO - Stretching vibration

[0616] 1 H-NMR (D2O 400MHz): δ3.31(t,6H,N + C H2 CH2OH),δ3.85(t,6H,N + CH2C H2 OH),δ8.34(m,4H,C H CCOO - ).

[0617] 13 C-NMR (D2O 100MHz):δ55.4(N + C H2CH2OH),δ55.6(N + CH2 C H2OH),δ128.8(CH C HCCOO - ),δ131.2( C COO - ),δ175.7( C OO - ).

[0618] <Example 65> Synthesis of Compound 65

[0619]

[0620] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2958cm -1 :C-H stretching vibration 1714cm -1 :COOH stretching vibration 1558cm -1 :COO - Stretching vibration

[0621] 1H-NMR (D2O 400MHz): δ3.29-3.35(m,1H,HOCH2C H (N + H3)CH2OH), δ3.58-3.74(m,4H,HOC H2 CH(N + H3)C H2 OH),δ8.34(m,4H,C H CCOO - ).

[0622] 13 C-NMR(D2O 100MHz): δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ128.8(CH C HCCOO - ),δ131.2( C COO - ),δ175.7( C OO - ).

[0623] <Example 66> Synthesis of Compound 66

[0624]

[0625] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1578cm -1 :COO - Stretching vibration

[0626] 1 H-NMR(D2O 400MHz): δ3.08(t,2H,N + C H2 CH2OH),δ3.76(t,2H,N + CH2C H2 OH),δ6.85(m,2H,C(OH)C H CH,C(COO - )CHC H CH),δ7.35(m,1H,C H CHC(OH)),δ7.71(m,1H,C(COOH)C H CH).

[0627] 13 C-NMR (D2O 100MHz): δ41.3 (N + C H2CH2OH),δ57.6(N + CH2 C H2OH),δ116.3(C(OH) C HCH),δ118.0(CH C (COO - )C(OH)),δ119.4(C(COO - )CH C HCH),δ130.5(C(COO - ) C HCH),δ134.0( C HCHC(OH)),δ159.6(C C (OH)C),δ175.5(C C OO - ).

[0628] <Example 67> Synthesis of Compound 67

[0629]

[0630] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1543cm -1 :COO - Stretching vibration

[0631] 1 H-NMR (D2O 400MHz): δ0.73-0.77(m,3H,NH3 + C(CH2OH)2CH2C H3 ),δ1.50-1.56(m,2H,NH3 + C(CH2OH)2C H2 CH3),δ3.49-3.50(m,4H,NH3 + C(C H2 OH)2CH2CH3),δ6.85(m,2H,C(OH)C H CH,C(COO - )CHC H CH),δ7.35(m,1H,C H CHC(OH)),δ7.71(m,1H,C(COOH)C H CH).

[0632] 13 C-NMR (D2O 100MHz):δ6.3(NH3 + C(CH2OH)2CH2 C H3),δ23.2(NH3 + C(CH2OH)2 C H2CH3),δ60.5(NH3 + C (CH2OH)2CH2CH3),δ63.3(NH3 + C( C H2OH)2CH2CH3),δ116.3(C(OH) C HCH),δ118.0(CH C (COO - )C(OH)),δ119.4(C(COO - )CH C HCH),δ130.5(C(COO - ) C HCH),δ134.0( C HCHC(OH)),δ159.6(C C (OH)C),δ175.5(C C OO - ).

[0633] <Example 68> Synthesis of Compound 68

[0634]

[0635] FT-IR(KBr):3145cm -1 :O-H stretching vibration 2946cm -1 :C-H stretching vibration 1572cm -1 :COO - Stretching vibration

[0636] 1 H-NMR(D2O 400MHz): δ3.57(s,6H,NH3 + C(C H2 OH)3),δ6.85(m,2H,C(OH)C H CH,C(COO - )CHC H CH),δ7.35(m,1H,C H CHC(OH)),δ7.71(m,1H,C(COOH)C H CH).

[0637] 13 C-NMR(D2O 100MHz): δ59.2(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3),δ116.3(C(OH) C HCH),δ118.0(CH C (COO - )C(OH)),δ119.4(C(COO - )CH C HCH),δ130.5(C(COO - ) C HCH),δ134.0( C HCHC(OH)),δ159.6(C C (OH)C),δ175.5(C C OO - ).

[0638] <Example 69> Synthesis of Compound 69

[0639]

[0640] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1578cm -1 :COO - Stretching vibration

[0641] 1 H-NMR(D2O 400MHz): δ3.08(t,2H,N + C H2 CH2OH),δ3.76(t,2H,N + CH2C H2 OH),δ6.83(d,2H,C(COO - )C H CH),δ7.73(d,2H,C(OH)C H CH).

[0642] 13 C-NMR (D2O 100MHz): δ41.3 (N + C H2CH2OH),δ57.6(N + CH2 C H2OH),δ114.9(C(OH) C HCH),δ128.2(C (COO - )),δ131.2(C(COO - ) C HCH),δ158.4( C (OH)),δ175.3(C( C OO - )).

[0643] <Example 70> Synthesis of Compound 70

[0644]

[0645] FT-IR(KBr):3360cm -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1558cm -1 :COO - Stretching vibration

[0646] 1 H-NMR (D2O 400MHz): δ3.31(t,6H,N + C H2 CH2OH),δ3.85(t,6H,N + CH2C H2 OH),δ6.83(d,2H,C(COO - )C H CH),δ7.73(d,2H,C(OH)C H CH).

[0647] 13 C-NMR (D2O 100MHz):δ55.4(N + C H2CH2OH),δ55.6(N + CH2 C H2OH),δ114.9(C(OH) C HCH),δ128.2( C (COO - )),δ131.2(C(COO - ) C HCH),δ158.4( C (OH)),δ175.3(C( C OO - )).

[0648] <Example 71> Synthesis of Compound 71

[0649]

[0650] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2958cm -1 :C-H stretching vibration 1558cm -1 :COO - Stretching vibration

[0651] 1 H-NMR (D2O 400MHz): δ3.29-3.35(m,1H,HOCH2C H (N + H3)CH2OH), δ3.58-3.74(m,4H,HOC H2 CH(N + H3)C H2 OH),δ6.83(d,2H,C(COO － )C H CH),δ7.73(d,2H,C(OH)C H CH).

[0652] 13 C-NMR(D2O 100MHz): δ54.1(HOCH2 C H(N + H3)CH2OH),δ58.6(HO C H2CH(N + H3) C H2OH),δ114.9(C(OH) C HCH),δ128.2( C (COO - )),δ131.2(C(COO - ) C HCH),δ158.4( C (OH)),δ175.3(C( C OO - )).

[0653] <Example 72> Synthesis of Compound 72

[0654]

[0655] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1578cm -1 :COO - Stretching vibration

[0656] 1H-NMR(D2O 400MHz): δ3.08(t,2H,N + C H2 CH2OH),δ3.76(t,2H,N + CH2C H2 OH),δ4.94(s,1H,C H (OH)(COO - )),δ7.34(m,5H,(C H )5).

[0657] 13 C-NMR (D2O 100MHz): δ41.3 (N + C H2CH2OH),δ57.6(N + CH2 C H2OH),δ75.0( C H(OH)(COO - )),δ127.1((CH)2 C H(CH)2),δ128.2( C HCHCCH(OH)(COO - )),δ128.8( C HCCH(OH)(COO - )),δ140.6( C CH(OH)(COO - )),δ179.4( C OO - ).

[0658] <Example 73> Synthesis of Compound 73

[0659]

[0660] FT-IR(KBr):3167cm -1 :O-H stretching vibration 2920cm -1 :C-H stretching vibration 1573cm -1 :COO - Stretching vibration

[0661] 1 H-NMR(D2O 400MHz): δ2.53(d,3H,C H3 ),δ2.94-3.13(m,2H,HOCH2(CH(OH))3CH(OH)C H2 NH3 + ),δ3.51-3.72(m,5H,HOC H2 (C H(OH))3CH(OH)CH2NH3 + ),δ3.89-3.96(m,1H,HOCH2(CH(OH))3C H (OH)CH2NH3 + ).

[0662] 13 C-NMR (D2O 100MHz): δ25.5( C H3),δ41.7(HOCH2(CH(OH))3CH(OH) C H2NH3 + ),δ62.6(HO C H2(CH(OH))3CH(OH)CH2NH3 + ),δ68.9-70.9(HOCH2( C H(OH))3 C H(OH)CH2NH3 + ),δ161.4( C OO - ),δ193.7(CH3 C =O).

[0663] <Example 74> Synthesis of Compound 74

[0664]

[0665] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1543cm -1 :COO - Stretching vibration

[0666] 1 H-NMR (D2O 400MHz): δ0.73-0.77(m,3H,NH3 + C(CH2OH)2CH2C H3 ),δ1.50-1.56(m,2H,NH3 + C(CH2OH)2C H2 CH3),δ3.27(s,3H,C H3 OCH2COO - ),δ3.49-3.50(m,4H,NH3 + C(C H2 OH)2CH2CH3),δ3.77(s,2H,CH3OC H2 COO - ).

[0667] 13 C-NMR (D2O 100MHz):δ6.3(NH3 + C(CH2OH)2CH2 C H3),δ23.2(NH3 + C(CH2OH)2 C H2CH3),δ57.6( C H3OCH2COO - ),δ60.5(NH3 + C (CH2OH)2CH2CH3),δ63.3(NH3 + C( C H2OH)2CH2CH3),δ71.2(CH3O C H2COO - ),δ178.0(CH3OCH2 C OO - ).

[0668] <Example 75> Synthesis of Compound 75

[0669]

[0670] FT-IR(KBr):3313m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1679cm -1 :COO - Stretching vibration

[0671] 1 H-NMR(D2O 400MHz): δ3.08(t,2H,N + C H2 CH2OH),δ3.76(t,2H,N + CH2C H2 OH).

[0672] 13 C-NMR (D2O 100MHz): δ41.3 (N + C H2CH2OH),δ57.6(N + CH2 C H2OH),δ114.6( C F3COO - ),δ165.1(CF3 C OO - ).

[0673] <Example 76> Synthesis of Compound 76

[0674]

[0675] FT-IR(KBr):3332m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1665cm -1 :COO - Stretching vibration

[0676] 1 H-NMR (D2O 400MHz): δ0.73-0.77(m,3H,NH3 + C(CH2OH)2CH2C H3 ),δ1.50-1.56(m,2H,NH3 + C(CH2OH)2C H2 CH3),δ3.49-3.50(m,4H,NH3 + C(C H2 OH)2CH2CH3).

