Compositions containing energy-sensitive adducts of acetylenic compounds

Abstract

The present invention provides energy-sensitive adducts of an acetylenic compound having at least 25 carbon atoms with at least one substance, compositions containing the adducts, and industrial uses thereof, such as dosimetry. The adducts and compositions are sensitive to energy arising from radiation sources such as ionizing radiation, electromagnetic radiation, or heat. The X-ray structure of a salt of n-butanoic acid and morpholine shows two distinct hydrogen-bonding interactions.

Description

[Technical Field]

[0001] The disclosed and / or claimed inventive concept(s) provide energy sensitive adducts of acetylenic compounds. [Background technology]

[0002] In facilities where radiation sources are used, such as hospitals where cancer patients receive radiation therapy or blood banks where blood products are irradiated, various methods are used to quantitatively measure radiation exposure. These methods include the use of thermoluminescent dosimeters (TLDs), ionizing radiation detectors, photographic film, and radiochromic materials. TLDs are inconvenient because they require a complex and time-consuming reading process. Ionizing radiation detectors are inconvenient, cumbersome, and require complex setup. Photographic film requires a time-consuming chemical development process before reading. Radiochromic materials require a complex series of steps to calculate the radiation dose.

[0003] Photochromic polyacetylenes that respond to radiation exposure have been disclosed in various U.S. patents, namely, U.S. Pat. Nos. 4,066,676, 4,581,315, 3,501,302, 3,501,297, 3,501,303, 3,501,308, 3,772,028, 3,844,791, and 3,954,816. Recording images or radiation dose information using these polyacetylene compounds presents various problems and drawbacks, including insufficient resolution, clarity, and color instability of the imaged patterns. Other drawbacks include relatively slow development and, in some cases, the need for imaging at extremely low temperatures or excessively high radiation dose levels, which can be impractical.

[0004] A preferred radiation-sensitive material in a radiation dosimeter is a dispersion of crystalline 10,12-pentacosadiynoic acid (PCDA). Exposing monomeric PCDA crystals to ionizing radiation leads to polymerization, as the degree of polymerization increases with radiation exposure. The amount of polymerization (and therefore radiation exposure) can be determined by measuring either the optical density or spectral absorption of the exposed dosimeter. However, these parameters have been found to vary with the temperature of the device used during the measurement, as well as the thickness of the PCDA dispersion. To maximize the accuracy of radiation dosimetry, the effects of temperature and thickness must be accounted for.

[0005] Dosimetry film provides a method for measuring radiation exposure at a point, but its primary use is to obtain a two-dimensional map of radiation exposure, i.e., radiation exposure at multiple points in a two-dimensional array. A typical user can measure an 8" x 10" piece of film with a spatial resolution of 75 dpi, producing a map of radiation exposure at 450,000 points. Of course, other resolutions can be used to produce a map of radiation exposure.

[0006] U.S. Patent No. 5,637,876 discloses a radiation dosimeter for measuring radiation levels to which a patient is exposed during radiation therapy, typically comprising a substrate having a layer of radiation-sensitive material thereon. The radiation-sensitive material has an optical density that varies systematically with the degree of radiation exposure. The dosimeter may be in the form of a card or flexible substrate that can be mounted on the patient or irradiation target and can be mounted or slid into a radiation dose reader equipped with a reflection or transmission densitometer.

[0007] The solid-state 1,4-addition polymerization of diacetylenes can be initiated by radiation and heat, leading to conjugated ene-yne ​​polymer chains. This reaction is believed to occur only when the topochemical parameters of the diacetylene packing are optimal. The first report of a topochemical reaction in the solid state was in 1964 for alkene systems, described by Schmidt, who proposed that the carbon-carbon double bonds must be separated by a maximum distance of 4.2 Å for successful polymerization. In 1969, Wegner reported the first example of solid-state diacetylene polymerization. Fifteen years later, Enkelmann proposed strict criteria for diacetylene reactions: adjacent diacetylene monomers react when the reactive groups have an optimal orientation angle (θ) relative to the crystallographic axis of 45°, the C1-C4' contact distance (d) is ≤3.8 Å, and the translational repeat interval (r) is ≤4.9 Å. Diacetylene polymerization parameters highlight the importance of molecular organization in topochemical reactions.

[0008] The monomer-to-polymer transition can be clearly observed by a color change from colorless to blue due to rearrangement of the diacetylene monomer to yield an ene-yne ​​chromophore. The blue color is due to a π-π* transition in the regularly conjugated chain, accompanied by chain rearrangements that control the degree of diacetylene polymerization. Additional external stimuli on polymerized diacetylenes (polydiacetylenes), such as prolonged heating, pH changes, treatment with organic solvents, mechanical stress, and ligand-receptor interactions, can induce polydiacetylenes to exhibit colors ranging from blue to red to yellow. These color changes can be explained by conformational rearrangements within the polydiacetylene assemblies that disrupt the conjugated backbone, reducing π-orbital overlap and widening the HOMO-LUMO energy gap, thereby allowing polydiacetylenes to absorb higher-energy light.

[0009] PCDA, a commercially important diacetylene, is used to produce colorimetric changes in practical chemical sensors, biosensors, and dosimeters. Although PCDA is moderately photoreactive, further tuning of the photoreactivity is of considerable interest, especially for radiation dosimetry applications. Covalent modification provides a viable strategy for producing tailored photoreactivity in PCDA analogs.

[0010] Because the solid-state reactivity of diacetylenes is due to their crystal packing arrangement, a simpler strategy is to address the reactivity of dialkynes by modifying noncovalent interactions through the formation of cocrystals or salts. Whether a cocrystal or salt forms depends on the difference in pKa of the two components. For cocrystals, the ΔpKa should be <2-3 log units, while for salt formation, the difference is expected to be larger.

[0011] In the Journal of Applied Polymer Science, 2011, Vol. 20(5), 2809-2820, Scoville and Shirley studied the thermal color change of PCDA combined with four aromatic compounds, benzene, furan, thiophene, and cyclopentadiene, when sequentially exposed to UV radiation. Using Raman spectroscopy and solid-state fluorescence spectroscopy, no difference was observed between PCDA itself and benzene, furan, or thiophene, with the blue-to-red color change occurring between 80 and 100°C. However, the addition of cyclopentadiene resulted in a color change at significantly higher temperatures, in the range of 180 to 200°C.

[0012] In Radiation Physics and Chemistry, 2012, Vol. 81(1), pp. 70-76, Abdel-Fattah et al. investigated the dosimetry properties of gamma-radiation-sensitive labels based on polyvinyl butyral and PCDA. The color intensity of the label was proportional to the absorbed radiation dose. The useful radiation dose range was 15 Gy to 2 kGy, depending on the concentration of PCDA monomer.

