COMPONENT, CHEMOSENSOR DEVICE COMPLETING THE COMPONENT, MACHINE COMPLETING THE CHEMOSENSOR DEVICE AND METHOD FOR DETECTING AN ION IN AN AQUEOUS SAMPLE

Abstract

Compound with a structure having formula (Ia) or salts thereof: in which X is, independently at each occurrence, a bond, CH2, O, S, NH or N(CH3); R2 is, independently at each occurrence, a cyclic group of 5 to 12 members, optionally having at least one double bond between two adjacent ring atoms, wherein R2 optionally has at least one ring atom N, O or S, and wherein R2 optionally is substituted with 1, 2, 3 or 4 RB; RB is, independently at each occurrence, selected from the group consisting of -CH3, -CH2CH3, -CH2OH, -CH2NH2, -COCH3, -COOH, -CONH2, -CN, -OH, -OCH3, -NH2, -NHCH3, -N(CH3)2, -SH, -SCH3, halogen and halomethyl; G is a cyclic fluorophore, wherein G is attached to the starting molecular unit via a ring atom and wherein G is optionally substituted with -LT is substituted;L is a linker selected from the group consisting of a bond, C1-4-alkylene, OC1-4-alkylene, NHC1-4-alkylene, SO2C1-4-alkylene and C1-4-alkylene-C6H4, T is selected from the group consisting of a leaving group, -OH, -NH2, -C(O)OH, a protected hydroxy group, a protected amino group and a protected carboxyl group.

Description

BACKGROUND

[0001] Drinking water quality remains a central issue in many regions worldwide. This is primarily due to the wide variety of drinking water sources, such as boreholes, lakes, rivers, and rainwater. Heavy metals as contaminants in drinking water are among the most dangerous pollutants, which can be harmful to health upon prolonged exposure. Lead is one of the classic pollutants found in drinking water that must be monitored. Other toxic heavy metals include arsenic, mercury, chromium, and cadmium. The World Health Organization's limit for lead (Pb) is 10 micrograms per liter. However, this level of contaminant is difficult to detect, especially at low cost. Therefore, there remains a need for chemical sensors with high sensitivity to water pollutants that can be manufactured more cost-effectively. SUMMARY

[0002] In one aspect, the present revelation provides a connection with formula (I) or salts thereof: R 1 -CH2NH-G (I), in the R 1 a cyclic group with 5 to 12 members, wherein at least one ring atom is N, O or S, which optionally has at least one double bond between two adjacent ring atoms, wherein R 1 optionally with 1, 2, 3 or 4 R A is substituted and where R 1 optionally with 1 or 2 -(XR 2 ) is substituted; X is a bond, CH2, O, S, NH or N(CH3) at each occurrence independently; R 2 In each occurrence, independently, it is a cyclic group with 5 to 12 members, which optionally has at least one double bond between two adjacent ring atoms, where R 2 optionally includes at least one ring atom N, O or S, and wherein R 2 optionally with 1, 2, 3 or 4 R Bis substituted; R A and R B each occurrence is independently selected from the group consisting of -CH3, -CH2CH3, -CH2OH, -CH2NH2, -COCH3, -COOH, -CONH2, -CN, -OH, -OCH3, -NH2, -NHCH3, -N (CH3) 2, -SH, -SCH3, halogen and halomethyl; G is a cyclic fluorophore, wherein G is attached to the starting molecular unit via a ring atom and wherein G is optionally substituted with -LT; L is a leftist selected from the group consisting of a bond, C 1-4 -Alkylene, OC 1-4 -Alkylene, NHC 1-4 -Alkylene, SO2C1-4-alkylene and C1-4-alkylene-C6H4, T is selected from the group consisting of a leaving group, -OH, -NH2, -C(O)OH, a protected hydroxy group, a protected amino group and a protected carboxyl group.

[0003] In another aspect, the present disclosure provides a chemosensor device comprising: a compound as described above or a salt thereof, an optical detector a light source and a recording designed to touch an aqueous sample.

[0004] In yet another aspect, the present disclosure provides a method for detecting an ion in an aqueous sample, comprising: Touching the aqueous sample with a chemosensor device as described herein; Irradiation of the aqueous sample with light, whereupon the compound of the chemosensor device binds to the ion, causing the compound to generate a fluorescence signal; and Detecting the fluorescence signal.

[0005] Further aspects of the application will become apparent when considering the detailed description and attached drawings. List of characters Fig.Figure 1 shows a representative real-time heavy metal ion sensor for water purifiers. Fig. Figure 2 shows a representative receptor-spacer-fluorophore sensor described herein. Fig. Figure 3 shows a simulated bonding configuration of a chemosensor with pyrimidinyl ethanolamine as receptor spacer groups. The simulation shows that the molecule would not fluoresce despite the Pb bond due to the proximity between the ion and the fluorophore. DETAILED DESCRIPTION

[0006] Before describing embodiments of the application in detail, it should be understood that the application is not limited to the design details and component arrangements set out in the following description or illustrated in the following drawings. Further embodiments are possible under the application, and it can be implemented or carried out in practice in various ways.

[0007] The terms "comprise" or "comprises", "exhibit" or "exhibits", "with", "include" or "includes", "can" or "can", "contains" or "contains", and variants thereof, when used in this document, are intended to be open transitional phrases, terms, or words that do not preclude the possibility of additional actions or structures. The singular forms "a", "an", as well as "the", "a", and "a" encompass plural references unless the context clearly indicates otherwise. This disclosure also includes further embodiments that "comprise", "consist of", and "consist substantially of" the embodiments or elements described herein, regardless of whether this is expressly stated.