[0677] 13 C-NMR (D2O 100MHz):δ6.3(NH3 + C(CH2OH)2CH2 C H3),δ23.2(NH3 + C(CH2OH)2 C H2CH3),δ60.5(NH3 + C (CH2OH)2CH2CH3),δ63.3(NH3 + C( C H2OH)2CH2CH3),δ114.6( C F3COO - ),δ165.1(CF3 C OO - ).

[0678] <Example 77> Synthesis of Compound 77

[0679]

[0680] FT-IR(KBr):3332m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1665cm -1 :COO - Stretching vibration

[0681] 1H-NMR(D2O 400MHz): δ3.57(s,6H,NH3 + C(C H2 OH)3).

[0682] 13 C-NMR(D2O 100MHz): δ59.2(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3),δ114.6( C F3COO - ),δ165.1(CF3 C OO - ).

[0683] <Example 78> Synthesis of Compound 78

[0684]

[0685] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2959cm -1 : C-H stretching vibration

[0686] 1 H-NMR(D2O 400MHz): δ3.65(s,6H,NH3 + C(C H2 OH)3).

[0687] 13 C-NMR(D2O 100MHz): δ59.4(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3).

[0688] <Example 79> Synthesis of Compound 79

[0689]

[0690] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2959cm -1 : C-H stretching vibration

[0691] 1 H-NMR(D2O 400MHz): δ3.65(s,6H,NH3 + C(C H2 OH)3).

[0692] 13 C-NMR(D2O 100MHz): δ59.4(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3).

[0693] <Example 80> Synthesis of Compound 80

[0694]

[0695] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2959cm -1 : C-H stretching vibration

[0696] 1 H-NMR (D2O 400MHz): δ3.35-3.41(m,1H,HOCH2C H (N + H3)CH2OH),δ3.64-3.80(m,4H,HOC H2 CH(N + H3)C H2 OH).

[0697] 13 C-NMR (D2O 100MHz): δ54.2 (HOCH2 C H(N + H3)CH2OH),δ58.7(HO C H2CH(N + H3) C H2OH).

[0698] <Example 81> Synthesis of Compound 81

[0699]

[0700] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2959cm -1 : C-H stretching vibration

[0701] 1 H-NMR(D2O 400MHz): δ3.65(s,6H,NH3 + C(C H2 OH)3).

[0702] 13C-NMR(D2O 100MHz): δ59.4(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3).

[0703] <Example 82> Synthesis of Compound 82

[0704]

[0705] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2959cm -1 : C-H stretching vibration

[0706] 1 H-NMR (D2O 400MHz): δ2.86-3.05(m,2H,HOCH2(CH(OH))3CH(OH)C H2 NH3 + ),δ3.41-3.68(m,5H,HOC H2 (C H (OH))3CH(OH)CH2NH3 + ),δ3.83-3.88(m,1H,HOCH2(CH(OH))3C H (OH)CH2NH3 + ).

[0707] 13 C-NMR(D2O 100MHz): δ41.7(HOCH2(CH(OH))3CH(OH) C H2NH3 + ),δ62.6(HO C H2(CH(OH))3CH(OH)CH2NH3 + ),δ69.2-70.8(HOCH2( C H(OH))3 C H(OH)CH2NH3 + ).

[0708] <Example 83> Synthesis of Compound 83

[0709]

[0710] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2959cm -1 : C-H stretching vibration

[0711] 1 H-NMR(D2O 400MHz): δ3.65(s,6H,NH3 + C(C H2 OH)3).

[0712] 13 C-NMR(D2O 100MHz): δ59.4(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3).

[0713] <Example 84> Synthesis of Compound 84

[0714]

[0715] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2959cm -1 : C-H stretching vibration

[0716] 1 H-NMR (D2O 400MHz): δ2.86-3.05(m,2H,HOCH2(CH(OH))3CH(OH)C H2 NH3 + ),δ3.41-3.68(m,5H,HOC H2 (C H (OH))3CH(OH)CH2NH3 + ),δ3.83-3.88(m,1H,HOCH2(CH(OH))3C H (OH)CH2NH3 + ).

[0717] 13 C-NMR(D2O 100MHz): δ41.7(HOCH2(CH(OH))3CH(OH) C H2NH3 + ),δ62.6(HO C H2(CH(OH))3CH(OH)CH2NH3 + ),δ69.2-70.8(HOCH2( C H(OH))3 C H(OH)CH2NH3 + ).

[0718] <Example 85> Synthesis of Compound 85

[0719]

[0720] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2959cm -1 : C-H stretching vibration

[0721] 1 H-NMR (D2O 400MHz): δ3.35-3.41(m,1H,HOCH2C H (N + H3)CH2OH),δ3.64-3.80(m,4H,HOC H2 CH(N + H3)C H2 OH).

[0722] 13 C-NMR (D2O 100MHz): δ54.2 (HOCH2 C H(N + H3)CH2OH),δ58.7(HO C H2CH(N + H3) C H2OH).

[0723] <Example 86> Synthesis of Compound 85

[0724]

[0725] FT-IR(KBr):3388cm -1 :O-H stretching vibration 2959cm -1 : C-H stretching vibration

[0726] 1 H-NMR(D2O 400MHz): δ3.65(s,6H,NH3 + C(C H2 OH)3).

[0727] 13 C-NMR(D2O 100MHz): δ59.4(NH3 + C (CH2OH)3),δ61.4(NH3 + C( C H2OH)3).

[0728] <Example 87> Synthesis of Compound 87

[0729]

[0730] FT-IR(KBr):3388cm-1 :O-H stretching vibration 2959cm -1 : C-H stretching vibration

[0731] 1 H-NMR (D2O 400MHz): δ2.86-3.05(m,2H,HOCH2(CH(OH))3CH(OH)C H2 NH3 + ),δ3.41-3.68(m,5H,HOC H2 (C H (OH))3CH(OH)CH2NH3 + ),δ3.83-3.88(m,1H,HOCH2(CH(OH))3C H (OH)CH2NH3 + ).

[0732] 13 C-NMR(D2O 100MHz): δ41.7(HOCH2(CH(OH))3CH(OH) C H2NH3 + ),δ62.6(HO C H2(CH(OH))3CH(OH)CH2NH3 + ),δ69.2-70.8(HOCH2( C H(OH))3 C H(OH)CH2NH3 + ).

[0733] <Example 88> Synthesis of Compound 88

[0734]

[0735] After 2-amino-2-ethyl-1,3-propanediol (25.00 g, 0.210 mol) and 3-chloro-1,2-propanediol (116.07 g, 1.050 mol) were reacted in 1000 mL of 1-propanol under reflux for 48 hours, 1-propanol was removed by distillation under reduced pressure, THF was added to the obtained liquid, and heated and washed to obtain a white powder. Sodium hydroxide was added to the obtained white powder, stirred at room temperature for 2 hours, ethanol was added, and after the precipitated crystals were filtered and separated, the filtrate was removed by distillation under reduced pressure, and the obtained liquid was refined by column chromatography to obtain the amine compound 1 described in Example 88 of Table 10.

[0736] Amine compound 1 (2.50 g, 0.013 mol) and succinic acid (1.53 g, 0.013 mmol) were reacted in 50 mL of water at room temperature for 3 hours, and then water was distilled off under reduced pressure to obtain a white solid. The obtained solid was washed to obtain compound 88 (ammonium succinate) as a white solid.

[0737] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1715cm -1 :COOH stretching vibration 1578cm -1 :COO - Stretching vibration

[0738] 1 H-NMR (D2O 400MHz): δ0.86-0.92(m,3H,NH2 + C(CH2OH)2CH2C H3 ),δ1.44(m,2H,NH2 + C(CH2OH)2C H2 CH3),δ2.51(s,4H,HOOCC H2 C H2 COO － ),δ2.78-2.96(m,2H,NH2 + C H 2CH(OH)),δ3.61-3.78(m,6H,NH2 + C(C H2 OH)2CH2CH 3, NH2 + CH2CH(OH)C H2 OH),δ3.83-3.88(m,1H,NH2 + CH2C H (OH)

[0739] 13 C-NMR (D2O 100MHz): δ9.6 (NH2 + C(CH2OH)2CH2 C H3),δ22.7(CH3 C H2CH2),δ24.6(NH2 + C(CH2OH)2 C H2CH3),δ31.4(HOOC C H2 C H2COO - ),δ43.6(NH2 +C (CH2OH)2CH2CH3),δ45.8(NH2 + C H2CH(OH)),δ60.2(NH2 + C( C H2OH)2CH2CH3),δ62.8(NH2 + CH2CH(OH) C H2OH),δ71.1(NH2 + CH2 C H(OH) C H2OH),δ179.7( C OOH, C OO - ).

[0740] <Example 89> Synthesis of Compound 89

[0741]

[0742] After D-glucosamine (25.00 g, 0.138 mol) and 3-chloro-1,2-propanediol (76.26 g, 0.690 mol) were reacted in 1000 mL of 1-propanol under reflux conditions for 48 hours, 1-propanol was distilled off under reduced pressure, THF was added to the obtained liquid, and heated and washed to obtain a white powder. Sodium hydroxide was added to the obtained white powder, stirred at room temperature for 2 hours, and then ethanol was added. After the precipitated crystals were filtered and separated, the filtrate was distilled off under reduced pressure, and the obtained liquid was purified by column chromatography to obtain the amine compound 2 described in Example 89 of Table 10.

[0743] Amine compound 2 (2.50 g, 0.010 mol) and succinic acid (1.16 g, 0.010 mol) were reacted in 50 mL of water at room temperature for 3 hours, and then water was distilled off under reduced pressure to obtain a yellow solid. The obtained solid was washed to obtain compound 89 (ammonium succinate) as a yellow solid.

[0744] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1715cm -1 :COOH stretching vibration 1578cm -1 :COO - Stretching vibration

[0745] 1 H-NMR(D2O 400MHz): δ2.51(s,4H,HOOCC H2C H2 COO - ), δ 3.00-3.23 (m, 4H, HOCH2(CH(OH))3CH(OH)C H2 NH2 + , NH2 + C H 2CH(OH)), δ 3.51-3.74 (m, 7H, HOC H2 (C H (OH))3CH(OH)CH2NH2 + , NH2 + CH2CH(OH)C H2 OH), δ 3.94-3.98 (m, 1H, NH2 + CH2C H (OH), δ 4.03-4.09 (m, 1H, HOCH2(CH(OH))3C H (OH)CH2NH2 + ).