[0013] Compounds and compositions according to the disclosed and / or claimed inventive concept(s) have been found to have excellent phototonation performance, which can be used as radiation-sensitive materials in radiation-sensitive devices for detecting and measuring high-energy radiation, such as chemical sensors, biosensors, and dosimeters, in various industrial and medical applications. These compounds and compositions have excellent energy sensitivity to a wide range of energy sources, including heat, electromagnetic radiation, ionizing radiation, gamma rays, UV rays, infrared rays, visible radiation, and X-rays. Summary of the Invention

[0014] In a first aspect, the disclosed and / or claimed inventive concept(s) provides an energy sensitive adduct derived from at least one functionalized or non-functionalized acetylenic compound having at least 25 carbons and at least one substance.

[0015] In a second aspect, the disclosed and / or claimed inventive concept(s) provides a composition comprising an energy sensitive adduct derived from at least one functionalized or non-functionalized acetylenic compound having at least 25 carbons and at least one substance.

[0016] In a third aspect, the disclosed and / or claimed inventive concept(s) provides a radiation sensitive device for detecting and measuring high energy radiation, comprising a radiation dosimeter including an energy sensitive adduct derived from at least one functionalized or non-functionalized acetylenic compound having at least 25 carbons and at least one substance.

[0017] In a fourth aspect, the disclosed and / or claimed inventive concept(s) provides an energy sensitive adduct derived from 10,12-pentacosadiynoic acid and at least one material selected from the group consisting of functionalized or non-functionalized alkylamines, dialkylamines, trialkylamines, quaternary amines, pyridines, azopyridines, bipyridyls, pyrimidines, pyrazines, piperidines, bipiperidines, morpholines, and combinations thereof.

[0018] In a fifth aspect, the disclosed and / or claimed inventive concept(s) provides a composition comprising an energy sensitive adduct derived from 10,12-pentacosadiynoic acid and at least one material selected from the group consisting of functionalized or functionalized alkylamines, dialkylamines, trialkylamines, quaternary amines, pyridines, azopyridines, bipyridyls, pyrimidines, pyrazines, piperidines, bipiperidines, morpholines, and combinations thereof.

[0019] In a sixth aspect, the disclosed and / or claimed inventive concept(s) provides a radiation sensitive device for detecting and measuring high energy radiation comprising a radiation dosimeter comprising an energy sensitive adduct derived from 10,12-pentacosadiynoic acid and at least one material selected from the group consisting of functionalized or functionalized alkylamines, dialkylamines, trialkylamines, quaternary amines, pyridines, azopyridines, bipyridyls, pyrimidines, pyrazines, piperidines, bipiperidines, morpholines, and combinations thereof. [Brief explanation of the drawings]

[0020] [Figure 1] 1 shows the X-ray structure of a salt of n-butanoic acid and morpholine, showing two different hydrogen bonding interactions. DETAILED DESCRIPTION OF THE INVENTION

[0021] Before describing in detail at least one aspect of the disclosed and / or claimed inventive concept(s), it is to be understood that the disclosed and / or claimed inventive concept(s) are not limited in their application to the details of construction or arrangement of parts, steps, or methodologies set forth in the following description or drawings. The disclosed and / or claimed inventive concept(s) may be embodied in other embodiments or practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting.

[0022] Unless otherwise defined herein, terminology used in connection with the disclosed and / or claimed inventive concept(s) should be understood to have the meaning commonly understood by those of ordinary skill in the art. Further, unless otherwise required by context, singular terms include plurals and plural words include the singular.

[0023] All patents, published patent applications, and non-patent literature referenced in any portion of this application are expressly incorporated by reference herein in their entirety to the same extent as if each individual patent or application were specifically and individually indicated to be incorporated by reference.

[0024] All of the articles and / or methods disclosed herein can be made and executed without undue experimentation based on the present disclosure. While the articles and methods of the disclosed and / or claimed inventive concept(s) have been described in terms of embodiments, it will be apparent to those skilled in the art that changes may be made to the articles and / or methods, or in the steps or sequence of steps, described herein without departing from the concept, spirit and scope of the disclosed and / or claimed inventive concept(s). All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the disclosed and / or claimed inventive concept(s).

[0025] Unless otherwise indicated, as used in accordance with the present disclosure, the following terms shall be understood to have the following meanings:

[0026] When used in conjunction with the term "comprising," the use of the words "a" or "an" can mean "one," but is also consistent with the meanings "one or more," "at least one," and "one or more than one." The use of the term "or" is used to mean "and / or," unless expressly intended to refer only to alternatives when alternatives are mutually exclusive, although this disclosure supports definitions that refer only to alternatives and "and / or."

[0027] Throughout this application, the term "about" is used to indicate that a value includes the variation of inherent error of the device for measuring the quantity, and this technique is used to determine the value or variation present in the research question. For example, and not by way of limitation, when the term "about" is used, the specified value may vary by plus or minus 12 percent, or plus or minus 11 percent, or plus or minus 10 percent, or plus or minus 9 percent, or plus or minus 8 percent, or plus or minus 7 percent, or plus or minus 6 percent, or plus or minus 5 percent, or plus or minus 4 percent, or plus or minus 3 percent, or plus or minus 2 percent, or plus or minus 1 percent.

[0028] Use of the term "at least one" should be understood to include not only 1 but any number greater than 1, such as, but not limited to, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc. The term "at least one" can extend up to 100 or 1000 or more depending on the accompanying term. Furthermore, 100 / 1000 numbers are not considered limiting, as higher or lower numbers will also provide sufficient results. Additionally, use of the term "at least one of X, Y and Z" should be understood to include not only X alone, Y alone, and Z alone, but also any combination of X, Y, and Z. The use of conventional ordinal terms (i.e., "first," "second," "third," "fourth," etc.) is for the sole purpose of distinguishing between two or more items and does not imply any consequential, sequential, or important nature of one item relative to another, unless otherwise specified.