[0008] The modifier "approximately" used with a quantity includes the specified value and has the meaning given by the context (for example, it includes at least the degree of error associated with the measurement of the specific quantity). It should be noted that the modifier "approximately" also reveals the range defined by the absolute values ​​of the two endpoints. The expression "from approximately 2 to approximately 4," for example, also reveals the range "from 2 to 4." The term "approximately" can refer to plus or minus 10% of the specified number. Thus, for example, "approximately 10%" can indicate a range of 9% to 11%, and "approximately 1" can mean 0.9 to 1.1. Other meanings of "approximately" can arise from the context, such as rounding; for example, "approximately 1" can also mean 0.5 to 1.4.

[0009] When specifying numerical ranges in this document, every intermediate number is explicitly considered with the same degree of precision. For example, in the range from 6 to 9, the numbers 7 and 8 are included in addition to 6 and 9, and in the range from 6.0 to 7.0, the numbers 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, and 7.0 are explicitly included.

[0010] The term "alkylene," as used here, refers to a divalent group derived from an unbranched or branched hydrocarbon with 1 to 10 carbon atoms, for example, with 1 to 4 carbon atoms. Representative examples of alkylenes include, but are not limited to, -CH₂CH₂-, -CH₂CH₂CH₂-, and -CH₂CH₂CH₂CH₂-.

[0011] The term "aryl," as used here, refers to a phenyl group or fused ring systems of bicyclic or tricyclic aryls. Bicyclic fused ring systems are exemplified by a phenyl group attached to the parent molecular unit and fused to a phenyl group. Tricyclic fused ring systems are exemplified by a phenyl group attached to the parent molecular unit and fused to two other phenyl groups. Representative examples of bicyclic aryls include, but are not limited to, naphthyl. Representative examples of tricyclic aryls include, but are not limited to, anthracenyl. The monocyclic, bicyclic, and tricyclic aryls are linked to the parent molecular unit via any carbon atom contained in the rings.

[0012] The term "cycloalkyl," as used here, refers to a carbocyclic ring system containing three to ten carbon atoms and no heteroatoms, and optionally containing one or two double bonds. Representative examples of a cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cycloononyl, and cyclodecyl.

[0013] The term “halogen” or “halo”, as used here, means Cl, Br, I or F.

[0014] The term "halomethyl," as used here, refers to a methyl group in which one, two, or three hydrogen atoms are replaced by a halogen. Representative examples of halomethyl include, but are not limited to, chloromethyl, difluoromethyl, and trifluoromethyl.

[0015] The term "heteroaryl," as used here, refers to an aromatic monocyclic ring, an aromatic bicyclic ring system, or an aromatic tricyclic ring system. Aromatic monocyclic rings are five- or six-membered rings containing at least one heteroatom independently selected from the group consisting of N, O, and S (e.g., 1, 2, 3, or 4 heteroatoms independently selected from O, S, and N). The five-membered aromatic monocyclic rings have two double bonds, and the six-membered aromatic monocyclic rings have three double bonds.The bicyclic heteroaryl groups are exemplified by a monocyclic heteroaryl ring attached to the starting molecular unit and fused to a monocyclic cycloalkyl group, a monocyclic aryl group, a monocyclic heteroaryl group, or a monocyclic heterocycle as defined herein. The tricyclic heteroaryl groups are exemplified by a monocyclic heteroaryl ring attached to the starting molecular unit and fused to two groups consisting of a monocyclic cycloalkyl group, a monocyclic aryl group, a monocyclic heteroaryl group, or a monocyclic heterocycle as defined herein.Representative examples of a monocyclic heteroaryl include, but are not limited to, pyridinyl (including pyridin-2-yl, pyridin-3-yl, and pyridin-4-yl), pyrimidinyl, pyrazinyl, thienyl, furyl, thiazolyl, thiadiazolyl, isoxazolyl, pyrazolyl, and 2-oxo-1,2-dihydropyridinyl. Representative examples of a bicyclic heteroaryl include, but are not limited to, chromenyl, benzothienyl, benzodioxolyl, benzotriazolyl, quinolinyl, thienopyrrolyl, thienothienyl, imidazothiazolyl, benzothiazolyl, benzofuranyl, indolyl, quinolinyl, imidazopyridine, benzooxadiazolyl, and benzopyrazolyl. Representative examples of a tricyclic heteroaryl include, but are not limited to, dibenzofuranyl and dibenzothienyl. The monocyclic, bicyclic and tricyclic heteroaryls are linked to the starting molecular unit via any carbon or nitrogen atom contained in the rings.