[0746] 13 C-NMR (D2O 100MHz): δ 31.4 (HOOC C H2 C H2COO - ), δ 43.2 (HOCH2(CH(OH))3CH(OH) C H2NH2 + ), δ 45.8 (NH2 + C H2CH(OH)), δ 62.8 (NH2 + CH2CH(OH) C H2OH), δ 64.7 (HO C H2(CH(OH))3CH(OH)CH2NH2 + ), δ 70.7-72.9 (HOCH2( C H(OH))3 C H(OH)CH2NH3 + , NH2 + CH2 C H(OH) C H2OH), δ 179.7 ( C OOH, C OO - ).

[0747] <Example 90> Synthesis of Compound 90

[0748]

[0749] After the amine compound 1 (10.00 g, 0.052 mol) and 3-chloro-1,2-propanediol (28.74 g, 0.260 mol) were reacted in 500 mL of 1-propanol under reflux conditions for 48 hours, the 1-propanol was removed by distillation under reduced pressure, and THF was added to the obtained liquid, and heated and washed to obtain a white powder. Sodium hydroxide was added to the obtained white powder, and stirred at room temperature for 2 hours, and then ethanol was added. After the precipitated crystals were filtered and separated, the filtrate was removed by distillation under reduced pressure, and the obtained liquid was refined by column chromatography to obtain the amine compound 3 described in Example 90 of Table 10.

[0750] Amine compound 3 (2.50 g, 0.013 mol) and oleic acid (1.53 g, 0.013 mmol) were reacted in 50 mL of water at room temperature for 3 hours, and then water was distilled off under reduced pressure to obtain a white solid. The obtained solid was washed to obtain compound 90 (oleic acid ammonium salt) as a white solid.

[0751] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1578cm -1 :COO - Stretching vibration

[0752] 1 H-NMR(D2O 400MHz): δ2.51(s,4H,HOOCC H2 C H2 COO － ),δ3.00-3.23(m,4H,HOCH2(CH(OH))3CH(OH)C H2 NH2 + ,NH2 + C H 2CH(OH)),δ3.51-3.74(m,7H,HOC H2 (C H (OH))3CH(OH)CH2NH2 + ,NH2 + CH2CH(OH)C H2 OH),δ3.94-3.98(m,1H,NH2 + CH2C H (OH),δ4.03-4.09(m,1H,HOCH2(CH(OH))3C H (OH)CH2NH2 + ).δ0.89(t,3H,C H3CH2),δ1.27(m,20H,CH3(C H2 )6CH2,(C H2 )4CH2CH2COO － ),δ1.53(m,2H,C H2 CH2COO － ),δ2.00(m,4H,C H2 CH=CHC H2 ),δ2.14(t,2H,CH2C H2 COO － ),δ5.32(m,2H,C H =C H ).

[0753] 13 C-NMR(D2O 100MHz):δ31.4(HOOC C H2 C H2COO － ),δ43.2(HOCH2(CH(OH))3CH(OH) C H2NH2 + ),δ45.8(NH2 + C H2CH(OH)),δ62.8(NH2 + CH2CH(OH) C H2OH),δ64.7(HO C H2(CH(OH))3CH(OH)CH2NH2 + ),δ70.7-72.9(HOCH2( C H(OH))3 C H(OH)CH2NH3 + ,NH2 + CH2 C H(OH) C H2OH).δ14.0( C H3CH2),δ22.6(CH3 C H2),δ26.4( C H2CH2COO - ),δ27.2( C H2CH=CH C H2),δ29.3(CH3CH2CH2( C H2)4,( C H2)4CH2CH2COO - ),δ31.9(CH3CH2 C H2),δ37.8( C H2CH2COO -),δ129.7( C H= C H),δ181.7( C OO - ).

[0754] <Example 91> Synthesis of Compound 91

[0755]

[0756] After the amine compound 2 (10.00 g, 0.039 mol) and 3-chloro-1,2-propylene glycol (21.56 g, 0.195 mol) were reacted in 500 mL of 1-propanol under reflux conditions for 48 hours, the 1-propanol was removed by distillation under reduced pressure, and THF was added to the obtained liquid, and heated and washed to obtain a white powder. Sodium hydroxide was added to the obtained white powder, and stirred at room temperature for 2 hours, and then ethanol was added. After the precipitated crystals were filtered and separated, the filtrate was removed by distillation under reduced pressure, and the obtained liquid was refined by column chromatography to obtain the amine compound 4 described in Example 91 of Table 10.

[0757] Amine compound 4 (2.50 g, 0.009 mol) and oleic acid (2.64 g, 0.009 mmol) were reacted in 50 mL of water at room temperature for 3 hours, and then water was distilled off under reduced pressure to obtain a yellow solid. The obtained solid was washed to obtain compound 91 (oleic acid ammonium salt) as a yellow solid.

[0758] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1578cm -1 :COO - Stretching vibration

[0759] 1 H-NMR (D2O 400MHz): δ3.00-3.23(m,6H,HOCH2(CH(OH))3CH(OH)C H2 NH + ,NH + C H 2CH(OH)),δ3.51-3.74(m,9H,HOC H2 (C H (OH))3CH(OH)CH2NH + ,NH + CH2CH(OH)C H2 OH),δ3.94-3.98(m,2H,NH + CH2C H(OH),δ4.03-4.09(m,2H,HOCH2(CH(OH))3C H (OH)CH2NH + ).δ0.89(t,3H,C H3 CH2),δ1.27(m,20H,CH3(C H2 )6CH2,(C H2 )4CH2CH2COO － ),δ1.53(m,2H,C H2 CH2COO － ),δ2.00(m,4H,C H2 CH=CHC H2 ),δ2.14(t,2H,CH2C H2 COO － ),δ5.32(m,2H,C H =C H ).

[0760] 13 C-NMR(D2O 100MHz):δ43.2(HOCH2(CH(OH))3CH(OH) C H2NH + ),δ45.8(NH + C H2CH(OH)),δ62.8(NH + CH2CH(OH) C H2OH),δ64.7(HO C H2(CH(OH))3CH(OH)CH2NH + ),δ70.7-72.9(HOCH2( C H(OH))3 C H(OH)CH2NH + ,NH + CH2 C H(OH) C H2OH).δ14.0( C H3CH2),δ22.6(CH3 C H2),δ26.4(CH2CH2COO － ),δ27.2( C H2CH=CH C H2),δ29.3(CH3CH2CH2( C H2)4,( C H2)4CH2CH2COO － ),δ31.9(CH3CH2 C H2),δ37.8(C H2CH2COO － ),δ129.7( C H= C H),δ181.7( C OO － ).

[0761] <Example 92> Synthesis of Compound 92

[0762]

[0763] The synthesis was carried out by the same synthesis method as in Example 90 and at the blending molar ratio described in Table 10. The physical property values ​​are shown below.

[0764] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1715cm -1 :COOH stretching vibration 1578cm -1 :COO - Stretching vibration

[0765] 1 H-NMR(D2O 400MHz): δ2.51(s,4H,HOOCC H2 C H2 COO - ),δ3.00-3.23(m,4H,HOCH2(CH(OH))3CH(OH)C H2 NH2 + ,NH2 + C H 2CH(OH)),δ3.51-3.74(m,7H,HOC H2 (C H (OH))3CH(OH)CH2NH2 + ,NH2 + CH2CH(OH)C H2 OH),δ3.94-3.98(m,1H,NH2 + CH2C H (OH),δ4.03-4.09(m,1H,HOCH2(CH(OH))3C H (OH)CH2NH2 + ).δ2.51(s,4H,HOOCC H2 C H2 COO - ).

[0766] 13C-NMR (D2O 100MHz): δ31.4 (HOOC C H2 C H2COO - ),δ43.2(HOCH2(CH(OH))3CH(OH) C H2NH2 + ),δ45.8(NH2 + C H2CH(OH)),δ62.8(NH2 + CH2CH(OH) C H2OH),δ64.7(HO C H2(CH(OH))3CH(OH)CH2NH2 + ),δ70.7-72.9(HOCH2( C H(OH))3 C H(OH)CH2NH3 + ,NH2 + CH2 C H(OH) C H2OH).δ31.4(HOOC C H2 C H2COO - ),δ179.7( C OOH, C OO - ).

[0767] <Example 93> Synthesis of Compound 93

[0768]

[0769] The synthesis was carried out by the same synthesis method as in Example 91 and at the blending molar ratio described in Table 10. The physical property values ​​are shown below.

[0770] FT-IR(KBr):3162m -1 :O-H stretching vibration 2950cm -1 :C-H stretching vibration 1715cm -1 :COOH stretching vibration 1578cm -1 :COO - Stretching vibration

[0771] 1 H-NMR (D2O 400MHz): δ3.00-3.23(m,6H,HOCH2(CH(OH))3CH(OH)C H2 NH + ,NH + C H2CH(OH)), δ 3.51 - 3.74 (m, 9H, HOC H2 (C H (OH))3CH(OH)CH2NH + , NH + CH2CH(OH)C H2 OH), δ 3.94 - 3.98 (m, 2H, NH + CH2C H (OH), δ 4.03 - 4.09 (m, 2H, HOCH2(CH(OH))3C H (OH)CH2NH + ). δ 2.51 (s, 4H, HOOCC H2 C H2 COO - ).

[0772] 13 C - NMR (D2O 100 MHz): δ 43.2 (HOCH2(CH(OH))3CH(OH) C H2NH + ), δ 45.8 (NH + C H2CH(OH)), δ 62.8 (NH + CH2CH(OH) C H2OH), δ 64.7 (HO C H2(CH(OH))3CH(OH)CH2NH + ), δ 70.7 - 72.9 (HOCH2( C H(OH))3 C H(OH)CH2NH + , NH + CH2 C H(OH) C H2OH). δ 31.4 (HOOC C H2 C H2COO － ), δ 179.7 ( C OOH, C OO - ).

[0773] <Example 94> Synthesis of Compound 94

[0774]

[0775] After the amine compound 3 (10.00 g, 0.037 mol) and 3-chloro-1,2-propanediol (40.90 g, 0.370 mol) were reacted in 200 mL of acetonitrile under pressure at 130° C. for 4 hours, the acetonitrile was removed by distillation under reduced pressure, and THF was added to the obtained solid and heated and washed to obtain a light yellow powder. The light yellow powder after adding water was separated by anion exchange resin to obtain the amine compound 5 described in Example 94 of Table 10.

[0776] Amine compound 5 (5.00 g, 0.014 mol) and isostearic acid (3.98 g, 0.0140 mol) were reacted in 50 mL of water at room temperature for 3 hours, and then water was distilled off under reduced pressure to obtain a yellow solid. The obtained solid was washed to obtain compound 94 (isostearate quaternary ammonium salt) as a yellow solid.