[0029] As used herein, the words "comprising" (and any form of "comprising," such as "comprise" and "comprises"), "having" (and any form of "having," such as "have" and "has"), "including" (and any form of "including," such as "includes" and "include"), or "containing" (and any form of "containing," such as "contains" and "contain") are inclusive, i.e., open-ended, and do not exclude additional, unrecited elements or method steps. As used herein, the term "or combinations thereof" refers to all permutations and combinations of the listed items preceding the term. For example, "A, B" Xn , BXn+1 , or a combination thereof (A, B Xn ,B Xn+1 , or combinations thereof)" means A, B Xn , B Xn+1 , A.B. Xn , A.B. Xn+1 , B Xn B Xn+1 , or AB Xn B Xn+1 and, if the order is important in the particular context, B Xn A, B Xn+1 A, B Xn+1 B Xn , B Xn+1 B Xn A, B Xn B Xn+1 A, AB Xn+1 B Xn , B Xn AB Xn+1 , or B Xn+1 AB Xn Continuing with this example, B Xn B Xn , AAA, M.B. Xn , B Xn B Xn B Xn+1 , AAAB Xn B Xn+1 B Xn+1 B Xn+1 B Xn+1 , B Xn+1 B Xn B Xn AAA, B Xn+1 AB Xn AB Xn B Xn Those skilled in the art will understand that, unless otherwise clear from the context, there is typically no limit to the number of items or terms in any combination.

[0030] The term "each independently selected from the group consisting of" means that when a group occurs more than once in a structure, the group may be independently selected on each occurrence.

[0031] The term "hydrocarbyl" includes straight and branched chain alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl groups, and combinations thereof, optionally with heteroatom(s). Hydrocarbyl groups may be monovalent, divalent, or polyvalent.

[0032] The term "alkyl" refers to a functionalized or non-functionalized monovalent branched or cyclic C-C alkyl group, optionally with one or more heteroatoms. 60 In one non-limiting embodiment, alkyl is a C-C 45 In another non-limiting embodiment, alkyl is a C-C hydrocarbyl group. 30 It is a hydrocarbyl group. Non-limiting examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, tert-octyl, iso-norbornyl, n-dodecyl, tert-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. The definition of "alkyl" also includes groups resulting from a combination of linear, branched, and / or cyclic structures.

[0033] The term "aryl" refers to a functionalized or non-functionalized monovalent aromatic hydrocarbyl group, optionally containing one or more heteroatoms. The definition of aryl includes carbocyclic and heterocyclic aromatic groups. Non-limiting examples of aryl groups include phenyl, naphthyl, indenyl, indanyl, azulenyl, fluorenyl, anthracenyl, furyl, thienyl, pyridyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, 2-pyrazolinyl, pyrazolidinyl, isoxazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,3-triazolyl, 1,3,4-thiadiazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-triazinyl, 1,3,5-trithianyl, indolizinyl, Examples include indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furanyl, 2,3-dihydrobenzofuranyl, benzo[b]thiophenyl, 1H-indazolyl, benzimidazolyl, benzthiazolyl, purinyl, 4H-quinolizinyl, isoquinolizinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 1,8-naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and pyrazolo[1,5-c]triazinyl.

[0034] The term "aralkyl" refers to an alkyl group containing one or more aryl substituents, where "aryl" and "alkyl" are defined above. Non-limiting examples of aralkyl groups include benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like.

[0035] The term "alkylene" refers to a functionalized or non-functionalized, divalent, straight-chain, branched-chain, or cyclic C-C alkylene, optionally with one or more heteroatoms. 40In one non-limiting embodiment, alkylene is a C-C 30 In another non-limiting example, alkylene is a C-C group. 20 Non-limiting examples of alkylene groups include: [ka] Examples include:

[0036] The term "arylene" refers to a functionalized or unfunctionalized divalent aromatic hydrocarbyl group, optionally containing one or more heteroatoms. The definition of arylene includes carbocyclic and heterocyclic groups. Non-limiting examples of arylene groups include phenylene, naphthylene, pyridinylene, and the like.

[0037] The term "heteroatom" refers to oxygen, nitrogen, sulfur, silicon, phosphorus, or a halogen. Heteroatom(s) may be present as part of a functional group containing one or more heteroatoms. Non-limiting examples of heteroatom-containing functional groups include ether groups, hydroxy groups, epoxy groups, carbonyl groups, carboxamide groups, carboxylic ester groups, carboxylic acid groups, imine groups, imide groups, amine groups, sulfone groups, sulfonamide groups, phosphonic groups, and silane groups. Heteroatom(s) may also be present as part of a ring, such as in heteroaryl and heteroarylene groups.

[0038] The term "halogen" or "halo" refers to Cl, Br, I, or F.

[0039] The term "ammonium" includes protonated NH3 and protonated primary, secondary, and tertiary organic amines.

[0040] The term "functionalized" with respect to any moiety refers to the presence of one or more functional groups on the moiety. Various functional groups can be introduced to the moiety by functionalization reactions known to those skilled in the art. Non-limiting examples of functionalization reactions include alkylation, epoxidation, sulfonation, hydrolysis, amidation, esterification, hydroxylation, dihydroxylation, amination, ammonolysis, acylation, nitration, oxidation, dehydration, elimination, hydration, dehydrogenation, hydrogenation, acetalization, halogenation, dehydrohalogenation, Michael addition, aldol condensation, Cannizzaro reaction, Mannich reaction, Claisen condensation, Suzuki coupling, and the like. In one non-limiting embodiment, the term "functionalized" with respect to any moiety refers to another functional group on the moiety selected from the group consisting of alkyl, alkenyl, hydroxyl, carboxyl, halogen, alkoxy, amino, imino, and combinations thereof.

[0041] The term "monomer" refers to a small molecule that, during polymerization, chemically bonds with one or more monomers of the same or different type to form a polymer.

[0042] The term "polymer" refers to a large molecule comprising one or more types of monomer residues (repeating units) joined by covalent chemical bonds. By this definition, a polymer encompasses compounds in which the number of monomer units can range from very few, which may more commonly be referred to as oligomers, to very many. Non-limiting examples of polymers include homopolymers and non-homopolymers such as copolymers, terpolymers, tetrapolymers, and higher composites. Polymers can have a random, block, and / or alternating structure.

[0043] The term "homopolymer" refers to a polymer consisting essentially of a single monomer type.

[0044] The term "non-homopolymer" refers to a polymer that contains more than one monomer type.

[0045] The term "copolymer" refers to a non-homopolymer containing two different monomer types.

[0046] The term "terpolymer" refers to a non-homopolymer containing three different monomer types.

[0047] The term "branched" refers to any non-linear molecular structure. The term includes both branched and hyperbranched structures.

[0048] All percentages, ratios and proportions used herein are by weight unless otherwise specified.

[0049] In a first aspect, the disclosed and / or claimed inventive concept(s) provides an energy sensitive adduct derived from at least one functionalized or non-functionalized acetylenic compound having at least 25 carbons and at least one substance.

[0050] In non-limiting embodiments, functionalized or non-functionalized acetylenic compounds according to the disclosed and / or claimed inventive concept(s) comprise at least one acetylenic moiety and, optionally, at least one reactive moiety. In other non-limiting embodiments, functionalized or non-functionalized acetylenic compounds according to the disclosed and / or claimed inventive concept(s) comprise at least one acetylenic moiety and at least one reactive moiety.