[0016] The term "heterocycle" or "heterocyclic" as used here refers to a monocyclic, bicyclic, or tricyclic heterocycle. A monocyclic heterocycle is a three-, four-, five-, six-, seven-, or eight-membered ring containing at least one heteroatom independently selected from the group consisting of O, N, and S. A three- or four-membered ring contains no or one double bond and one heteroatom selected from the group consisting of O, N, and S. A five-membered ring contains no or one double bond and one, two, or three heteroatoms selected from the group consisting of O, N, and S. A six-membered ring contains no, one, or two double bonds and one, two, or three heteroatoms selected from the group consisting of O, N, and S.The seven- and eight-membered ring contains no, one, two or three double bonds and one, two or three heteroatoms selected from the group consisting of O, N and S. Representative examples of monocyclic heterocycles include azetidinyl, azepanyl, aziridinyl, diazepanyl, 1,3-dioxanyl, 1,3-dioxolanyl, 1,3-dithiolanyl, 1,3-dithianyl, 1,3-dimethylpyrimidine-2,4(1H,3H)-dione, imidazolinyl, imidazolidinyl, Isothiazolinyl, isothiazolidinyl, isoxazolinyl, isoxazolidinyl, morpholinyl, oxadiazolinyl, oxadiazolidinyl, oxazolinyl, oxazolidinyl, oxetanyl, piperazinyl, piperidinyl, pyranyl, pyrazolinyl, pyrazolidinyl, pyrrolinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, Tetrahydropyridinyl, tetrahydrothienyl, thiadiazolinyl, thiadiazolidinyl, 1,2-Thiazinanyl, 1,3-Thiazinanyl, Thiazolinyl, Thiazolidinyl, Thiomorpholinyl, 1,1-Dioxidothiomorpholinyl (Thiomorpholine sulfone), Thiopyranyl and Trithianyl, without being limited thereto.The bicyclic heterocycle is a monocyclic heterocycle condensed to a phenyl group, or a monocyclic heterocycle condensed to a monocyclic cycloalkyl, or a monocyclic heterocycle condensed to a monocyclic cycloalkenyl, or a monocyclic heterocycle condensed to a monocyclic heterocycle, or a spiroheterocyclic group, or a monocyclic heterocycle bridging ring system in which two non-adjacent atoms of the ring are linked via an alkylene bridge with 1, 2, 3 or 4 carbon atoms or an alkenylene bridge with two, three or four carbon atoms. Representative examples of bicyclic heterocycles include benzopyranyl, benzothiopyranyl, chromanyl, 2,3-dihydrobenzofuranyl, 2,3-dihydrobenzothienyl, 2,3-dihydroisoquinoline, 2-azaspiro[3.3]heptan-2-yl, azabicyclo[2.2.1]heptyl (including 2-azabicyclo[2.2.1]hept-2-yl), 2,3-dihydro-1H-indolyl, isoindolinyl, octahydrocyclopenta[c]pyrrolyl, octahydropyrrolopyridinyl, and tetrahydroisoquinolinyl, but not limited thereto. Tricyclic heterocycles are exemplified by a bicyclic heterocycle fused to a phenyl group, or a bicyclic heterocycle fused to a monocyclic cycloalkyl, or a bicyclic heterocycle fused to a monocyclic cycloalkenyl, or a bicyclic heterocycle fused to a monocyclic heterocycle, or a bicyclic heterocycle in which two non-adjacent atoms of the bicyclic ring are linked via an alkylene bridge with 1, 2, 3, or 4 carbon atoms or an alkenylene bridge with two, three, or four carbon atoms.Examples of tricyclic heterocycles include octahydro-2,5-epoxypentalene, hexahydro-2H-2,5-methanocyclopenta[b]furan, hexahydro-1H-1,4-methanocyclopenta[c]furan, aza-adamantane (1-azatricyclo[3.3.1.1. 3,7 ] decane) and oxaadamantane (2-oxatricyclo [3.3.1.1 3,7 ] decane), without being limited to it. The monocyclic, bicyclic and tricyclic heterocycles are linked to the starting molecular unit via any carbon or nitrogen atom contained in the rings.

[0017] The term "hydroxy", as used here, stands for an -OH group.

[0018] In some cases, the number of carbon atoms in a hydrocarbyl substituent (e.g., alkylene, alkyl, or cycloalkyl) is indicated by the prefix "C x-y “specified, where x is the minimum number and y the maximum number of carbon atoms in the substituent. For example, “C 1-4-Alkylene" refers to an alkylene containing 1 to 4 carbon atoms.

[0019] One approach to ion detection is fluorescence-based detection, in which the ion binds to a molecule that either causes or quenches fluorescence. The optical signal (e.g., coupled to electronics such as a photodiode) can be used to determine the ion concentration. A class of sensors based on fluorophore / spacer / receptor chemistry has been used as a sodium sensor. While the fluorophore is natively fluorescent upon excitation, for example, no phosphor is observed when the metal ion is not bound to the receptor due to photoinduced electron transfer (PET) between the receptor and the fluorophore, which competes with fluorescence emission. Binding to a metal ion adjusts the receptor energy level, thereby quenching the competing PET and "activating" the fluorescence signal.

[0020] The present disclosure relates to fluorescence-based chemical sensors with a short spacer (e.g., methylamine, -CH2NH-) between a rigid ion receptor group and a fluorophore. It is noteworthy that the sensors described here can prevent the "folding quenching" that occurs in conventional sensors and that they can provide improved sensitivity to water pollutants.