[0777] FT-IR(KBr):3350cm -1 :O-H stretching vibration 2940cm -1 :C-H stretching vibration 1560cm -1 :COO - Stretching vibration

[0778] 1 H-NMR (D2O 400MHz): δ0.86-0.92(m,6H,N + C(CH2OH)2CH2C H3 ,C H3 CH2CH2),δ1.44(m,2H,N + C(CH2OH)2C H2 CH3),δ2.78-2.96(m,6H,N + C H 2CH(OH)),δ3.61-3.78(m,10H,N + C(C H2 OH)2CH2CH 3, N + CH2CH(OH)C H2 OH),δ3.83-3.88(m,3H,N + CH2C H (OH)).δ0.83-0.90(m,6H,C H3 (CH2)8CH((CH2)6C H3 )COO - ),δ1.08-1.58(m,28H,CH3(C H2 )8CH((C H2 )6CH3)COO -), δ 2.24 - 2.28 (m, 1H, CH3(CH2)8C H ((CH2)6CH3)COO - ).

[0779] 13 C - NMR (D2O 100 MHz): δ 9.6 (N + C(CH2OH)2CH2 C H3), δ 24.6 (N + C(CH2OH)2 C H2CH3), δ 43.6 (N + C (CH2OH)2CH2CH3), δ 45.8 (N + C H2CH(OH)), δ 60.2 (N + C( C H2OH)2CH2CH3), δ 62.8 (N + CH2CH(OH) C H2OH), δ 71.1 (N + CH2 C H(OH) C H2OH). δ 14.1 ( C H3CH2), δ 22.7 (CH3 C H--2CH2), δ 27.1 ( C H2CH2CHCOO - ), δ 30.0 (CH3CH2CH2( C H2)4CH2CH2CH(CH2CH2( C H2)2CH2CH2CH3)COO - , CH2 C H2CHCOO - ), δ 31.9 (CH3CH2 C H2), δ 37.2 ( C HCOO - ), δ 182.1 (CH C OO - ).

[0780] <Example 95> Synthesis of Compound 95

[0781]

[0782] After the amine compound 4 (10.00 g, 0.030 mol) and 3-chloro-1,2-propanediol (33.16 g, 0.300 mol) were reacted in 200 mL of acetonitrile under pressure at 130° C. for 4 hours, the acetonitrile was removed by distillation under reduced pressure, and THF was added to the obtained solid, which was heated and washed to obtain a light yellow powder. The light yellow powder after adding water was separated by anion exchange resin to obtain the amine compound 6 described in Example 95 of Table 10.

[0783] Amine compound 6 (5.00 g, 0.012 mol) and succinic acid (1.42 g, 0.012 mol) were reacted in 50 mL of water at room temperature for 3 hours, and then water was distilled off under reduced pressure to obtain a yellow solid. The obtained solid was washed to obtain compound 95 (quaternary ammonium succinate) as a yellow solid.

[0784] FT-IR(KBr):3344cm -1 :O-H stretching vibration 2920cm -1 :C-H stretching vibration 1715cm -1 :COOH stretching vibration 1554cm -1 :COO - Stretching vibration

[0785] 1 H-NMR (D2O 400MHz): δ3.00-3.23(m,8H,HOCH2(CH(OH))3CH(OH)C H2 N + ,N + C H 2CH(OH)),δ3.51-3.74(m,11H,HOC H2 (C H (OH))3CH(OH)CH2N + ,N + CH2CH(OH)C H2 OH),δ3.94-3.98(m,3H,N + CH2C H (OH)),δ4.03-4.09(m 1H,HOCH2(CH(OH))3C H (OH)CH2N + ).δ2.51(s,4H,HOOCC H2 C H2 COO - ).

[0786] 13C-NMR (D2O 100MHz): δ43.2(HOCH2(CH(OH))3CH(OH) C H2N + ),δ45.8(N + C H2CH(OH)),δ62.8(N + CH2CH(OH) C H2OH),δ64.7(HO C H2(CH(OH))3CH(OH)CH2N + ),δ70.7-72.9(HOCH2( C H(OH))3 C H(OH)CH2N + ,N + CH2 C H(OH)CH2OH).δ31.4(HOOC C H2 C H2COO - ),δ179.7( C OOH, C OO - ).

[0787] <Examples 96 to 108>

[0788] Compounds 96 to 101, 103, 105, and 107 of Examples 96 to 101, 103, 105, and 107 shown in Table 6 were synthesized by the same synthesis method as Example 94 and the blending molar ratios described in Table 10. In addition, compounds 102, 104, 106, and 108 of Examples 102, 104, 106, and 108 were synthesized by the same synthesis method as Example 95 and the blending molar ratios described in Table 10. The physical property values ​​are shown below.

[0789] <Example 96> Synthesis of Compound 96

[0790]

[0791] FT-IR(KBr):3398cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1715cm -1 :COOH stretching vibration 1560cm -1 :COO - Stretching vibration

[0792] 1 H-NMR(D2O 400MHz): δ0.86-0.92(m,6H,N +C(CH2OH)2CH2C H3 ,C H3 CH2CH2), δ1.44 (m, 2H, N + C(CH2OH)2C H2 CH3), δ2.78-2.96 (m, 6H, N + C H 2CH(OH)), δ3.61-3.78 (m, 10H, N + C(C H2 OH)2CH2CH 3, N + CH2CH(OH)C H2 OH), δ3.83-3.88 (m, 3H, N + CH2C H (OH)). δ2.51 (s, 4H, HOOCC H2 C H2 COO - ).

[0793] 13 C-NMR (D2O 100MHz): δ9.6 (N + C(CH2OH)2CH2 C H3), δ24.6 (N + C(CH2OH)2 C H2CH3), δ43.6 (N + C (CH2OH)2CH2CH3), δ45.8 (N + C H2CH(OH)), δ60.2 (N + C( C H2OH)2CH2CH3), δ62.8 (N + CH2CH(OH) C H2OH), δ71.1 (N + CH2 C H(OH) C H2OH). δ31.4 (HOOC C H2 C H2COO - ), δ179.7 ( C OOH, C OO - ).

[0794] <Example 97> Synthesis of Compound 97

[0795]

[0796] FT-IR(KBr):3398cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1715cm -1 :COOH stretching vibration 1560cm -1 :COO - Stretching vibration

[0797] 1 H-NMR(D2O 400MHz): δ0.86-0.92(m,6H,N + C(CH2OH)2CH2C H3 ,C H3 CH2CH2),δ1.44(m,2H,N + C(CH2OH)2C H2 CH3),δ2.78-2.96(m,6H,N + C H 2CH(OH)),δ3.61-3.78(m,10H,N + C(C H2 OH)2CH2CH 3, N + CH2CH(OH)C H2 OH),δ3.83-3.88(m,3H,N + CH2C H (OH)).δ2.66-2.83(m,4H,HOOCC H2 C(OH)(COOH)C H2 COO - ).

[0798] 13 C-NMR (D2O 100MHz): δ9.6 (N + C(CH2OH)2CH2 C H3),δ24.6(N + C(CH2OH)2 C H2CH3),δ43.6(N + C (CH2OH)2CH2CH3),δ45.8(N + C H2CH(OH)),δ60.2(N + C( C H2OH)2CH2CH3),δ62.8(N + CH2CH(OH) C H2OH),δ71.1(N + CH2 C H(OH)C H2OH).δ43.7(HOOC C H2C(OH)(COOH) C H2COO - ),δ73.8(HOOCCH2 C (OH)(COOH)CH2COO - ),δ174.7(HOO C CH2C(OH)(COOH)CH2 C OO - ),δ178.6(HOOCCH2C(OH)( C OOH)CH2COO - ).

[0799] <Example 98> Synthesis of Compound 98

[0800]

[0801] FT-IR(KBr):3398cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1560cm -1 :COO - Stretching vibration

[0802] 1 H-NMR(D2O 400MHz): δ0.86-0.92(m,6H,N + C(CH2OH)2CH2C H3 ,C H3 CH2CH2),δ1.44(m,2H,N + C(CH2OH)2C H2 CH3),δ2.78-2.96(m,6H,N + C H 2CH(OH)),δ3.61-3.78(m,10H,N + C(C H2 OH)2CH2CH 3, N + CH2CH(OH)C H2 OH),δ3.83-3.88(m,3H,N + CH2C H (OH)).δ6.80-6.86(m,2H,C(OH)C H CH,C(COO － )CHC H CH),δ7.35-7.39(m,1H,C HCHC(OH)),δ7.68-7.73(m,1H,C(COOH)C H CH).

[0803] 13 C-NMR (D2O 100MHz): δ9.6 (N + C(CH2OH)2CH2 C H3),δ24.6(N + C(CH2OH)2 C H2CH3),δ43.6(N + C (CH2OH)2CH2CH3),δ45.8(N + C H2CH(OH)),δ60.2(N + C( C H2OH)2CH2CH3),δ62.8(N + CH2CH(OH) C H2OH),δ71.1(N + CH2 C H(OH) C H2OH).δ116.2(C(OH) C HCH),δ118.0(CH C (COO - )C(OH)),δ119.3(C(COO - )CH C HCH),δ130.5(C(COO - ) C HCH),δ133.9( C HCHC(OH)),δ159.6(C C (OH)C),δ175.5(C C OO - ).

[0804] <Example 99> Synthesis of Compound 99

[0805]

[0806] FT-IR(KBr):3398cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1560cm -1 :COO - Stretching vibration

[0807] 1 H-NMR(D2O 400MHz): δ0.86-0.92(m,6H,N+ C(CH2OH)2CH2C H3 ,C H3 CH2CH2),δ1.44(m,2H,N + C(CH2OH)2C H2 CH3),δ2.78-2.96(m,6H,N + C H 2CH(OH)),δ3.61-3.78(m,10H,N + C(C H2 OH)2CH2CH 3, N + CH2CH(OH)C H2 OH),δ3.83-3.88(m,3H,N + CH2C H (OH)).δ0.99(s,3H,C H3 CH2OCH2COO - ),δ3.34-3.39(q,2H,CH3C H2 OCH2COO - ),δ3.49-3.64(m,2H,CH3CH2OC H2 COO - ).

[0808] 13 C-NMR(D2O 100MHz):δ9.6(N + C(CH2OH)2CH2 C H3),δ24.6(N + C(CH2OH)2 C H2CH3),δ43.6(N + C (CH2OH)2CH2CH3),δ45.8(N + C H2CH(OH)),δ60.2(N + C( C H2OH)2CH2CH3),δ62.8(N + CH2CH(OH) C H2OH),δ71.1(N + CH2 C H(OH) C H2OH).δ14.0( C H3CH2O),δ66.4(CH3 C H2O),δ69.1(CH3CH2O C H2COO -),δ178.1(CH3CH2OCH2 C OO - ).