[0051] In one non-limiting embodiment, a functionalized or non-functionalized acetylenic compound according to the disclosed and / or claimed inventive concept(s) comprises at least two acetylenic moieties and, optionally, at least one reactive moiety. In another non-limiting embodiment, a functionalized or non-functionalized acetylenic compound according to the disclosed and / or claimed inventive concept(s) comprises at least two acetylenic moieties and at least one reactive moiety.

[0052] In one non-limiting embodiment, the reactive moiety is selected from the group consisting of functionalized or non-functionalized carboxyl, hydroxy, epoxy, amino, aldehyde, keto, amide, ester, nitrile, (meth)acryloyl, urethane, ether, and combinations thereof.

[0053] In one non-limiting embodiment, the reactive moiety is a functionalized or non-functionalized carboxyl moiety.

[0054] In one non-limiting embodiment, the functionalized or non-functionalized acetylenic compound according to the disclosed and / or claimed inventive concept(s) is selected from the group consisting of pentacosadiynoic acid, hexacosadiynoic acid, heptacosadiynoic acid, octacosadiynoic acid, nonacosadiynoic acid, triacontanediynoic acid, and combinations thereof.

[0055] In one non-limiting embodiment, the functionalized or non-functionalized acetylenic compound is 10,12-pentacosadiynoic acid.

[0056] In one non-limiting embodiment, the material according to the disclosed and / or claimed inventive concept(s) is selected from the group consisting of a polar material, a non-polar material, an organic material, an inorganic material, and an organometallic material.

[0057] In one non-limiting embodiment, the material according to the disclosed and / or claimed inventive concept(s) is selected from the group consisting of functionalized or non-functionalized aliphatic hydrocarbons, alicyclic hydrocarbons, heterocyclic hydrocarbons, aromatic hydrocarbons, heteroaromatic hydrocarbons, olefinic hydrocarbons, and polyolefinic hydrocarbons.

[0058] In one non-limiting embodiment, the substance according to the disclosed and / or claimed inventive concept(s) is selected from the group consisting of an organic acid, an organic base, an inorganic acid, an inorganic base, a complex former, a crystal former, a co-crystal former, and combinations thereof.

[0059] In one non-limiting embodiment, the material according to the disclosed and / or claimed inventive concept(s) is selected from the group consisting of functionalized or non-functionalized aliphatic amines, cycloaliphatic amines, heterocyclic amines, aromatic amines, heteroaromatic amines, and combinations thereof.

[0060] In one non-limiting embodiment, the material according to the disclosed and / or claimed inventive concept(s) is selected from the group consisting of functionalized or non-functionalized alkylamines, dialkylamines, trialkylamines, quaternary amines, pyridines, azopyridines, bipyridyls, pyrimidines, pyrazines, piperidines, bipiperidines, morpholines, and combinations thereof.

[0061] Non-limiting examples of organic bases include 4,4'-azopyridine, 4,4'-bipyridyl, trans-1,2-bis(4-pyridyl)ethylene, 4,4'-bipiperidine, morpholine, diethylamine, n-butylamine, and combinations thereof. Other suitable examples of organic bases are listed in Ullmann's Encyclopedia of Industrial Chemistry, 7 th Edition, 2002, Wiley-VCH Verlag GmbH & Co. KGaA, the contents of which are incorporated herein by reference in their entirety.

[0062] In one non-limiting embodiment, the substance according to the disclosed and / or claimed inventive concept(s) is selected from the group consisting of inorganic bases.

[0063] In one non-limiting embodiment, the material according to the disclosed and / or claimed inventive concept(s) is selected from the group consisting of hydrides, oxides, hydroxides, cyanides, carbonates, bicarbonates, and combinations thereof of alkali metal and alkaline earth metal elements.

[0064] Other suitable examples of inorganic bases are listed in Ullmann's Encyclopedia of Industrial Chemistry, 7 th Edition, 2002, Wiley-VCH Verlag GmbH & Co. KGaA, the contents of which are incorporated herein by reference in their entirety.

[0065] In one non-limiting embodiment, an energy sensitive adduct derived from at least one functionalized or non-functionalized acetylenic compound having at least 25 carbons and at least one substance in accordance with the disclosed and / or claimed inventive concept(s) is more energy sensitive than the acetylenic compound without the substance present.

[0066] In another non-limiting embodiment, an energy sensitive adduct derived from at least one functionalized or non-functionalized acetylenic compound having at least 25 carbons and at least one substance in accordance with the disclosed and / or claimed inventive concept(s) has reduced energy sensitivity compared to the acetylenic compound in the absence of the substance.

[0067] In one non-limiting embodiment, the energy sensitive adduct in accordance with the disclosed and / or claimed inventive concept(s) is sensitive to energy derived from ionizing radiation, electromagnetic radiation, or heat. In another non-limiting embodiment, the energy sensitive adduct in accordance with the disclosed and / or claimed inventive concept(s) is sensitive to ionizing radiation, including gamma rays or x-rays. In yet another embodiment, the energy sensitive adduct in accordance with the disclosed and / or claimed inventive concept(s) is sensitive to electromagnetic radiation, including visible light, ultraviolet light, or infrared light.

[0068] In one non-limiting embodiment, the energy sensitive adduct according to the disclosed and / or claimed inventive concept(s) is in the form of a salt, a co-crystal, a polymorph, or an amorphous solid solution. In another embodiment, the energy sensitive adduct according to the disclosed and / or claimed inventive concept(s) is in the form of a salt or a co-crystal.

[0069] In a second aspect, the disclosed and / or claimed inventive concept(s) provides a composition comprising an energy sensitive adduct derived from at least one functionalized or non-functionalized acetylenic compound having at least 25 carbons and at least one substance.

[0070] In one non-limiting embodiment, the composition comprising an energy-sensitive adduct derived from at least one functionalized or non-functionalized acetylenic compound having at least 25 carbons and at least one substance includes at least one functional ingredient selected from the group consisting of a binder, a plasticizer, an activator, a solvent, a second energy-sensitive material, a dye, a transducer material, a surfactant, a catalyst, and combinations thereof.