[0021] In one aspect, the present revelation provides a connection with formula (I) or salts thereof: R 1 -CH2NH-G (I), in the R 1 a cyclic group with 5 to 12 members, wherein at least one ring atom is N, O or S, which optionally has at least one double bond between two adjacent ring atoms, wherein R 1 optionally with 1, 2, 3 or 4 R A is substituted and where R 1 optionally with 1 or 2 -(XR 2) is substituted; X is a bond, CH2, O, S, NH or N(CH3) at each occurrence independently; R 2 In each occurrence, independently, it is a cyclic group with 5 to 12 members, which optionally has at least one double bond between two adjacent ring atoms, where R 2 optionally includes at least one ring atom N, O or S, and wherein R 2 optionally with 1, 2, 3 or 4 R B is substituted; R A and R B in each occurrence is independently selected from the group consisting of -CH3, -CH2CH3, -CH2OH, -CH2NH2, -COCH3, -COOH, -CONH2, -CN, -OH, -OCH3, -NH2, -NHCH3, -N(CH3)2, -SH, -SCH3, halogen and halomethyl; G is a cyclic fluorophore, wherein G is attached to the starting molecular unit via a ring atom and wherein G is optionally substituted with -LT; L is a leftist selected from the group consisting of a bond, C 1-4-Alkylene, OC 1-4 -Alkylene, NHC 1-4 -Alkylene, SO2C1-4-alkylene and C1-4-alkylene-C6H4, T is selected from the group consisting of a leaving group, -OH, -NH2, -C(O)OH, a protected hydroxy group, a protected amino group and a protected carboxyl group.

[0022] R 1 can be a rigid cyclic group capable of forming a chelate or complex with an ion. In some embodiments, R comprises 1 at least one double bond between two adjacent ring atoms. R 1 It can, for example, contain 1, 2, 3, 4, or 5 double bonds between ring atoms. In some embodiments, R 1 an optionally substituted heteroaryl. R 1 This could be, for example, an optionally substituted thiazole, an optionally substituted diazine (such as 1,2-diazine, 1,3-diazine, or 1,4-diazine), or an optionally substituted pyridine. In some embodiments, R1 an optionally substituted thiazole.

[0023] In some embodiments, R is missing. A In some embodiments, at least one R A present. In some embodiments, R 1 with 1 or 2 R A substituted, each independently selected from -CH3, -CH2CH3, -CH2OH, -CH2NH2, -COCH3, -COOH, -CONH2, -CN, -OH, -OCH3, -NH2, -NHCH3, -N(CH3)2, -SH, -SCH3, halogen and halomethyl. In some embodiments, R 1 by 1 or 2 R A substituted, each one independently selected from -N(CH3)2, -SCH3 and -CF3. R 2 can be a rigid cyclic group optionally comprising 1, 2, or 3 heteroatoms selected from N, O, and S. In some embodiments, R comprises 2 at least one double bond exists between two adjacent ring atoms. In some embodiments, R 2An optionally substituted aryl, an optionally substituted heteroaryl, or an optionally substituted heterocycle with at least one double bond between two adjacent ring atoms. R 2 It could be, for example, an optionally substituted phenyl, an optionally substituted pyrrolidine, or an optionally substituted pyrimidine.

[0024] In some embodiments, R is missing. B In some embodiments, at least one R B present. In some embodiments, R 2 with 1 or 2 R B substituted, each independently selected from -CH3, -CH2CH3, -CH2OH, -CH2NH2, -COCH3, -COOH, -CONH2, -CN, -OH, -OCH3, -NH2, -NHCH3, -N(CH3)2, -SH, -SCH3, halogen and halomethyl. In some embodiments, R 2 by 1 or 2 R B substituted, each independently selected from -N(CH3)2, -SCH3 and -CF3.

[0025] In some embodiments, X is a bond. In some embodiments, XO, S, or NH is.

[0026] In some embodiments, the compounds with formula (I) or salts thereof have a structure with formula (Ia): in the X, R 2 and G as defined in formula (I).

[0027] In some embodiments, the compounds have a structure with formula (Ia), in which X is a bond. In some embodiments, the compounds have a structure with formula (Ia), in which R 2 or is.

[0028] In some embodiments, the compounds with formula (I) or a salt thereof have a structure with formula (Ib): in the R A and G as defined in formula (I).

[0029] In some embodiments, the compounds have a structure with formula (Ib), in which R A -N(CH3)2 is.

[0030] G can be any suitable fluorophore, such that when an ion binds to the compound, it produces a significantly stronger fluorescence signal compared to the signal produced when no ion is bound. For example, when no ion is bound, the compounds might produce only negligible or even undetectable fluorescence. When bound to an ion, however, the compounds can produce a stable, readily measurable fluorescence signal.

[0031] Suitable fluorophores include, but are not limited to, xanthene derivatives (e.g., fluorescein, rhodamine), benzene, anthracene, naphthalene and derivatives (e.g., dansyl, prodan), oxadiazole derivatives (e.g., pyridyloxazole, nitrobenzoxadiazole, benzoxadiazole, etc.), pyrene derivatives (e.g., Cascade Blue), oxazine derivatives (e.g., Nile Red, Nile Blue, cresyl violet, oxazine 170, etc.), acridine derivatives (e.g., proflavin, acridine orange, acridine yellow, etc.), arylmethine derivatives (e.g., auramine, crystal violet, malachite green, etc.), tetrapyrrole derivatives (e.g., porphine, phthalocyanine, bilirubin, etc.), and 1,2-bis(2-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid (BAPTA). 2-(2'-Morpholino-2'-oxoethoxy)-N,N-bis(hydroxycarbonylmethyl)aniline (MOBHA), carbazole, diphenylfuran and 1,8-naphthalimide.

[0032] In some embodiments, the compounds have a structure with formula (I), (Ia), or (Ib), in which G is or are anthracene, benzene, carbazole, diphenylfuran, naphthalene, 1,8-naphthalimide, porphyrin, pyrene, or derivatives thereof. In some embodiments, G is unsubstituted. In some embodiments, G is substituted with an -LT group as described in this document. In some embodiments, G is 1,8-naphthalimide optionally substituted with -LT. In some embodiments, G is optionally substituted with -LT.

