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Abstract— The photooxidation of octaethyl-2, 3-dihydrobilindione ( 2 ) as a model for the Pr -chromophore has been studied in acidic methanol. When 2 is titrated with HCl to the cation and irradiated under N2 with an excess of I2 , violin and rhodin type pigments are formed bearing methoxy-substituents at either C-4,5 or C-15,16, respectively. The reaction is slowed down as compared to neutral conditions, it is no longer regioselective at the C-5 methine bridge, and the formation of dimers is suppressed. From the data of this and earlier chemical model studies on the photooxidation of 2 , and the known properties of phytochrome, a reaction for the Pr → Pfr phototransformation is suggested, in which the chromophore is attacked by the protein moiety in a sequence of oxidation and nucleophilic substitution, which may lead to a primary redox signal for the physiological response. 相似文献
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Abstract— –From the A-dihydrobilindione 3. the pyridinium derivatives 6a, b and analogues therwf have been obtained by a formal nucleophilic substitution. The reaction is rationalized as a photochemically assisted oxidation of 3 with a subsequent regioselective addition of pyridine at C-5. By thermolysis. 6a.b yields back the parent bilin 3, together with an oxidation product. The significance of the reaction with respect to the phytochrome interconversion is discussed. 相似文献
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S. Bandyopadhyay D. Chattopadhyay S. K. Ghosh B. Chakrabarti 《Photochemistry and photobiology》1992,55(5):765-772
Fluorometric studies of cataractous and non-cataractous human lenses were carried out to study the emission characteristics and the distribution and solubility of lenticular pigments. Most of the detected fluorophores were well distributed over the cortical and nuclear portion of the lens. The decrease in solubility of proteins with aging and cataract formation is concomitant with increasing photolysis of tryptophan. However, this is likely a phenomenon independent of the photochemical transformations of the lens proteins. The number of emitting species in the diseased lenses are higher than in the normal mature lenses. A species emitting around 375 or 388 nm is of particular interest (lambda cx 330 nm) in that the emission characteristics of this fluorophore resemble kynurenic acid which has a high photosensitizing efficiency. The concentration of fluorescent pigments in the lenses of Indian origin is significantly high. The intense pigmentation could be attributed largely to the formation of photoproducts in the absence of normal endogenous antioxidant accumulation that is dependent on nutrition standard. If, indeed, any of these fluorescent pigments, because of their photosensitizing ability, are responsible for lenticular opacity, it is not the abundance of sunlight alone but also malnutrition that could account for the high incidence of cataract in India. 相似文献
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S. Bandyopadhyay D. Chattopadhyay S. K. Ghosh B. Chakrabarti 《Photochemistry and photobiology》1984,39(6):765-772
Abstract— Fluorometric studies of cataractous and non-cataractous human lenses were carried out to study the emission characteristics and the distribution and solubility of lenticular pigments. Most of the detected fluorophores were well distributed over the cortical and nuclear portion of the lens. The decrease in solubility of proteins with aging and cataract formation is concomitant with increasing photolysis of tryptophan. However, this is likely a phenomenon independent of the photochemical transformations of the lens proteins. The number of emitting species in the diseased lenses are higher than in the normal mature lenses. A species emitting around 375 or 388 nm is of particular interest (λcx , 330 nm) in that the emission characteristics of this fluorophore resemble kynurenic acid which has a high photosensitizing efficiency. The concentration of fluorescent pigments in the lenses of Indian origin is significantly high. The intense pigmentation could be attributed largely to the formation of photoproducts in the absence of normal endogenous antioxidant accumulation that is dependent on nutrition standard. If, indeed, any of these fluorescent pigments, because of their photosensitizing ability, are responsible for lenticular opacity, it is not the abundance of sunlight alone but also malnutrition that could account for the high incidence of cataract in India. 相似文献
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Fluorescence spectra of normal mature human lenses have been measured and at least eight species with distinct emission characteristics identified. To determine the specific photochemical and photophysical processes responsible for the origin and development of these fluorophores, emission behavior of the products generated by successive irradiation of young human lenses (3-6 y old) as well as of L-tryptophan solution have been systematically monitored. Fluorescent products that resulted from this irradiation were comparable to many of the fluorophores detected in aged lenses, indicating that light plays a major role in the development of these pigments. In addition to photogenerated species, there are other compounds in human lenses, presumably advanced glycosylated end products, with marked fluorescence properties. Several oxidation products of tryptophan including N-formylkynurenine or its derivatives, beta-carboline or its derivatives, and anthranilic acid have been identified in the mature human lens. The development of several photoproducts also was attributed to endogenous ascorbate-mediated Maillard reaction products, which undergo photoconversion by the visible light. Although some of these chromophores could act as photosensitizers, the sensitizing efficiency of many are low. Conversely, the near-UV filtering capability of these colored compounds conceivably could protect the vitreous and retina from development of any photochemical lesion. 相似文献