[0071] Non-limiting examples of binders include homopolymers, copolymers, graft copolymers, block copolymers, polymer alloys, and mixtures thereof. Numerous monomers and oligomers can be used to make these polymer binders. Non-limiting examples of such monomers include methyl methacrylate, methyl acrylate, styrene, acrylic acid, butanediol 1,4-dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, hexanediol-1,6-dimethacrylate, methylstyrene pentaerythriol triacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, triethylene glycol dimethacrylate, 4-(vinyloxy)butyl benzoate, bis[4-(vinyloxy)butyl]adipate, bis[4-(vinyloxy)butyl]succinate, methyl methacrylate ... and unsaturated monomers such as olefins, vinyls, acrylates, and (meth)acrylates, such as bis[4-(vinyloxy)butyl]isophthalate, bis[4-(vinyloxy)butyl]trimellitate, 4-(vinyloxy)butyl stearate, bis[4-(vinyloxy)butyl]hexanediylbiscarbamate, bis[[4-[(vinyloxy)methyl]cyclohexyl]methyl], bis[[4-[(vinyloxy)methyl]cyclohexyl]methyl], bis[4-(vinyloxy)butyl](4-methyl-1,3-phenylene), and combinations thereof.

[0072] Non-limiting examples of solvents include butoxy-2-ethyl stearate, butyrolactone, diethyl fumarate, dimethyl maleate, dimethyl carbonate, dioctyl phthalate, ethylene glycol dimethyl ether ethyl salicylate, polyethylene glycol dimethyl ether, propylene carbonate, triacetin, benzyl ether, dodecyl-1,2-methylpyrrolidone, ethoxyethyl acetate, ethylene glycol diacetate, ethylene trichloroacetate, methylpyrrolidone, methyl sulfoxide, polyethylene glycols of different molecular weights, dimethylformamide, cyclohexane, p-dioxane, tetrahydrofuran, and high-boiling solvents such as p-xylene.

[0073] Non-limiting examples of dyes include new fuchsine cyanide, hexahydroxyethyl violet cyanide, pararosaniline cyanide, leucocrystal violet, leucomalachite green, and carbinol dyes such as malachite green base and p-rosalinin base, which are described in U.S. Patent Nos. 2,877,169, 3,079,955, and 4,377,751, each of which is incorporated herein by reference in its entirety. Other examples of dyes can be found in European Patent No. 1,529,089, which is incorporated herein by reference in its entirety.

[0074] Non-limiting examples of activators include halocarbons, haloniums, sulfoniums, ethyl trichloroacetate, heptachloropropane, ethyl trichloroacetate, chloroacetic acid, chloropropionic acid, hexachlorocyclohexane, methyl trichloroacetimidate, trichloroacetic acid, trichloroacetamide, trichloroethanol, trichloromethylbenzyl acetate, trichloromethylpropanol hydrate, trichloropropane, chlorinated polymers, diphenyliodonium iodide, diphenyliodonium hexafluoroarsenate, diphenyliodonium chloride, trimethylsulfonium iodide, and triphenylsulfonium hexafluoroantimonate.

[0075] In a third aspect, the disclosed and / or claimed inventive concept(s) provides a radiation sensitive device for detecting or measuring high energy radiation, comprising a radiation dosimeter including an energy sensitive adduct derived from at least one functionalized or non-functionalized acetylenic compound having at least 25 carbons and at least one substance.

[0076] In a fourth aspect, the disclosed and / or claimed inventive concept(s) provides energy sensitive adducts derived from 10,12-pentacosadiynoic acid and at least one material selected from the group consisting of functionalized or non-functionalized alkylamines, dialkylamines, trialkylamines, quaternary amines, pyridines, azopyridines, bipyridines, pyrimidines, pyrazines, piperidines, bipiperidines, morpholines, and combinations thereof.

[0077] In a fifth aspect, the disclosed and / or claimed inventive concept(s) provides a composition comprising an energy sensitive adduct derived from 10,12-pentacosadiynoic acid and at least one material selected from the group consisting of functionalized or non-functionalized alkylamines, dialkylamines, trialkylamines, quaternary amines, pyridines, azopyridines, bipyridines, pyrimidines, pyrazines, piperidines, bipiperidines, morpholines, and combinations thereof.

[0078] In a sixth aspect, the disclosed and / or claimed inventive concept(s) provides a radiation sensitive device for detecting or measuring high energy radiation, comprising a radiation dosimeter comprising an energy sensitive adduct derived from 10,12-pentacosadiynoic acid and at least one material selected from the group consisting of functionalized or non-functionalized alkylamines, dialkylamines, trialkylamines, quaternary amines, pyridines, azopyridines, bipyridyls, pyrimidines, pyrazines, piperidines, bipiperidines, morpholines, and combinations thereof.

[0079] High-energy radiation is used in a variety of applications, such as curing coatings, cross-linking polymers, recording images and information, radiography, non-destructive testing, and diagnostic and radiotherapy procedures that require radiation exposure for measurement. By way of non-limiting example, radiation-sensitive devices according to the disclosed and / or claimed inventive concept(s) include materials in the form of coatings, films, fibers, rods, plaques, or blocks. A general method for preparing radiation-sensitive devices can be found in EP 1529089, which is incorporated herein by reference in its entirety.

[0080] Further insight into the properties, functionality, and application(s) of the adducts and compositions according to the disclosed and / or claimed inventive concept(s) is disclosed in Chemical Science, 2020, volume 11, 8025-8035 by Hall et al., the disclosure of which is incorporated herein by reference in its entirety.

[0081] Adducts and compositions according to the disclosed and / or claimed inventive concept(s) may be prepared according to the examples provided below, which are presented herein to illustrate the disclosed and / or claimed inventive concept(s) and are not intended to limit the preparation of, for example, the adducts or compositions. [Example]

[0082] Example 1: Preparation and Characterization of PCDA Cocrystals Cocrystal 12·2 was obtained by milling PCDA (1) and 4,4′-azopyridine (2) in a 2:1 ratio in a Retsch MM200 mixer mill for 1 hour. This powder was characterized by PXRD and used to seed the cocrystal of 1 and 2 in acetone. After solvent evaporation at room temperature for one week, plate-like crystals of 12·2 formed and were analyzed by single-crystal X-ray diffraction (SC-XRD). The structure of 12·2 reveals a 2:1 stoichiometry with the diacetylene substituent in an anti conformation similar to that of 1, with an OH...N hydrogen bond from the carboxylic acid proton of 1 to the pyridyl nitrogen atom of 2. The O...N distance of 2.677(4) Å is consistent with a strong carboxylic acid OH...pyridyl hydrogen bond. The carboxylic acid proton was experimentally located on the carboxylic acid oxygen atom, ruling out the possibility of salt formation. The unit cell of 12·2 has a shorter crystallographic c-axis of 39.920(2) Å (equivalent to 6.87 Å) compared to 1 itself, suggesting a more oblique lamellar structure. Compared to 1, cocrystal 12·2 has a significantly shorter internal alkyne C1-C4′ distance of 3.633(1) Å, but the translation repeat distance of 5.354(1) Å deviates from the distance desired for topochemical reactions. The tilt angle of 1 in the cocrystal is 48.4°, which is greater than the optimal value.