[0033] The -LT group can form a covalent bond with a support material or a stationary phase such as a polymer. For example, the -LT group can react with a functional group of a polymer coating on a substrate, thereby forming a covalent bond and immobilizing the compounds on the substrate as described in this document.

[0034] In some embodiments, L is a bond, SO2C 1-4 -Alkylene or C 1-4 -Alkylene-C6H4. In some embodiments, L is CH2C6H4, for example, in some embodiments, L is SO2C2H4.

[0035] In some embodiments, T is a leaving group such as chloride, bromide, iodide, tosylate, mesylate, or triflate. In some embodiments, T is -OH, -NH₂, or -C(O)OH.

[0036] In some embodiments, T is a hydroxy, amino, or carboxyl group protected by a protecting group. The protected groups can be unprotected, yielding an -OH, -NH₂, or -C(O)OH group, respectively. The term "protecting group" refers to a unit that prevents chemical reactions from occurring at a heteroatom (such as N, O, or S) to which this protecting group is attached. Various protecting groups are well known in the field and include those described in detail in *Protective Groups in Organic Synthesis*, T.W. Greene and P.G. Wuts, 5th edition, John Wiley & Sons, 2014, which is incorporated herein in its entirety by reference.Suitable amino protecting groups include, but are not limited to, carbobenzyloxy (-NHCO-OCH2C6H5 or -NH-Cbz); t-butyloxycarbonyl (-NHCO-OC(CH3)3 or -NH-Boc); 9-fluorenylmethyloxycarbonyl (-NH-Fmoc); 2,2,2-trichloroethyloxycarbonyl (-NH-Troc); and allyloxycarbonyl (-NH-Alloc). In each of the preceding groups, -NH- represents the nitrogen from the amino group being protected. Suitable hydroxy protecting groups include, but are not limited to, methoxymethyl ether (MOM), tetrahydropyranyl ether (THP), t-butyl ether, allyl ether, benzyl ether, trimethylsilyl (TMS), t-butyldimethylsilyl (TBDMS), acetyl, benzoyl, and pivalic acid esters. Suitable carboxy protecting groups include, but are not limited to, methyl esters, t-butyl esters and benzyl esters.

[0037] In some embodiments, -LT is used; in some embodiments, G is used.

[0038] In some embodiments, the compounds described herein are selected from and / or a salt thereof.

[0039] In another aspect, the present disclosure provides a chemosensor device comprising: a compound as described above or a salt thereof, an optical detector a light source and a recording designed to touch an aqueous sample.

[0040] The compounds described here can be used as fluorescence-based chemical sensors (chemosenser compounds). It is noteworthy that these compounds can prevent the "folding quenching" of the fluorescence signal and that they can provide improved sensitivity in the detection of ions in an aqueous sample.

[0041] The chemosensor device can include any optical detector capable of detecting and / or measuring a fluorescence signal. In some embodiments, the optical detector includes a photodiode. The light source can include any source of visible light. In some embodiments, the light source includes a light-emitting diode (LED). The receptacle can be a tube, channel, or surface designed to contact the aqueous sample. The selection of optical detectors, light sources, and receptacles is part of the established knowledge in the field. For example, the chemosensor device can include a photodiode as the optical detector, an LED as the light source, and an inlet tube as the receptacle for the sample to be detected (as in [reference]). Fig. 1 shown).

[0042] The chemosensor device may have a surface on which the chemosensor compounds are immobilized. In some embodiments, the surface comprises a polymer coating or polymer layer. The polymer may, for example, be applied to a solid substrate. Suitable polymers include those with a functional group (for example, a hydroxyl, amino, or leaving group) that can react with the T-group of a compound as described herein, forming a covalent bond that causes the compound to be immobilized on the polymer surface or polymer layer. Non-restrictive examples of polymers include, for example, aminocellulose.

[0043] The chemosensor device may additionally include one or more functional units for operating the device, for example a power source, a control panel, a digital processor, a recording device, a data storage unit and a printer.

[0044] In some embodiments, the chemosensor device is connected to one or more chemical processing units. This allows, for example, real-time analysis of aqueous samples obtained from the chemical processing units and the recording of the results.

[0045] In another aspect, the present disclosure provides a machine comprising a chemosensor device as described herein. The machine can be used in an application where a volume of water is present and the water quality is monitored. The machine can be, for example, a water desalinator, a water softener, a water purifier, a water testing device, a fuel testing device, a coffee machine, a washing machine, an ice machine, a boiler, or a blood testing device. In some embodiments, an aqueous sample is taken during operation of the machine and fed to the chemosensor so that it can detect ions in the sample.

[0046] In yet another aspect, the present disclosure provides a method for detecting an ion in an aqueous sample, comprising: Touching the aqueous sample with a chemosensor device as described herein; Irradiation of the aqueous sample with light, whereupon the compound of the chemosensor device binds to the ion, causing the compound to generate a fluorescence signal; and Detecting the fluorescence signal.

[0047] The aqueous sample can be taken from any natural or industrial water source, or from any industrial, medical, or household appliance that uses, treats, or transports water. In some embodiments, the aqueous sample is taken from a water desalinator, water softener, water purifier, water testing device, fuel testing device, coffee maker, washing machine, ice machine, boiler, or blood testing device.