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Abstract
Fluorescence spectra of normal mature human lenses have been measured and at least eight species with distinct emission characteristics identified. To determine the specific photochemical and photophysical processes responsible for the origin and development of these fluorophores, emission behavior of the products generated by successive irradiation of young human lenses (3–6 y old) as well as of L-tryptophan solution have been systematically monitored. Fluorescent products that resulted from this irradiation were comparable to many of the fluorophores detected in aged lenses, indicating that light plays a major role in the development of these pigments. In addition to photogenerated species, there are other compounds in human lenses, presumably advanced glycosylated end products, with marked fluorescence properties.
Several oxidation products of tryptophan including N -formylkynurenine or its derivatives, β-carboline or its derivatives, and anthranilic acid have been identified in the mature human lens. The development of several photoproducts also was attributed to endogenous ascorbate-mediated Maillard reaction products, which undergo photoconversion by the visible light. Although some of these chromophores could act as photosensitaizers, the sensitizing efficiency of many are low. Conversely, the near-UV filtering capability of these colored compounds conceivably could protect the vitreous and retina from development of any photochemical lesion. 相似文献
Fluorescence spectra of normal mature human lenses have been measured and at least eight species with distinct emission characteristics identified. To determine the specific photochemical and photophysical processes responsible for the origin and development of these fluorophores, emission behavior of the products generated by successive irradiation of young human lenses (3–6 y old) as well as of L-tryptophan solution have been systematically monitored. Fluorescent products that resulted from this irradiation were comparable to many of the fluorophores detected in aged lenses, indicating that light plays a major role in the development of these pigments. In addition to photogenerated species, there are other compounds in human lenses, presumably advanced glycosylated end products, with marked fluorescence properties.
Several oxidation products of tryptophan including N -formylkynurenine or its derivatives, β-carboline or its derivatives, and anthranilic acid have been identified in the mature human lens. The development of several photoproducts also was attributed to endogenous ascorbate-mediated Maillard reaction products, which undergo photoconversion by the visible light. Although some of these chromophores could act as photosensitaizers, the sensitizing efficiency of many are low. Conversely, the near-UV filtering capability of these colored compounds conceivably could protect the vitreous and retina from development of any photochemical lesion. 相似文献
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M. M. Mathews 《Photochemistry and photobiology》1963,2(1):1-8
Abstract— Aninvestigation was made of the location, function and characteristics of production of carotenoid pigments of a strain of Mycobacterium marinum , an organism which produces its pigments only when exposed to light.
It was found that light-grown cells of this organism contain only one pigment. The intracellular location of this pigment was found to be the cell envelope. The pigment was found to be capable of protecting the cells against lethal photo-oxidations mediated by the dye, toluidine blue.
These studies also revealed that in dark-grown cells exposed to light, pigment production occurred after a short lag and then remained constant during logarithmic growth. Pigment was produced by starved cells, but to a lesser degree than son-starved cells; the addition of a carbon or nitrogen source to starved cells increased pigmentation to the level in non-starved cells. Pigmentation did not occur in the absence of oxygen. Cells exposed to light at 4°C were not pigmented immediately after exposure, but became so if incubated at 30°C. Production of pigment was found to obey the Bunsen-Roscoe reciprocity law. The determination of an action spectrum for the production of pigment indicates that maximum pigment productiion occurs in the vicinity of 410 and 439 mµ, with smaller maxima in the vicinity of 502 , 528 and 560 mµ. 相似文献
It was found that light-grown cells of this organism contain only one pigment. The intracellular location of this pigment was found to be the cell envelope. The pigment was found to be capable of protecting the cells against lethal photo-oxidations mediated by the dye, toluidine blue.