[0083] In conjunction with SC-XRD, 12·2 was characterized by differential scanning calorimetry (DSC), which showed an onset melting temperature of 69 °C, which is between the melting temperatures of the individual components. The Fourier transform infrared (FTIR) spectrum showed a peak at 1690 cm for pure 1. -1 Compared to 1695cm -1 At 120°C, the cocrystal exhibits a hydrogen-bonded carbonyl stretching band, suggesting slightly weaker hydrogen bonding. The cocrystal exhibits a significant anisotropic thermal expansion along the c-axis between 120 and 273 K, increasing from 39.33 Å to 40.99 Å. Although differences in the unit cell make it difficult to compare the calculated and experimental PXRD data, it is clear that the single crystal studied is representative of the bulk material.

[0084] Two additional cocrystals, 12·3 (3 = 4,4′-bipyridyl) and 12·4 (4 = trans-1,2-bis(4-pyridyl)ethylene), were synthesized from 4,4′-bipyridyl and trans-1,2-bis(4-pyridyl)ethylene, respectively, by grinding the coformers with PCDA in a 2:1 ratio in a mixer mill for 45 min, resulting in powdered cocrystals. Samples were characterized by PXRD and used for seed crystallization in acetone. After 1 week of solvent evaporation at room temperature, these experiments yielded plates of 12·3 and 12·4, respectively. Single crystals of 12·3 were analyzed at 100 K on the I19 beamline at Diamond Light Source, while crystals of 12·4 were analyzed at 120 K on a Burker D8 Venture diffractometer. The two materials were isostructural and crystallized in the monoclinic space group P21 / c. The X-ray structures of cocrystals 12·3 and 12·4 show that the O…N distance is 2.652 Å in 12·3 and 2.6579 Å in 12·4, consisting of a hydrogen bond between the carboxylic acid hydrogen atom of the coformer 1 and the pyridyl nitrogen atom. Interestingly, the dialkyne moiety in both structures adopts a syn conformation, as opposed to the anti conformation in 1 and 12·2, indicating that subtle modifications can significantly affect the crystal packing mode and, therefore, photoreactivity. The ethylene bond in 12·4 is disordered across two positions. The syn conformation of the dialkyne substituents allows for an interdigitated bilayer packing arrangement, which translates into a much longer crystallographic c-axis surrounding the four folded molecules in the cocrystals of 3 and 4, as opposed to the two extended molecules in 12·2.

[0085] The differential scanning calorimetry (DSC) thermogram of 12·3 shows a melting onset endotherm of 77.8°C (compared to the melting temperatures of the coformers of 67°C and 114°C for 1 and 3, respectively), while 12·4 shows a melting onset temperature of 75.8°C compared to 150°C for 4. FTIR spectra of these cocrystals show a melting onset of 1690 cm for pure 1. -1 compared to 1683 cm -1 and 1688 cm-1 At 12·2, the cocrystals 12·3 and 12·4 exhibit a significant anisotropic thermal expansion during temperature increase, which may explain the slight differences in the calculated PXRD patterns from the experimental patterns at room temperature.

[0086] Example 2: Preparation and Characterization of PCDA Salts Cocrystals of PCDA with difunctional coformers 2-4 appear to yield structures unlikely to be photoreactive based on topochemical metrics. Therefore, both mono- and difunctional coformers of higher basicity were tested, with the intention of deprotonating the PCDA acid functional groups, altering the hydrogen-bonding pattern, and changing the stacking of the PCDA units. Salt formation was performed with difunctional diamines (5), cyclic amines (6), linear secondary amines (7), and linear terminal amines (8). Mechanochemical grinding of PCDA and compounds 5-8 (5 = 4,4′-bipiperidine, 6 = morpholine, 7 = diethylamine, and 8 = n-butylamine) in a mixer mill afforded new salts, as indicated by FTIR analysis. The asymmetric carboxylate carbonyl stretching mode resulted in a 1653 cm band for 12·5 and 1·6. -1 , 1627cm in 12·7 -1 , and 1·8 is 1649 cm -1 It has a carbonyl stretch at 1690cm and is a free acid ( -1 ), suggesting stronger hydrogen bonding in the salt than in the cocrystal and delocalized carboxylate anion structures. The X-ray structure of 12·5 reveals a salt with two anions of 1 and a doubly protonated dication of 5, with an N...O distance of 2.717(1) Å, consisting of an N...O hydrogen bond from the amine hydrogen atom of 5 and an oxygen atom of 1, respectively, in a 2:1 stoichiometry. Salt 12·5 is 12·2 crystallized with the same symmetry as 1 and 12·2, with the shortest crystallographic c-axis observed to date at 23.0041(15) Å. The C1-C4′ internal alkyne distance between adjacent molecules of 1 was 3.760(2) Å, within the topochemical conditions for diacetylene reactions (≤3.8 Å). However, the tilt angle of the salt cocrystal was 24.1°, lower than the desired value (45°), and the translational repeat distance was 5·577(2) Å, outside the maximum distance for this parameter (≤4.9 Å), again suggesting limited photoreactivity.

[0087] The morpholinium salt 1·6 was crystallized by slow evaporation of acetone at room temperature; however, poor crystal quality after repeated crystallization precluded SC-XRD analysis of 1·6. To model the interaction between the two components, the butanoic acid (BuA) salt of 6 was synthesized. Equimolar amounts of the reagents were allowed to stand overnight in a sealed flask, resulting in the formation of large single crystals of BuA·6. The X-ray structure, shown in Figure 1, reveals a salt with a butanoate anion and a morpholinium cation. This structure contains two unique N-H...O hydrogen-bonding interactions with N...O distances of 2.673(1) Å and 2.732(1) Å. Similar pK values ​​for 1 and butanoic acid were observed. a Based on this, 1·6 can also be expected to be a salt with a similar headgroup structure.