[0048] In some embodiments, a chemosensor device or a machine incorporating this device, as described herein, is connected to one or more chemical process units, and the ion detection method is performed continuously. For example, the aqueous sample can be continuously fed into the device or machine, and the detection method can be performed continuously so that the water quality in the sample is recorded and / or monitored. The continuous feeding, detection, recording, and / or monitoring process can be automated and performed according to a programmable schedule.

[0049] In some embodiments, the chemosensor device is designed to detect an ion consisting of Pb. 2+ , Ca 2+ , K + , N / a + , Cr 3+ , Hg 2+ , CD 2+ , Mg 2+ , As 3+ , As5+ and a combination thereof. In some embodiments, the ion is Pb. 2+ , Ca 2+ , Hg 2+ , CD 2+ , Mg 2+ or a combination thereof. In certain embodiments, the ion is Pb. 2+ , for example Pb 2+ in a natural water source or Pb 2+ in a sample taken from a water desalinator, a water softener, a water purifier, a water testing device, a fuel testing device, a coffee machine, a washing machine, an ice machine, a boiler or a blood testing device. Example

[0050] Using computer modeling, binding energies and fluorescence spectra of different spacers and receptors for the binding of a lead ion (Pb) are determined. 2+) simulated. As examples, the investigated molecules exhibit a 1,8-naphthalimide fluorophore, a methylamine or ethylamine spacer, and an optionally substituted thiazole group as a receptor for Pb binding. 2+ on ( Fig. 2) The molecules described herein can be synthesized using common (including commercially available) precursors and standard organic synthesis methods known in the field.

[0051] The bond strength depends on the dissociation constant (and thus the titration curve) based on the known equation K. d = c 0 e ΔG / k B T together, in the K d the dissociation constant, c° the standard reference concentration (1 mol), ΔG the free binding energy (usually on the order of -50 to -1,000 meV) and k BT is the Boltzmann constant multiplied by the absolute temperature. Further corrections can be made for correlated effects (Hill coefficient). The binding energy is calculated as the total energy of the molecule with the ion minus the total energy of the molecule and ion separated (i.e., ΔE). Bindung = E 0,gesamt - (E 0,Molekül + E 0,Ion ), where E0 is the calculated internal energy that can be extracted from the simulation).

[0052] The quantum chemistry code ORCA is used for these calculations. Several basis sets are employed in the calculation procedures. The geometry is optimized using a local density approximation (LDA) with the implicit solvation model CPCM (water) and a basis set def2-svp (Karlsruhe valence double zeta with polarization). The total energy is calculated using RI-MP2, again with CPCM / def2-svp. For LDA, a basis set correction is applied up to def2-qzvpp (quadruple zeta basis set), and for def2-svp (no solvation), an independent correlation correction from DLPNO-CCSD (T) is applied. These are the binding energies shown in Table 1. The fluorescence is calculated without solvation using a geometry of BLYP / def2-svp, a Hessian matrix of the normal state using BLYP / def2-svp, and a spectrum using TD-DFT BLYP / def2-svp.Fluorescence is calculated using the ORCA-ASA module.

[0053] The simulation methods are validated as follows. The binding energies are compared with literature on known receptor / ion pairs. These are often 10 to 30 times higher than expected because the formation energies are calculated using implicit solvation instead of explicit solvation. However, the results accurately indicate a qualitative ranking of the binding strengths. The optical spectra are compared with a naphthalimide-methylamine-thiazole molecule. Using BLYP / def2-svp, fluorescence can be successfully predicted, in agreement with experimental measurements, precisely when the Pb ion is bound.

[0054] The receptor-spacer chemistry does not reveal which of these would be suitable and which would not. It is noteworthy, however, that by conducting this review, some important properties for an effective fluorophore can be identified. All the molecules studied show calculated fluorescence when the Pb ion is bound at the lowest energy site and no fluorescence when the Pb is not bound (to some extent, with the exception of pyrimidinyl ethanolamine as a receptor spacer). Each receptor-spacer chemistry specifies an optimal binding site for the nitrogen atom of the spacer and one or more of the nitrogen and sulfur atoms of the receptor.

[0055] The geometry optimizations indicate that every chemistry with the ethylamine spacer resulted in a folded configuration in which the receptor is folded closer to the fluorophore. The energy gain from this folding is approximately 100 meV per molecule (LSD CPCM / def2-svp), suggesting a stable normal state. For at least one receptor (pyrimidinyl ethanolamine), subsequent Pb binding and fluorescence calculations indicate a stable binding site located close to the fluorophore. Fig.3) which causes PET to quench the fluorescence. Therefore, receptor / spacer pairs that allow proximity between an ion binding site and a fluorophore can generally be omitted. In particular, the number of bonds that can rotate (i.e., single bonds) can be minimized to prevent this "folding quenching." For high sensitivity (high binding strength), a longer measurement time is required among the unfolded structures, so different compounds may be suitable depending on the context—for a fast measurement with low sensitivity, "weak receptor" structures can be used, whereas for a longer measurement with high sensitivity, "strong receptor" structures can be used.