[0809] <Example 100> Synthesis of Compound 100

[0810]

[0811] FT-IR(KBr):3398cm -1 :O-H stretching vibration 2922cm -1 :C-H stretching vibration 1665cm -1 :COO - Stretching vibration

[0812] 1 H-NMR(D2O 400MHz): δ0.86-0.92(m,6H,N + C(CH2OH)2CH2C H3 ,C H3 CH2CH2),δ1.44(m,2H,N + C(CH2OH)2C H2 CH3),δ2.78-2.96(m,6H,N + C H 2CH(OH)),δ3.61-3.78(m,10H,N + C(C H2 OH)2CH2CH 3, N + CH2CH(OH)C H2 OH),δ3.83-3.88(m,3H,N + CH2C H (OH)).

[0813] 13 C-NMR (D2O 100MHz): δ9.6 (N + C(CH2OH)2CH2 C H3),δ24.6(N + C(CH2OH)2 C H2CH3),δ43.6(N + C (CH2OH)2CH2CH3),δ45.8(N + C H2CH(OH)),δ60.2(N + C( C H2OH)2CH2CH3),δ62.8(N + CH2CH(OH)C H2OH),δ71.1(N + CH2 C H(OH) C H2OH).δ114.6( C F3COO - ),δ165.1(CF3 C OO - ).

[0814] <Example 101> Synthesis of Compound 101

[0815]

[0816] FT-IR(KBr):3398cm -1 :O-H stretching vibration 2922cm -1 : C-H stretching vibration

[0817] 1 H-NMR (D2O 400MHz): δ0.86-0.92(m,6H,N + C(CH2OH)2CH2C H3 ,C H3 CH2CH2),δ1.44(m,2H,N + C(CH2OH)2C H2 CH3),δ2.78-2.96(m,6H,N + C H 2CH(OH)),δ3.61-3.78(m,10H,N + C(C H2 OH)2CH2CH 3, N + CH2CH(OH)C H2 OH),δ3.83-3.88(m,3H,N + CH2C H (OH)).

[0818] 13 C-NMR (D2O 100MHz): δ9.6 (N + C(CH2OH)2CH2 C H3),δ24.6(N + C(CH2OH)2 C H2CH3),δ43.6(N + C (CH2OH)2CH2CH3),δ45.8(N + C H2CH(OH)),δ60.2(N +C( C H2OH)2CH2CH3),δ62.8(N + CH2CH(OH) C H2OH),δ71.1(N + CH2 C H(OH) C H2OH).

[0819] <Example 102> Synthesis of Compound 102

[0820]

[0821] FT-IR(KBr):3344cm -1 :O-H stretching vibration 2920cm -1 : C-H stretching vibration

[0822] 1 H-NMR (D2O 400MHz): δ3.00-3.23(m,8H,HOCH2(CH(OH))3CH(OH)C H2 N + ,N + C H 2CH(OH)),δ3.51-3.74(m,11H,HOC H2 (C H (OH))3CH(OH)CH2N + ,N + CH2CH(OH)C H2 OH),δ3.94-3.98(m,3H,N + CH2C H (OH)),δ4.03-4.09(m 1H,HOCH2(CH(OH))3C H (OH)CH2N + ).

[0823] 13 C-NMR(D2O 100MHz): δ43.2(HOCH2(CH(OH))3CH(OH) C H2N + ),δ45.8(N + C H2CH(OH)),δ62.8(N + CH2CH(OH) C H2OH),δ64.7(HO C H2(CH(OH))3CH(OH)CH2N + ),δ70.7-72.9(HOCH2( CH(OH))3 C H(OH)CH2N + ,N + CH2 C H(OH)CH2OH).

[0824] <Example 103> Synthesis of Compound 103

[0825]

[0826] FT-IR(KBr):3398cm -1 :O-H stretching vibration 2922cm -1 : C-H stretching vibration

[0827] 1 H-NMR (D2O 400MHz): δ0.86-0.92(m,6H,N + C(CH2OH)2CH2C H3 ,C H3 CH2CH2),δ1.44(m,2H,N + C(CH2OH)2C H2 CH3),δ2.78-2.96(m,6H,N + C H 2CH(OH)),δ3.61-3.78(m,10H,N + C(C H2 OH)2CH2CH 3, N + CH2CH(OH)C H2 OH),δ3.83-3.88(m,3H,N + CH2C H (OH)).δ2.75(s,3H,C H3 SO3 - ).

[0828] 13 C-NMR (D2O 100MHz): δ9.6 (N + C(CH2OH)2CH2 C H3),δ24.6(N + C(CH2OH)2 C H2CH3),δ43.6(N + C (CH2OH)2CH2CH3),δ45.8(N + C H2CH(OH)),δ60.2(N + C( CH2OH)2CH2CH3),δ62.8(N + CH2CH(OH) C H2OH),δ71.1(N + CH2 C H(OH) C H2OH).δ38.5( C H3SO3 - ).

[0829] <Example 104> Synthesis of Compound 104

[0830]

[0831] FT-IR(KBr):3344cm -1 :O-H stretching vibration 2920cm -1 : C-H stretching vibration

[0832] 1 H-NMR (D2O 400MHz): δ3.00-3.23(m,8H,HOCH2(CH(OH))3CH(OH)C H2 N + ,N + C H 2CH(OH)),δ3.51-3.74(m,11H,HOC H2 (C H (OH))3CH(OH)CH2N + ,N + CH2CH(OH)C H2 OH),δ3.94-3.98(m,3H,N + CH2C H (OH)),δ4.03-4.09(m 1H,HOCH2(CH(OH))3C H (OH)CH2N + ).δ2.75(s,3H,C H3 SO3 - ).

[0833] 13 C-NMR (D2O 100MHz): δ43.2(HOCH2(CH(OH))3CH(OH) C H2N + ),δ45.8(N + C H2CH(OH)),δ62.8(N + CH2CH(OH) C H2OH),δ64.7(HO CH2(CH(OH))3CH(OH)CH2N + ),δ70.7-72.9(HOCH2( C H(OH))3 C H(OH)CH2N + ,N + CH2 C H(OH)CH2OH).δ38.5( C H3SO3 - ).

[0834] <Example 105> Synthesis of Compound 105

[0835]

[0836] FT-IR(KBr):3398cm －1 :O-H stretching vibration 2922cm －1 : C-H stretching vibration

[0837] 1 H-NMR(D2O 400MHz): δ0.86-0.92(m,6H,N + C(CH2OH)2CH2C H3 ,C H3 CH2CH2),δ1.44(m,2H,N + C(CH2OH)2C H2 CH3),δ2.78-2.96(m,6H,N + C H 2CH(OH)),δ3.61-3.78(m,10H,N + C(C H2 OH)2CH2CH 3, N + CH2CH(OH)C H2 OH),δ3.83-3.88(m,3H,N + CH2C H (OH)).

[0838] 13 C-NMR (D2O 100MHz): δ9.6 (N + C(CH2OH)2CH2 C H3),δ24.6(N + C(CH2OH)2 C H2CH3),δ43.6(N + C (CH2OH)2CH2CH3),δ45.8(N +C H2CH(OH)),δ60.2(N + C( C H2OH)2CH2CH3),δ62.8(N + CH2CH(OH) C H2OH),δ71.1(N + CH2 C H(OH) C H2OH).

[0839] <Example 106> Synthesis of Compound 106

[0840]

[0841] FT-IR(KBr):3344cm -1 :O-H stretching vibration 2920cm -1 : C-H stretching vibration

[0842] 1 H-NMR (D2O 400MHz): δ3.00-3.23(m,8H,HOCH2(CH(OH))3CH(OH)C H2 N + ,N + C H 2CH(OH)),δ3.51-3.74(m,11H,HOC H2 (C H (OH))3CH(OH)CH2N + ,N + CH2CH(OH)C H2 OH),δ3.94-3.98(m,3H,N + CH2C H (OH)),δ4.03-4.09(m 1H,HOCH2(CH(OH))3C H (OH)CH2N + ).

[0843] 13 C-NMR (D2O 100MHz): δ43.2(HOCH2(CH(OH))3CH(OH) C H2N + ),δ45.8(N + C H2CH(OH)),δ62.8(N + CH2CH(OH) C H2OH),δ64.7(HO C H2(CH(OH))3CH(OH)CH2N+ ),δ70.7-72.9(HOCH2( C H(OH))3 C H(OH)CH2N + ,N + CH2 C H(OH)CH2OH).

[0844] <Example 107> Synthesis of Compound 107

[0845]

[0846] FT-IR(KBr):3398cm -1 :O-H stretching vibration 2922cm -1 : C-H stretching vibration

[0847] 1 H-NMR (D2O 400MHz): δ0.86-0.92(m,6H,N + C(CH2OH)2CH2C H3 ,C H3 CH2CH2),δ1.44(m,2H,N + C(CH2OH)2C H2 CH3),δ2.78-2.96(m,6H,N + C H 2CH(OH)),δ3.61-3.78(m,10H,N + C(C H2 OH)2CH2CH 3, N + CH2CH(OH)C H2 OH),δ3.83-3.88(m,3H,N + CH2C H (OH)).

[0848] 13 C-NMR (D2O 100MHz): δ9.6 (N + C(CH2OH)2CH2 C H3),δ24.6(N + C(CH2OH)2 C H2CH3),δ43.6(N + C (CH2OH)2CH2CH3),δ45.8(N + C H2CH(OH)),δ60.2(N + C( CH2OH)2CH2CH3),δ62.8(N + CH2CH(OH) C H2OH),δ71.1(N + CH2 C H(OH) C H2OH).

[0849] <Example 108> Synthesis of Compound 108

[0850]

[0851] FT-IR(KBr):3344cm -1 :O-H stretching vibration 2920cm -1 : C-H stretching vibration

[0852] 1 H-NMR (D2O 400MHz): δ3.00-3.23(m,8H,HOCH2(CH(OH))3CH(OH)C H2 N + ,N + C H 2CH(OH)),δ3.51-3.74(m,11H,HOC H2 (C H (OH))3CH(OH)CH2N + ,N + CH2CH(OH)C H2 OH),δ3.94-3.98(m,3H,N + CH2C H (OH)),δ4.03-4.09(m 1H,HOCH2(CH(OH))3C H (OH)CH2N + ).