[0088] Salts of PCDA with diethylamine and n-butylamine were crystallized by slow evaporation of acetone solutions at room temperature. Surprisingly, the crystals were highly colored, purple and blue, respectively, consistent with facile photopolymerization. However, X-ray structure determination revealed unpolymerized PCDA salts, suggesting that the coloration was a surface effect. Indeed, cutting a single crystal in half revealed a colorless inner core. The structure of the diethylammonium salt, formula 12·7, demonstrated a cocrystal salt with a neutral molecule of 1. The butylammonium compound is a 1:1 salt of formula 1·8. This structure adopts a stacked bilayer configuration. In 12·7, a hydrogen bond forms from the hydrogen atom of the NH of the ammonium to the oxygen of the carbonyl of 1, with an N...O distance of 2.737(1) Å. The carboxylic acid group of neutral PCDA hydrogen bonds with the carboxylate functional group of the PCDA anion with a very short O…O distance of 2.444(1) Å (the additional hydrogen atoms between PCDA and the PCDA anion are disordered). In the 1:1 salt 1·8, the NH…O distances are 2.671(1) Å, 2.725(1) Å, and 2.784(1) Å, respectively, and the NH3 + There are three distinct hydrogen-bonding interactions formed from the cation to the carboxylate oxygen atom of the PCDA anion. The structure of 12·7 has a long c-axis of 57.520(4) Å, the longest of all the structures examined, indicating a linear, parallel arrangement of the PCDA components. Salts 12·7 and 1·8 have similar C1-C4′ internal alkyne distances of 3.776(2) Å and 3.779(1) Å, tilt angles of 41.9° and 43.7°, and translational repeat distances of 4.644(3) Å and 4.593(1) Å, respectively. For these two salts, all three values ​​are in good agreement within the optimal topochemical conditions; therefore, significant photoreactivity as well as natural coloration of the crystal surfaces are expected.

[0089] DSC analysis of the PCDA salts 5-8 revealed a melting onset endotherm at 111 °C for 12·5 (compared to 67 °C and 170 °C for the parent compounds 1 and 5, respectively). This relatively high value indicates the presence of proton transfer, as well as the higher melting point of the bipiperidine coformer. The morpholinium salt 1·6 has a low melting onset temperature of 54 °C, consistent with morpholine being a liquid at room temperature (boiling at 128 °C). The DSC thermogram of 12·7 shows a melting onset endotherm at 50.7 °C, compared to 55 °C for 7, while 1·8 shows a melting onset endotherm at 63.1 °C, with the salt former 8 boiling at 77 °C.

[0090] (UV and X-ray Response of Cocrystals and Salts) The cocrystal and salt powders were placed on filter paper in a dark box and exposed to a 6-watt handheld UV light at 254 nm for up to 24 hours. Because azobenzene coformer 2 itself is known to photopolymerize to the cis-form when irradiated with synchrotron radiation at 365 nm, 12·2 was irradiated at this wavelength to investigate the photoreactivity of the conformer components within the cocrystal. The PCDA powder itself gradually darkened from white to a deep blue upon irradiation, indicating that all of the cocrystals with coformers 2–4 appear to be photostable despite their close proximity to the dialkyne functional groups within the topochemical conditions. However, the tilt angle of 1 within the cocrystal and the translational repeat distance of the cocrystal were outside the desired values. The irradiated cocrystals were analyzed by PXRD and solid-state CP-MAS. 13The cocrystal samples were analyzed by C NMR spectroscopy and FTIR spectroscopy. The data confirmed that the cocrystal samples remained essentially unchanged after irradiation. The data also indicate that the irradiated, deep blue samples of PCDA photopolymerized <1%, indicating that the highly visible color observed was only a surface effect and that the radiation did not penetrate into the bulk of the sample. The azobenzene cocrystal did not undergo significant change when irradiated at 365 nm. This lack of cis / trans photoreactivity of azobenzene in 12·2 indicates that the solid-state environment of the cocrystal stabilizes the trans isomer. All salts of monofunctional ammonium cations are highly photoactive. A significant visible color change occurs just 5 minutes after irradiation for salts 1·6, 12·7, and 1·8. The signal corresponding to the photopolymerized material was detected by CP-MAS. 13 This is clearly seen by C NMR spectroscopy. 13 C NMR spectroscopy revealed that salt 12·7 was the most sensitive to UV radiation, with the most significant changes occurring in the alkene region (100–140 ppm), consistent with functionalization of the ene-yne ​​photopolymer. However, even in these systems, the slow conversion and sharpness of the NMR resonances suggest a relatively low degree of oligomerization. This slow response reflects the solid-state nature of the process, resulting in poor radiation penetration into the bulk of the sample. However, this gradual response is favorable for dosimetric applications, making these materials highly interesting. The significant photoreactivity of 12·7 and 1·8 is consistent with the crystalline packing revealed by these structures, indicating that both are within the parameters revealed by topochemical conditions.

[0091] FTIR analysis of the irradiated salt cocrystals shows that salts 1·6, 12·7, and 1·8 begin to lose their volatile coformer and revert to the free carboxylic acid after prolonged UV exposure. This is due to the carboxylate asymmetric stretching band ν asymm (CO2) intensity (1653 cm for 1·6) -1 , 1627cm in 12·7-1 , and 1·8 is 1649 cm -1 ) becomes smaller, and when the sample is irradiated with radiation, -1 This is evidenced by the appearance of the free acid peak at 1000 nm, close to that of PCDA. This effect is most evident in the morpholinium salts 1 and 6, which revert to the free acid after just 1 h, while 7 and 8 begin to separate from their respective salts after 1 day of irradiation. The resulting carboxylic acid is a mixture of free PCDA and photopolymer. These findings are also supported by PXRD analysis of the irradiated salts. Interestingly, given the very limited photoreactivity of PCDA itself, the formation of the salt followed by amine removal in this manner provides an intriguing route to the free acid photopolymer, suggesting that transient amine complexation efficiently catalyzes the photopolymerization of PCDA itself.