[0056] The trend in binding energies shows that the primary descriptive feature for binding strength is the number of electronegative atoms (e.g., N and S) bonded to the ion. Therefore, the highest sensitivity can occur when three atoms are located near the binding site, and lower sensitivity (and consequently a shorter measurement time) when only two atoms are near the binding site. The electronegative atoms can be located (in a conformation) on the same side of the molecule to bind to the cation. Depending on its size, sensitivity, and durability, the sensor device can be adapted for use with different types of chemosensor molecules, as shown in Table 1. Table 1. Receptor spacer unit structure Lead-binding energy (eV) effect (Thiazol-4-yl)methanamino -1,681 Weak to moderate receptor ({2-[(Methylthio)methyl] -1,3-thiazol-4-yl}methyl) amino -2,22 Strong receptor 1-[2-(2-Pyrimidinyl)-1,3-thiazol-4-yl]methanamino -2, 102 Strong receptor 1-(2-Pyrrolidin-1-yl-1,3-thiazol-4-yl)methanamino -1,907 Moderate receptor (2-(N,N-Dimethylamino)thiazo 1-4-yl)methanamino -1,837 Moderate receptor (2-Methylthiazol-4-yl)methanamino -1,609 Weak receptor {2-[4-(Trifluoromethyl)phenyl]-1,3-thiazol-4-yl}methylamino - -1,524 Weak receptor 2-[2-(2-Pyrimidinyl)-1,3-thiazol-4-yl]ethanamino -2,427 Folding 2-(2-Isopropyl-1,3-thiazol-4-yl)ethanamino -1,769 Folding 2-(2-Methyl-1,3-thiazol-4-yl)ethylamino -1,668 Folding (2-{2-[(Methylthio)methyl]-1,3-thiazol-4-yl}ethyl)amino -2,145 Folding 2-(1,3-thiazol-4-yl)ethanamino -1,599 Folding 2-(2-Amino-(1,3-thiazol-4-yl))ethanamino -1,747 Folding Examples of implementation include the following:

[0057] Example 1. Compound with formula (I) or salts thereof: R 1 -CH2NH-G (I), in the R 1 a cyclic group with 5 to 12 members, wherein at least one ring atom is N, O or S, which optionally has at least one double bond between two adjacent ring atoms, wherein R 1 optionally with 1, 2, 3 or 4 R A is substituted and where R 1 optionally with 1 or 2 -(XR 2 ) is substituted; X is a bond, CH2, O, S, NH or N(CH3) at each occurrence independently; R 2 In each occurrence, independently, it is a cyclic group with 5 to 12 members, which optionally has at least one double bond between two adjacent ring atoms, where R 2 optionally includes at least one ring atom N, O or S, and wherein R 2 optionally with 1, 2, 3 or 4 R B is substituted; R A and R BEach occurrence is independently selected from the group consisting of -CH3, -CH2CH3, -CH2OH, -CH2NH2, -COCH3, -COOH, -CONH2, -CN, -OH, -OCH3, -NH2, -NHCH3, -N(CH3)2, -SH, -SCH3, halogen and halomethyl; G is a cyclic fluorophore, wherein G is attached to the starting molecular unit via a ring atom and wherein G is optionally substituted with -LT;

[0058] L is a leftist selected from the group consisting of a bond, C 1-4 -Alkylene, OC 1-4 -Alkylene, NHC 1-4 -Alkylene, SO2C1-4-alkylene and C1-4-alkylene-C6H4, T is selected from the group consisting of a leaving group, -OH, -NH2, -C(O)OH, a protected hydroxy group, a protected amino group and a protected carboxyl group.

[0059] Example 2. Compound according to claim Example 1 or a salt thereof, wherein R 1 is an optionally substituted heteroaryl.

[0060] Example 3. Connection according to Example 1 or 2, where R 1 is an optionally substituted thiazole.

[0061] Example 4. Connection according to one of examples 1 to 3, where R 2 is an optionally substituted aryl, an optionally substituted heteroaryl or an optionally substituted heterocycle with at least one double bond between two adjacent ring atoms.

[0062] Example 5. Compound according to Example 1 or a salt thereof, with a structure with the formula (Ia):

[0063] Example 6. Compound according to Example 5 or a salt thereof, where X is a bond.

[0064] Example 7. Compound according to Example 5 or 6 or a salt thereof, wherein R 2 or is.

[0065] Example 8. Compound according to Example 1 or a salt thereof, with a structural formula (Ib):

[0066] Example 9. Compound according to Example 8 or a salt thereof, where R A-N(CH3)2 is.

[0067] Example 10. Compound according to any of Examples 1 to 9 or a salt thereof, wherein G is anthracene, benzene, carbazole, diphenylfuran, naphthalene, 1,8-naphthalimide, porphyrin or pyrene; and wherein G is optionally substituted with -LT.

[0068] Example 11. Compound according to any of Examples 1 to 10 or a salt thereof, wherein G is 1,8-naphthalimide, optionally substituted with -LT.

[0069] Example 12. Compound according to any of Examples 1 to 11 or a salt thereof, where G is, optionally substituted with one or more -LTs.

[0070] Example 13. Compound according to any of Examples 1 to 12 or a salt thereof, where -LT is.

[0071] Example 14. Compound according to Example 1, selected from the group consisting of: and or a salt thereof.

[0072] Example 15. Chemosensor device comprising: a compound of Example 1 or a salt thereof, an optical detector, a light source and a receptacle designed to touch an aqueous sample.

[0073] Example 16. Chemosensor device according to Example 15, wherein the device is connected to one or more chemical process units.

[0074] Example 17. Machine comprising a chemosensor device according to Example 15, wherein the machine is a water desalinator, a water softener, a water purifier, a water testing device, a fuel testing device, a coffee machine, a washing machine, an ice machine, a boiler or a blood testing device.