These studies also revealed that in dark-grown cells exposed to light, pigment production occurred after a short lag and then remained constant during logarithmic growth. Pigment was produced by starved cells, but to a lesser degree than son-starved cells; the addition of a carbon or nitrogen source to starved cells increased pigmentation to the level in non-starved cells. Pigmentation did not occur in the absence of oxygen. Cells exposed to light at 4°C were not pigmented immediately after exposure, but became so if incubated at 30°C. Production of pigment was found to obey the Bunsen-Roscoe reciprocity law. The determination of an action spectrum for the production of pigment indicates that maximum pigment productiion occurs in the vicinity of 410 and 439 mµ, with smaller maxima in the vicinity of 502 , 528 and 560 mµ. 相似文献
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Abstract— Picrates of conjugated Schiff bases have C=N stretching frequencies similar to those of the respective free bases. This raises the question if the frequency of this vibration can provide proof for the protonation of the retinylidene Schiff base occurring in visual pigments. 相似文献
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《Journal of Coordination Chemistry》2012,65(3-4):217-221
Abstract Our recent work on Cu(II) and VO(IV) interactions with lactobionic acid have shown1,2 that this sugar acid has an unusually high ability to coordinate both metal ions. The carboxyl group is not a very effective donor for cupric ions3,4 and metal interations with the set of the protonated hydroxyl groups should have considerable effects on complex stability. This high stability of the lactobionic acid complexes can lead to the involvement of this ligand in formation of ternary complexes with ligands such as aminosugars.3–6 Both ligands are important chelating agents for Cu(II) ions in medicine, agriculture and food chemistry.7–9 Since ternary complexes may play an important role in natural systems we have decided to follow complex formation in solutions containing lactobionic acid and one an aminosugar, D-glucosamine. The anchoring group in D(+)-glucosamine (2-amino-2-deoxy-D-glucose) is an amino group which is much more effective donor than carboxylate which acts as an anchor in sugar acids. Thus in our study we have used excess lactobionic acid to promote the formation of ternary complexes as major species in the solutions studied. 相似文献
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Abstract The crystal and molecular structure of the title compound 4 have been determined by single crystal X-ray crystallography. The structure shows the typical S,-ruffled conformation observed for Ni(II) tetrapyrroles. Compared to the structure of the methyl ester of (132 -demethoxycarbonyl-pheophorbidato a)nickel(II), 4 shows a smaller Ca -Cm -Cm angle and a higher degree of conformational distortion at the methyl-substituted C20 position. This local distortion of the macrocycle might account for the bathochromic shifted absorption spectra of the bacteriochlorophylls c compared to the d-series. Crystal data: C35 H38 N4 NiO3 ; tetragonal, P43 21 2, a = 15.335(7) Å, c = 25.11(2) Å, V = 5904, Z = 8, λ(Mo Kα) = 0.71069 Å, μ= 0.701 mm−1 , P(000) = 2624, 130 K, R = 0.058 for 5700 reflections with F > 4.0σ(F). 相似文献
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在甲基丙烯酸甲酯(MMA)和丙烯酸正丁酯(BA)的无皂乳液共聚体系中,加入适量反应性乳化剂w-十一烯酸钠(SUA),在用量远低于其CMC时,分别讨论了SUA浓度、引发剂(K_2S_2O_8)浓度以及离子强度对反应动力学的影响,用SA-CP3型粒度分布仪、透射电镜(TEM)等考察了乳液粒子大小(D_w)、浓度(N_p)、形态及其增长过程;用凝胶渗透色谱仪、红外光增、离子交换-电导滴定等手段探讨了反应机理。结果表明:在该反应体系中,“均相沉淀”与“胶束”成核两种机理同时存在,两种成核方式几率的相对大小由SUA浓度、离子强度等所决定。 相似文献