[0092] In addition to UV irradiation, the effect of X-rays on PCDA and its derivatives was also analyzed. Free PCDA (1) was irradiated with 100 Gy of X-rays and analyzed by Raman spectroscopy. This resulted in a peak at 2253.3 cm -1 with a small residual dialkyne band at 2098.8 cm -1 The clear alkyne band of the ene-yne ​​polymer was revealed at 2298.8 cm. The excitation wavelength of the 785 nm laser overlapped with the absorption band of the photopolymer, resulting in a significant enhancement of the Raman band of the chromophore. -1 Despite the very limited photoreactivity at 2098.8 cm -1 The increased appearance of the band is a sign of the pre-resonance Raman effect, which indicates a very low degree of bulk conversion. 13 Although the C CP-MAS NMR data are consistent with the visual observation of some blue coloration, in contrast, irradiation of all three cocrystals with coformers 2-4 with 10 Gy of X-ray irradiation revealed a significant increase in the conjugated ene-yne ​​region (approximately 2100 cm) present before and after irradiation. -1) showed very little photoreactivity, as evidenced by a low-intensity peak at 2100.4 cm. Compared to the other two cocrystals, which likely arise from small amounts of 1 photopolymer present as contaminants in the starting PCDA, cocrystal 12 2 exhibited a peak at 2100.4 cm. -1 Similar to the cocrystal, salt 12·5 exhibits a small ene-in band at 2258.4 cm corresponding to the unreacted dialkyne, even after 100 Gy of X-ray irradiation, further reinforcing the photostability of the salt. -1 The band at 2100.3 cm -1 The small ene-yne ​​photopolymer band at 2088.1 cm likely arises from a small amount of photopolymerized PCDA impurity. In contrast, salt 1 6 exhibits a band at 2088.1 cm -1 The salts exhibit impressive X-ray sensitivity, as indicated by the presence of a prominent ene-in band at 2097.7 cm. This band is significantly red-shifted compared to photopolymerized PCDA, indicating a more planar, conjugated conformation of the chromophore. This is in contrast to 1 alone, which exhibits a torsional distortion on the π-band of the chromophore upon irradiation. Salt 1·6 also exhibits a significant additional visible color change upon irradiation compared to 1 alone. Increased hydrogen bonding in the salts would be expected to bring the monomers of 1 into a closer spatial arrangement, resulting in greater photosensitivity. After 100 Gy of X-ray irradiation, salt 12·7 possesses minimal residual dialkyne signals, at 2097.7 cm. -1 The photopolymer exhibits a prominent alkyne band at 1445 cm. Solid-state NMR results indicate approximately 53% polymerization, but the Raman signal for the colorless monomer is barely visible. Interestingly, the Raman spectrum of 12·7 shows broadening of the ene-yne ​​band and the typical dominant 1445 cm band. -1 1500 cm, at a wavenumber slightly higher than the alkene bands -1 The presence of an additional alkene peak at 2098.1 cm indicates multiple conformations of the polymerized material and suggests some structural differences in the resulting chromophore, indicating the existence of multiple conformations of the polymerized salt. For 1·8, Raman analysis of a sample irradiated with 100 Gy of X-rays showed that the salt gradually photopolymerized, resulting in a peak at 2098.1 cm. -1It has been shown that the photosensitive salt has an en-in band at 1300 cm and has similar radiation sensitivity as 1 alone. -1 From 1150cm -1 The progression of CH vibrations arising from the polymer side chains of 1 changes with irradiation, suggesting a conformational change compared to the lithium salt. The change in side chain conformation is due to differences in the phase angle of the pair of vibrations between the methylene groups. These differences in the progression of CH vibrations can be used as an additional conformational tool to detect the presence of PCDA polymers. Close examination of the frequency differences within the progression of vibrational modes may indicate stress on the side chains due to their proximity to each other as the polymer forms. Interestingly, at approximately 2100 cm -1 The position of the ene-yne ​​alkyne band of the irradiated diethylammonium salt and butylammonium salt is 2066.3 cm , which is the same as that obtained with the commercial lithium PCDA. -1 This significant red-shift indicates a much more planar, "ordered" chromophore in the lithium salt; the commercially available material exists in an ordered "blue state," while the use of organic salt formers results in a disordered "red state" photopolymer. -1 The value of is intermediate, suggesting that the order, and therefore potentially the color, of the polymer may be tunable.

Claims

1. at least one acetylenic compound having at least 25 carbons and one or more functional groups; and at least one substance; the acetylenic compound is selected from the group consisting of pentacosadiynoic acid, hexacosadiynoic acid, heptacosadiynoic acid, octacosadiynoic acid, nonacosadiynoic acid, triacontanediynoic acid, and combinations thereof; the substance is selected from the group consisting of alkylamines, dialkylamines, trialkylamines, pyridines, azopyridines, bipyridyls, pyrimidines, pyrazines, piperidines, bipiperidines, morpholines, and combinations thereof; sensitive to energy derived from ionizing radiation, electromagnetic radiation, or heat; The energy sensitive adduct in the form of a salt or co-crystal.

2. 2. The energy sensitive adduct of claim 1, wherein the acetylenic compound is 10,12-pentacosadiynoic acid.

3. 10. The energy-sensitive adduct of claim 1, wherein the adduct is more energy sensitive than the acetylenic compound in the absence of the substance.

4. 10. The energy sensitive adduct of claim 1, wherein the adduct has reduced energy sensitivity compared to the acetylenic compound in the absence of the substance.

5. The energy sensitive adduct of claim 1 , wherein the ionizing radiation comprises gamma rays or X-rays.

6. 10. The energy-sensitive adduct of claim 1, wherein the electromagnetic radiation comprises visible light, ultraviolet light, or infrared light.

7. at least one acetylenic compound having at least 25 carbons and one or more functional groups; and at least one substance; the acetylenic compound is selected from the group consisting of pentacosadiynoic acid, hexacosadiynoic acid, heptacosadiynoic acid, octacosadiynoic acid, nonacosadiynoic acid, triacontanediynoic acid, and combinations thereof; the substance is selected from the group consisting of alkylamines, dialkylamines, trialkylamines, pyridines, azopyridines, bipyridyls, pyrimidines, pyrazines, piperidines, bipiperidines, morpholines, and combinations thereof; sensitive to energy derived from ionizing radiation, electromagnetic radiation, or heat; A composition comprising an energy-sensitive adduct in the form of a salt or co-crystal.

8. at least one acetylenic compound having at least 25 carbons and one or more functional groups; and at least one substance; the acetylenic compound is selected from the group consisting of pentacosadiynoic acid, hexacosadiynoic acid, heptacosadiynoic acid, octacosadiynoic acid, nonacosadiynoic acid, triacontanediynoic acid, and combinations thereof; the substance is selected from the group consisting of alkylamines, dialkylamines, trialkylamines, pyridines, azopyridines, bipyridyls, pyrimidines, pyrazines, piperidines, bipiperidines, morpholines, and combinations thereof; sensitive to energy derived from ionizing radiation, electromagnetic radiation, or heat; A radiation sensitive device for detecting or measuring radiation, comprising a radiation dosimeter including an energy sensitive adduct in the form of a salt or co-crystal.

9. 10,12-pentacosadiynoic acid and at least one substance selected from the group consisting of alkylamines, dialkylamines, trialkylamines, pyridines, azopyridines, bipyridyls, pyrimidines, pyrazines, piperidines, bipiperidines, morpholines, and combinations thereof; sensitive to energy derived from ionizing radiation, electromagnetic radiation, or heat; A composition comprising an energy-sensitive adduct in the form of a salt or co-crystal.

10. 10,12-pentacosadiynoic acid and at least one substance selected from the group consisting of alkylamines, dialkylamines, trialkylamines, pyridines, azopyridines, bipyridyls, pyrimidines, pyrazines, piperidines, bipiperidines, morpholines, and combinations thereof; sensitive to energy derived from ionizing radiation, electromagnetic radiation, or heat; A radiation sensitive device for detecting or measuring high energy radiation, comprising a radiation dosimeter including an energy sensitive adduct in the form of a salt or co-crystal.

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