[0075] Example 18. Method for detecting an ion in an aqueous sample, comprising: touching the aqueous sample with a chemosensor device according to Example 15; irradiating the aqueous sample with light, whereupon the compound of the chemosensor device binds to the ion, causing the compound to generate a fluorescence signal; and detecting the fluorescence signal.

[0076] Example 19. Method according to Example 18, wherein the aqueous sample is taken from a water desalinator, a water softener, a water purifier, a water testing device, a fuel testing device, a coffee machine, a washing machine, an ice machine, a boiler or a blood testing device.

[0077] Example 20. Method according to Example 18, wherein the chemosensor device is connected to one or more chemical process units, and wherein the method is carried out continuously.

[0078] Example 21. Procedure according to Example 14, wherein the ion Pb 2+ , Ca 2+ , K + , N / a + , Cr 3+ , Hg 2+ , CD 2+ , Mg 2+ , As 3+ , As 5+ or a combination thereof.

[0079] Various features and advantages of the application are set out in the following claims.

Claims

[1] Compound of formula (I) or salts thereof: R 1- CH 2 NH-G (I), in the R 1 is a cyclic group having 5 to 12 members, wherein at least one ring atom is N, O or S, optionally having at least one double bond between two adjacent ring atoms, wherein R 1 optionally with 1, 2, 3 or 4 R A is substituted and where R 1 optionally with 1 or 2 -(XR 2 ) is substituted; X is independently a bond, CH2, O, S, NH or N(CH3) in each occurrence; R 2 at each occurrence independently represents a cyclic group of 5 to 12 members, optionally having at least one double bond between two adjacent ring atoms, where R 2 optionally has at least one ring atom N, O or S, and wherein R 2 optionally with 1, 2, 3 or 4 R B is substituted; R A and RB at each occurrence is independently selected from the group consisting of -CH3, -CH2CH3, -CH2OH, -CH2NH2, -COCH3, -COOH, -CONH2, -CN, -OH, -OCH3, -NH2, -NHCH3, -N(CH3)2, -SH, -SCH3, halogen and halomethyl; G is a cyclic fluorophore, wherein G is attached to the parent molecular moiety via a ring atom and wherein G is optionally substituted with -LT; L is a linker selected from the group consisting of a bond, C 1-4 -Alkylene, OC 1-4 -Alkylene, NHC 1-4 -alkylene, SO2C1-4-alkylene and C1-4-alkylene-C6H4, T is selected from the group consisting of a leaving group, -OH, -NH2, -C(O)OH, a protected hydroxy group, a protected amino group and a protected carboxy group. [2] A compound according to claim 1 or a salt thereof, wherein R 1 is an optionally substituted heteroaryl. [3] A compound according to claim 1, wherein R 1is an optionally substituted thiazole. [4] A compound according to Example 1 or a salt thereof, wherein R 2 an optionally substituted aryl, an optionally substituted heteroaryl or an optionally substituted heterocycle having at least one double bond between two adjacent ring atoms. [5] A compound according to claim 1 or a salt thereof, having a structure of formula (Ia): [6] A compound according to claim 5 or a salt thereof, wherein X is a bond. [7] A compound according to claim 5 or a salt thereof, wherein R 2 or is. [8] A compound according to claim 1 or a salt thereof, having a structural formula (Ib): [9] A compound according to claim 8 or a salt thereof, wherein R A - N(CH3)2. [10] A compound according to claim 1 or a salt thereof, wherein G is anthracene, benzene, carbazole, diphenylfuran, naphthalene, 1,8-naphthalimide, porphyrin or pyrene; and wherein G is optionally substituted with -LT. [11] A compound according to claim 1 or a salt thereof, wherein G is 1,8-naphthalimide optionally substituted with -LT. [12] A compound according to claim 1 or a salt thereof, wherein G is optionally substituted with one or more -LT. [13] A compound according to claim 1 or a salt thereof, wherein -LT is. [14] A compound according to claim 1 selected from the group consisting of: and or a salt thereof. [15] Chemosensor device comprising: a compound according to claim 1 or a salt thereof, an optical detector, a light source and a receptacle designed to contact an aqueous sample. [16] A chemosensor device according to claim 15, wherein the device is connected to a single or multiple chemical processing units. [17] A machine comprising a chemical sensor device according to claim 15, wherein the machine is a water desalinator, a water softener, a water purifier, a water testing device, a fuel testing device, a coffee maker, a washing machine, an ice maker, a boiler or a blood testing device. [18] A method for detecting an ion in an aqueous sample, comprising: Contacting the aqueous sample with a chemosensor device according to claim 15; irradiating the aqueous sample with light, whereupon the compound of the chemosensor device binds to the ion, causing the compound to generate a fluorescent signal; and Detecting the fluorescence signal. [19] The method of claim 18, wherein the aqueous sample is taken from a water demineralizer, a water softener, a water purifier, a water testing device, a fuel testing device, a coffee maker, a washing machine, an ice maker, a boiler, or a blood testing device. [20] The method of Example 18, wherein the chemosensor device is connected to a single or multiple chemical processing units, and wherein the method is carried out continuously. [21] The process of Example 14, wherein the ion Pb 2+ , Ca 2+ , K + , N / a + , Cr 3+ , Ed. 2+ , CD 2+ , Mg 2+ , As 3+ , As 5+ or a combination thereof.