[0853] 13 C-NMR(D2O 100MHz): δ43.2(HOCH2(CH(OH))3CH(OH) C H2N + ),δ45.8(N + C H2CH(OH)),δ62.8(N + CH2CH(OH) C H2OH),δ64.7(HO C H2(CH(OH))3CH(OH)CH2N + ),δ70.7-72.9(HOCH2( C H(OH))3C H(OH)CH2N + ,N + CH2 C H(OH)CH2OH).

[0854] <Example 109> Synthesis of Compound 109

[0855]

[0856] Compound 109 of Example 109 shown in Table 6 was synthesized by the same synthesis method as in Example 1 and at the blending molar ratio described in Table 10. The physical properties thereof are shown below.

[0857] FT-IR(KBr):3145cm -1 :O-H stretching vibration 2946cm -1 :C-H stretching vibration 1572cm -1 :COO － Stretching vibration

[0858] 1 H-NMR(D2O 400MHz): δ2.28(s,4H, - OOCC H2 C H2 COO - ),δ3.61(s,12H,NH3 + C(C H2 OH)3).

[0859] 13 C-NMR (D2O 100MHz):δ34.0( - OOC C H2 C H2COO - ),δ59.4(NH3 + C (CH2OH)3),δ61.3(NH3 + C( C H2OH)3),δ182.3( C OO - ).

[0860] [Table 1]

[0861]

[0862]

[0863] [Table 2]

[0864]

[0865]

[0866] [Table 3]

[0867]

[0868]

[0869] [Table 4]

[0870]

[0871]

[0872] [Table 5]

[0873]

[0874]

[0875] [Table 6]

[0876]

[0877]

[0878] <Comparative Example 1> Compound 110

[0879] Tributyl lactic acid ammonium salt

[0880] The synthesis was carried out by the method described in Japanese Patent Application Laid-Open No. 2014-131974.

[0881] <Comparative Example 2> Compound 111

[0882] Choline acetate

[0883] With reference to the method described in Japanese Patent Application Laid-Open No. 2014-131974, synthesis was carried out using choline hydroxide and acetic acid.

[0884] <Comparative Example 3> Compound 112

[0885] 1-Butyl-3-methylimidazolium bromide

[0886] The synthesis was carried out with reference to the method described in Japanese Patent Application Laid-Open No. 2016-041682 using 1-butyl-3-methylimidazolium tetrafluoroborate, an ion exchange resin, and hydrobromic acid.

[0887] <Comparative Example 4> Compound 113

[0888] As D(+)-glucose, a reagent manufactured by Kanto Chemical Co., Ltd. was used.

[0889] <Comparative Example 5> Compound 114

[0890] As gelatin, nippi peptide FCP-AS-L (manufactured by Nippi, Incorporated) was used.

[0891] <Comparative Example 6> Compound 115

[0892] As albumin, albumin manufactured by NACALAI TESQUE, INC. (derived from bovine, general grade, pH 5.2) was used.

[0893] <Comparative Example 7> Compound 116

[0894] As urease, a reagent (derived from Jack Bean) manufactured by Wako Pure Chemical Industries, Ltd. was used.

[0895] <Comparative Example 8> Compound 117

[0896] As a buffer for urease, a 10 mM aqueous solution of potassium dihydrogen phosphate adjusted to pH 7.5 with sodium hydroxide was used.

[0897] <Comparative Example 9> Compound 118

[0898] As cytochrome C, a reagent manufactured by NACALAI TESQUE, INC. (HorseHeart, molecular weight 12384) was used.

[0899] <Comparative Example 10> Compound 119

[0900] As a buffer for cytochrome C and DNA, a 50 mM phosphate buffer having a pH of 7.4 prepared with 50 mM potassium dihydrogen phosphate and 50 mM potassium hydrogen phosphate was used.

[0901] <Comparative Example 11> Compound 120

[0902] DNA prepared by the method described in Japanese Patent Application Laid-Open No. 2014-131974 was used.

[0903] <Comparative Example 12> Compound 121

[0904] As tetra-n-butylammonium bromide, a reagent manufactured by Kanto Chemical Co., Ltd. was used.

[0905] <Reference Example 1> Compound 122

[0906] The synthesis was carried out by the method described in Japanese Patent Application Laid-Open No. 2014-131974.

[0907] <Reference Example 2> Compound 123

[0908] The synthesis was carried out by the method described in Japanese Patent Application Laid-Open No. 2014-131974.

[0909] The compounds of the above-mentioned Examples and Comparative Examples were subjected to the following measurements and evaluations.

[0910] 1. Properties at room temperature (25°C)

[0911] The compounds of Examples 1 to 109 were added to a spiral tube and dried under reduced pressure. As an acid anhydride, their properties (liquid, solid) at room temperature (25°C) were confirmed. The results are shown in Tables 7 to 10. It should be noted that "solid" in Tables 7 to 10 means solid at room temperature (25°C). As a result of the reduced pressure drying treatment, the compounds of Examples 1 to 109 were all solid at room temperature (25°C).

[0912] Therefore, compared with conventional organic ammonium salts, the organic ammonium salt of the present invention is easy to crystallize because the hydrogen bonds in the molecule form a strong cationic structure by forming a polyhydroxyalkyl group, thereby clarifying that the organic ammonium salt of the present invention can be applied to the influence of the selection of functional groups and characteristic groups on the melting point and a wide range of various anions in the structural design.

[0913] [Table 7]

[0914]

[0915] [Table 8]

[0916]

[0917] [Table 9]

[0918]

[0919] [Table 10]

[0920]

[0921] 2. Long-term enzyme stability (1)

[0922] The compounds listed in Table 11 were used as stabilizers to prepare 50% aqueous solutions of the compounds, and after urease was added to dissolve the compounds to reach the enzyme concentration listed in Table 11, water was removed by reduced pressure distillation. After the reduced pressure distillation, the obtained solid samples were placed in a constant temperature and humidity chamber set at 40°C and 80%RH, which was higher than the temperature and humidity for storing enzymes in general. After being placed for a specified period of time, each sample was collected, and the activity retention rate of the enzymes stored in each compound was measured using the following method, thereby confirming the retention of the three-dimensional structure and the stabilization effect in the enzymes of each compound.

[0923] <Determination of Hydrolase: Urease Activity>

[0924] The activity of urease was determined using an indoxyl assay to quantify ammonium ions generated from the decomposition of urea by the enzymatic reaction of urease.

[0925] First, 100 mL of a 1 mM substrate solution (prepared by dissolving urea as a substrate in a 10 mM phosphate buffer at pH 7.5) was weighed into an Erlenmeyer flask and preheated at 30°C for about 30 minutes.

[0926] Then, under the conditions of the concentration and temperature set in Table 11, the sample left standing for a predetermined period was added to the substrate solution so that the amount of enzyme became 0.5 mg, and the reaction was carried out at 30°C for 60 minutes.

[0927] After the reaction, 0.1 mL of the reaction solution was taken, and 2 mL of a phenol solution (prepared by dissolving 10 g of phenol and 50 mg of sodium pentacyanonitrosylferrate (III) in ion exchange water and diluting the mixture to 1000 mL using a volumetric flask with ion exchange water) and 2 mL of a sodium hypochlorite solution (prepared by dissolving 5 g of sodium hydroxide and 8.4 mL of a 5% sodium hypochlorite solution in ion exchange water and diluting the mixture to 1000 mL using a volumetric flask with ion exchange water) were immediately added, and the mixture was reacted in a thermostatic bath at 37°C for 20 minutes.

[0928] The absorbance of the reaction solution at a wavelength of 635 nm was measured using an ultraviolet-visible spectrophotometer (V-550: JASCO Corporation), and the amount of ammonium ion generated was determined from the amount of indoxyl obtained, thereby calculating the urease activity. For the quantification of ammonium ions, an ammonium ion solution was prepared in a concentration range of 0.1 to 3.0 mM, and a calibration curve obtained by quantification using the indoxyl determination method was used in the same manner as described above.

[0929] It should be noted that the enzyme activity value as the enzyme activity retention rate benchmark is calculated as follows. The urease powder preserved under the appropriate temperature condition was dissolved in a buffer solution (10mM phosphate buffer of pH 7.5), thereby modulating an enzyme solution whose enzyme concentration is 50mg / mL. After modulation, as above-mentioned, this solution was added in the matrix solution immediately, and the enzyme amount was made to become 0.5mg. After carrying out the enzyme reaction, the ammonium ion amount quantitatively measured by the indoxyl assay method was used as a benchmark, thereby calculating the enzyme activity retention rate.

[0930] In the results under the condition of 40°C in Table 11, the activity retention rate of the enzyme stored in imidazolium organic ammonium salt, general additives and the enzyme without additives decreased to 0-3% after 30 days. In contrast, the compound of the present invention showed an activity retention rate higher than that of the comparative example after 30 days, regardless of the stabilizer: enzyme ratio.

[0931] In Reference Examples 1 and 2, which were liquid at 25°C, the enzyme could not be dissolved and was difficult to store when the ratio of stabilizer:enzyme was 1:1 and 0.1:1. However, since the compound of the present invention mixed solids, the enzyme could be stored at a high concentration.

[0932] That is, it is suggested that the compound of the present invention maintains the activity of the enzyme under the conditions of high concentration, high temperature and long time and has high retention of the steric structure of the enzyme.

[0933] [Table 11]

[0934]

[0935]

[0936] A 50% aqueous solution of the compound in Table 12 was prepared, and urease was added to dissolve it to achieve the enzyme concentration described in Table 12, and then placed in a constant temperature and humidity chamber set at 40°C and 80% RH, which is higher than the temperature and humidity for storing enzymes in general. After being placed for a predetermined period of time, each sample was collected, and the activity retention rate of the enzyme stored in each compound was measured by the following method, thereby confirming the retention of the three-dimensional structure in the enzyme of each compound and the stabilization effect.

[0937] In the results under 40°C conditions in the aqueous solution state in Table 12, the activity retention rate of the enzyme stored in the imidazolium organic ammonium salt, the enzyme stored in the 50% aqueous solution of the general additive, and the enzyme stored in the buffer solution decreased to 0-2% after 30 days. In contrast, the 50% aqueous solution to which the compound of the present invention was added still showed an activity retention rate higher than that of the comparative example after 30 days.

[0938] That is, it is suggested that the compound of the present invention can maintain the enzyme activity not only in a solid state but also in an aqueous solution under the conditions of high concentration, high temperature and long time, and has high retention of the three-dimensional structure of the enzyme.

[0939] [Table 12]

[0940]

[0941]

[0942] 3. Long-term stability of proteins

[0943] A 50% aqueous solution of the compound in Table 13 was prepared, and cytochrome C was added to dissolve it so as to reach the protein concentration described in Table 13, and then water was distilled off under reduced pressure. After distillation under reduced pressure, the obtained solid sample was placed in a constant temperature and humidity chamber set at 40°C and 80% RH, which is higher than the temperature and humidity for storing proteins in general. After being placed for a predetermined period of time, each sample was collected, and the IR spectrum and UV spectrum of the protein stored in each compound were measured by the following method to confirm the long-term stability of the protein.

[0944] First, the changes in amide absorption caused by IR spectroscopy were confirmed in detail, and the higher-order structure of the protein (turn, α-helix, random coil, β-sheet) was confirmed. The ATR method based on a Fourier transform infrared spectrophotometer (FT / IR-6100: JASCO Corporation) was used to measure the amide I region (1600-1700 cm -1 ), amide II region (1500-1600cm -1 ), and a peak was detected from the difference between an organic ammonium salt sample to which cytochrome C was not added (blank) and an organic ammonium salt sample to which cytochrome C was added (sample).

[0945] In addition, the active state of cytochrome c (Fe 2+ : Reduced form, Fe 3+ : Oxidized form). After the organic ammonium salt sample to which cytochrome C was added was diluted to 1% with 50 mM phosphate buffer (prepared with 50 mM potassium dihydrogen phosphate and 50 mM potassium hydrogen phosphate) at pH 7.4, the long-term stability of the protein in the sample in a quartz cuvette with a light path width of 2 mm was immediately measured using a UV-visible spectrophotometer.

[0946] The results are shown in Table 13. Proteins that showed long-term stability were marked with ○, and proteins that did not show long-term stability were marked with ×.

[0947] When the amide absorption was identified by IR spectroscopy, the higher-order structure of the protein was confirmed by comparing it with the literature values ​​(Chem. Commun 2005, 4804-4806, Biomacromolecules 2010, 11, 2944-2948, Archives of the Society for Protein Science, 2, e054 (2009)). When the powdered cytochrome c before addition was measured by IR, the absorption at 1645 cm in the amide I region was identified. -1 and 1537 cm in the amide II region -1Secondly, cytochrome C in phosphate buffer was confirmed to be undenatured (amide I region: 1653 cm -1 , amide II region: 1547 cm -1 ), and was confirmed to be an α-helical structure. Since the cytochrome C in the organic ammonium salt of the example was measured to be equivalent to that in the phosphate buffer solution (amide I region: 1652-1655 cm -1 、Amide II region: 1545-1549cm -1 ), therefore, it was confirmed that the cytochrome C stored in the organic ammonium salts of all the examples was not a denatured structure, but still maintained an α-helical structure. That is, by using the organic ammonium salt of the product of the present invention to dissolve the solid of the inactive denatured protein (cytochrome C), the activity of the protein was expressed, thereby showing the effect of expressing renaturation, and showing that the cytochrome C was still maintained in an undenatured state.

[0948] Cytochrome C transfers electrons to Fe 2+ (reduced form) and Fe 3+ (Oxidized form) is a state that changes reversibly, and cytochrome C maintains its secondary structure in the active state. In the absorption of the UV spectrum, the reduced form has peaks near 550nm in the α band, near 521nm in the β band, and near 415nm in the γ band; in the oxidized form, there are no clear peaks in the α band and the β band, and a low-wavelength shift is performed near 396nm in the γ band. Denatured in the inactivated state, the peaks of the α band, the β band, and the γ band disappear. Compared with the peaks of the comparative example, the embodiment shows the peaks of the reduced form in the α band, the β band, and the γ band, respectively. Thus, it is confirmed that the cytochrome C preserved in the organic ammonium salt of the product of the present invention maintains its secondary structure in the reduced active state.

[0949] That is, the product of the present invention is an excellent protein storage material that does not denature the protein even under high temperature conditions and over a long period of time, and is also useful as a protein renaturing agent.

[0950] [Table 13]

[0951]

[0952]

[0953] Furthermore, from the results of the aqueous solution at 40°C in Table 14, it was confirmed that even in a 50% aqueous solution to which the compound of the present invention was added, the renaturation effect and the maintenance of the secondary structure were exhibited similarly to the storage in the solid sample.

[0954] That is, the product of the present invention is an excellent protein preservation material that does not denature proteins even when used in the form of an aqueous solution and even under high temperature conditions and for a long period of time, and is also useful as a protein renaturing agent.

[0955] [Table 14]

[0956]

[0957]

[0958] 4. Long-term stability of DNA

[0959] A 50% aqueous solution of the compound in Table 15 was prepared, and after adding DNA to dissolve it to the concentration recorded in Table 15, water was distilled off under reduced pressure. After distillation under reduced pressure, the obtained solid sample was placed in a constant temperature and humidity chamber set at 40°C and 80% RH, which is higher than the temperature and humidity for storing DNA normally. After being placed for a specified period of time, each sample was taken, and the UV spectrum of the DNA stored in each compound was measured using the following method to confirm the long-term stability of the DNA.

[0960] The results are shown in Table 15. Those showing long-term stability to DNA were marked as ○, and those not showing long-term stability were marked as ×.

[0961] DNA maintains a double helix structure in an active state and has a peak near 260nm in UV spectrum absorption, but in the case of denaturation, the relative absorbance of DNA UV absorption increases significantly. For the example compounds shown in Table 15, a peak indicating the absorption of DNA in an organic ammonium salt was obtained at 258nm from the difference between a 0.1wt% DNA solution and a sample (blank) in which DNA was not dissolved, and it was the same peak as the absorption (259nm) of (1wt%) DNA dissolved in water, so it was determined that the DNA dissolved in the organic ammonium salt maintained a double helix structure in an active state.

[0962] That is, it is shown that the product of the present invention is excellent in the storage stability of DNA and is useful as a storage material for nucleic acids such as DNA.

[0963] [Table 15]

[0964]

[0965] Furthermore, from the results of the aqueous solution at 40°C in Table 16, it was confirmed that even in a 50% aqueous solution to which the compound of the present invention was added, DNA maintained its double helical structure in an active state, similar to the storage in a solid sample.

[0966] That is, it is shown that the product of the present invention has excellent storage stability for DNA even when used in the form of an aqueous solution and is useful as a storage material for nucleic acids such as DNA.

[0967] [Table 16]

[0968]

[0969] 5. Long-term enzyme stability (2)

[0970] The method for preparing the sample by distilling off the solvent from the dissolved solution in Table 17 is to prepare a 50% aqueous solution of the compound, add urease to dissolve it to the enzyme concentration recorded in Table 17, and then remove water by reduced pressure distillation to obtain a solid sample. On the other hand, mixing in a mortar is to mix the product of the present invention and urease at the enzyme concentration recorded in Table 17 in a mortar to obtain a solid sample.

[0971] Then, each sample was placed in a constant temperature and humidity chamber set at 40°C and 80% RH, which is higher than the temperature and humidity for storing enzymes in general. After being placed for a predetermined period of time, each sample was taken and the activity retention rate of the enzyme stored in each compound was measured using the following method, thereby confirming the retention of the three-dimensional structure in the enzyme of each compound and the stabilization effect.

[0972] Compared with the sample mixed in a mortar, the method of preparing a solid sample by dissolving the solution showed a high activity retention rate. According to the above results, by dissolving the product of the present invention and the enzyme, the three-dimensional structure inside the enzyme can be maintained, thereby obtaining a biological sample treatment agent showing high activity retention.

[0973] [Table 17]

[0974]

[0975]

[0976] 6. Metal oxide dispersion test

[0977] The dispersion state of the compounds of each example and comparative example shown in Table 18 was confirmed with naked eyes after mixing 0.25 g of each compound with 0.50 g of water and 0.10 g of zirconium (IV) oxide (Wako Pure Chemical Industries, Ltd.) at 2000 rpm for 1 min × 5 times. The state where zirconium oxide was dispersed was evaluated as ○, and the state where zirconium oxide was not dispersed but precipitated was evaluated as ×. The results are shown in Table 18.

[0978] The compounds of the examples all dispersed zirconium oxide well to obtain dispersions, whereas the compound of Comparative Example 12 immediately precipitated zirconium oxide and failed to disperse.

[0979] That is, it is believed that the organic ammonium salt of the present invention utilizes the structural characteristics of the quaternary ammonium cation composed of a large number of cations with hydrogen bond donating and coordinating hydroxyl groups, thereby increasing the affinity with the oxygen atoms of the hydrogen bond accepting zirconium oxide, and further, through the affinity between the hydroxyl groups of the quaternary ammonium salt and the metal atoms of the coordinating zirconium oxide, the zirconium oxide is well dispersed.

[0980] [Table 18]

[0981]

[0982] The compounds of each example and comparative example shown in Table 19 were visually confirmed after mixing 0.25 g of each compound with 0.50 g of water and 0.10 g of titanium (IV) oxide (Wako Pure Chemical Industries, Ltd.) at 2000 rpm for 1 min × 5 times. The state where titanium oxide was dispersed was evaluated as ○, and the state where titanium oxide was not dispersed but precipitated was evaluated as ×. The results are shown in Table 19.

[0983] The compounds of the examples all dispersed titanium oxide well to obtain dispersions, whereas the compound of Comparative Example 12 precipitated titanium oxide and had low dispersibility.

[0984] That is, it is believed that the organic ammonium salt of the present invention utilizes the structural characteristics of the quaternary ammonium cation composed of a large number of cations with hydrogen bond donating and coordinating hydroxyl groups, thereby increasing the affinity with the oxygen atoms of hydrogen bond accepting titanium oxide, and further, through the affinity between the hydroxyl groups of the quaternary ammonium salt and the metal atoms of the coordinating titanium oxide, the titanium oxide is well dispersed.

[0985] This result suggests that the organic ammonium salt of the present invention has excellent affinity with inorganic materials such as metals or metal oxides having a hydrogen bond accepting functional group and is useful for treating agents, cosmetics, and the like for these inorganic materials.

[0986] [Table 19]

[0987]

[0988] 7. Carbon nanotube dispersion test

[0989] The compounds of each example and comparative example shown in Table 20 were visually confirmed after mixing 0.25 g of each compound with 0.75 g of water and 0.025 g of carbon nanotubes (multilayer, 3 to 20 nm) (Wako Pure Chemical Industries, Ltd.) at 2000 rpm for 1 min × 5 times. The state in which the carbon nanotubes were dispersed was evaluated as ○, and the state in which the carbon nanotubes were not dispersed but precipitated was evaluated as ×. The results are shown in Table 20.

[0990] As a result, the compounds of the examples dispersed the carbon nanotubes well, and a low-viscosity dispersion with good handling properties was obtained. On the other hand, in the case of the compound of Comparative Example 12, the carbon nanotubes precipitated and were not dispersed.

[0991] That is, it is considered that the organic ammonium salt of the present invention utilizes the structural characteristics of quaternary ammonium cations composed of a large number of hydroxyl groups having hydrogen bond donating properties, thereby increasing the affinity with the carbon-carbon unsaturated bonds (π electron system) of the hydrogen bond accepting carbon nanotubes, thereby well dispersing the carbon nanotubes.

[0992] This result suggests that the organic ammonium salt of the present invention has excellent affinity for compounds or materials having a carbon-carbon unsaturated bond and is useful as a treatment agent for such materials.

[0993] [Table 20]

[0994]

[0995] 8. Organic dye dispersibility test

[0996] For the compounds of each embodiment and comparative example shown in Table 21, it was confirmed with naked eyes that 0.2g of each compound and 0.7g of water and 0.1g of organic dye Vali Fast Black 3830 (Orient Chemical Industry) were dispersed with ultrasonic waves and placed for 24 hours, and the dispersion state after mixing for 24 hours was determined. The state of the organic dye being dispersed was evaluated as ○, and the state of the particles being precipitated was evaluated as ×. The results are shown in Table 21.

[0997] As a result, all the Example compounds dispersed the organic dye well to obtain a uniform dispersion liquid. On the other hand, in the case of the compound of Comparative Example 12, the organic dye precipitated and failed to disperse.

[0998] That is, it is believed that the organic ammonium salt of the present invention utilizes the structural characteristics of the cation composed of a large number of hydroxyl groups with hydrogen bond donating and coordinating properties in the quaternary ammonium cation, thereby increasing the affinity with the nitrogen atoms and oxygen atoms of the hydrogen bond accepting organic dye, and further, the affinity between the hydroxyl group of the quaternary ammonium salt and the metal atom (chromium) of the coordinating organic dye is increased, thereby dispersing well.

[0999] This result suggests that the organic ammonium salt of the present invention is useful for treating agents of organic compounds having a hydrogen bond accepting functional group, such as organic dyes, and treating agents of materials.

[1000] [Table 21]

[1001]

[1002] 9. Redispersibility

[1003] The dispersions of zirconium oxide, titanium oxide, and organic dye Vali Fast Black 3830 of Examples 28, 36, 48, and 109 shown in Table 22 and Comparative Example 12 were dehydrated under reduced pressure for 3 hours at 50°C to obtain compounds in a dry state. Here, the dispersion state after adding 0.50 g of water to each sample of zirconium oxide and titanium oxide and adding 0.7 g of water to the sample of organic dye Vali Fast Black 3830 and mixing with a self-rotating revolution mixer (THINKYCORPORATION, ARE-310) at 2000 rpm and 1 min × 5 times was confirmed with the naked eye. As a result, the example compounds were all well dispersed to obtain a uniform dispersion. On the other hand, the precipitate was found immediately after the compound of the comparative example was mixed with a mixer.

[1004] Can confirm from this result, after making the compound drying after dispersion, even disperse again, also can disperse well.In addition, except adding metal oxide, organic dye in the aqueous solution of organic ammonium salt of the present invention and the dispersion method of its dispersed system, even in the powdered state of metal oxide, organic dye, add water and also can disperse well in its dispersed system, enlightenment thus can carry out the redispersion of the organic compound with hydrogen bond accepting functional group and the material with hydrogen bond accepting functional group, cosmetics etc., and these purposes are useful.

[1005] Furthermore, it is suggested that since the amine compound and the acid used as the compound raw material include compounds registered in the Japanese Standards of Quasi-drug Ingredients, the compound is highly safe and useful for these uses.

[1006] [Table 22]

[1007]

[1008] 10. Metal oxide dispersibility test 2

[1009] For the compounds of each example and comparative example shown in Table 23, the dispersion state after mixing 0.25 g of each compound, 0.50 g of water, and 0.10 g of zinc oxide (Ishihara Sangyo Co., Ltd.) at 2000 rpm and 1 min × 5 times was visually confirmed. The state where zinc oxide was dispersed was evaluated as ○, and the state where zinc oxide was not dispersed but precipitated was evaluated as ×. The results are shown in Table 23.

[1010] The compounds of the examples all dispersed zinc oxide well to obtain dispersions, whereas the compound of Comparative Example 12 immediately precipitated zinc oxide and failed to disperse.

[1011] That is, it is considered that the organic ammonium salt of the present invention utilizes the structural characteristics of the quaternary ammonium cation composed of a large number of cations having hydrogen bond donating and coordinating hydroxyl groups, thereby increasing the affinity with the oxygen atoms of zinc oxide that are hydrogen bond accepting, and further, the zinc oxide is well dispersed through the affinity between the hydroxyl groups of the quaternary ammonium salt and the metal atoms of the coordinating zinc oxide.

[1012] [Table 23]

[1013]

[1014] 11. Metal oxide dispersibility test 3

[1015] The compounds of each example and comparative example shown in Table 24 were visually checked for dispersion after mixing 0.25 g of each compound, 0.50 g of water, and 0.10 g of barium titanate (Kanto Chemical Co., Ltd., Japan) using a rotary and revolving stirrer (THINKY CORPORATION, ARE-310) at 2000 rpm for 1 min × 5 times. The state where the barium titanate was dispersed was evaluated as ○, and the state where it was not dispersed and precipitated was evaluated as ×. The results are shown in Table 24.

[1016] The compounds of Examples all dispersed barium titanate well to obtain dispersions, whereas the compound of Comparative Example 12 immediately precipitated barium titanate and failed to disperse.

[1017] That is, it is believed that the organic ammonium salt of the present invention utilizes the structural characteristics of the quaternary ammonium cation composed of a large number of cations with hydrogen bond donating and coordinating hydroxyl groups, thereby increasing the affinity with the oxygen atoms of the hydrogen bond accepting barium titanate, and further, through the affinity between the hydroxyl groups of the quaternary ammonium salt and the metal atoms of the coordinating zinc oxide, the barium titanate is well dispersed.

[1018] [Table 24]

[1019]

Claims

1. An organic ammonium salt, wherein The organic ammonium salt is solid at 25° C. and contains an anion and an ammonium cation represented by the following formula (I), N + R n H 4-n (I) In the formula, n represents an integer from 1 to 3, The R and the anion in formula (I) are any combination of the following (1) and (2-1) to (2-8), (1) R represents 1-hydroxyethyl, n is 1, and the anion is a caproic acid anion, a caprylic acid anion, a capric acid anion, a lauric acid anion, a cyclohexanecarboxylic acid anion, a crotonic acid anion, a cinchona acid anion, a tartaric acid anion, adipic acid anion, a terephthalic acid anion, a mandelic acid anion or a trifluoroacetic acid anion; or n is 2, and the anion is a lauric acid anion, a cinchona acid anion or a terephthalic acid anion; or n is 3, and the anion is a formic acid anion, a caprylic acid anion, a capric acid anion, a lauric acid anion, a cyclohexanecarboxylic acid anion, an adipic acid anion or a benzoic acid anion; (2-1) R represents 1,3-dihydroxy-2-ethylpropane-2-yl, n is 1, and the anion is a caprylic acid anion, a lauric acid anion, an oleic acid anion, a glycolic acid anion, a dihydroxystearic acid anion, a cinchona acid anion, a salicylic acid anion or a trifluoroacetic acid anion; (2-2) R represents 1,3-dihydroxy-2-hydroxymethylpropane-2-yl, n is 1, and the anion is a butyrate anion, a caproate anion, a caprylate anion, a laurate anion, a dihydroxystearate anion, a salicylate anion, a trifluoroacetic acid anion, a sulfate anion, a phosphoric acid anion or a dicyanamide anion; (2-3) R represents 1,3-dihydroxypropane-2-yl, n is 1, and the anion is a butyric acid anion, a caproic acid anion, a caprylic acid anion, a lauric acid anion, a cyclohexanecarboxylic acid anion, a dihydroxystearic acid anion, a cinchona acid anion, a 12-hydroxystearic acid anion, an adipic acid anion, a sebacic acid anion, a terephthalic acid anion, a p-hydroxybenzoic acid anion, a bis(trifluoromethylsulfonyl)imide anion or a dicyanamide anion; (2-4) R represents pentahydroxyhexane-1-yl, n is 1, and the anion is a butyrate anion, a caproate anion, a caprylate anion, a laurate anion, a dihydroxystearate anion, a pyruvate anion, a sulfate anion, a phosphate anion, or a dicyanamide anion; (2-5) n is 2, one R is 1,3-dihydroxy-2-ethylpropane-2-yl, the other R is 2,3-dihydroxypropane-1-yl, and the anion is a succinate anion; (2-6) n is 2, one R is pentahydroxyhexane-1-yl, the other R is 2,3-dihydroxypropane-1-yl, and the anion is a succinate anion; (2-7) n is 3, one R is 1,3-dihydroxy-2-ethylpropane-2-yl, two Rs are 2,3-dihydroxypropane-1-yl, and the anion is an oleate anion or a succinate anion; (2-8) n is 3, one R is pentahydroxyhexane-1-yl, two Rs are 2,3-dihydroxypropane-1-yl, and the anion is an oleic acid anion or a succinic acid anion.

2. The organic ammonium salt according to claim 1, wherein The R and the anion in formula (I) are a combination of (1).

3. The organic ammonium salt according to claim 1, wherein The R and the anion in formula (I) are any combination of (2-1) to (2-4).

4. The organic ammonium salt according to claim 1, wherein The R and the anion in formula (I) are any combination of (2-5) to (2-8).

5. Use of an organic ammonium salt in a treating agent, wherein: The organic ammonium salt is the organic ammonium salt according to claim 1, and the treating agent treats the hydrogen bonding material.

6. The use according to claim 5, wherein The hydrogen bonding material is a biological sample.

7. The use according to claim 6, wherein The biological sample is a biocatalyst, protein or nucleic acid.

8. The use according to claim 5, wherein The treating agent is prepared as a solid composition containing the treating agent and the hydrogen bonding material.

9. The use according to claim 8, wherein The hydrogen bonding material is stored in the state of the solid composition at 25° C. or higher.

10. The use according to claim 5, wherein The treating agent, the hydrogen bonding material, and a solvent are mixed into a liquid state, and then the solvent is removed to prepare a solid composition in which the hydrogen bonding material is uniformly mixed in the treating agent.

11. The use according to claim 5, wherein The treatment agent is prepared into a biological sample solution containing the treatment agent, a biological sample and a solvent.

12. The use according to claim 11, wherein After the solid composition including the treatment agent and the biological sample is stored in a solid state, the solvent is added to prepare the biological sample solution.

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