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1.
Abstract— The kinetic rate equation for the photoreversible photoisomerization between trans -urocanic acid (UA) and cis-UA following absorption of UV radiation has been solved and used to show that the maximum of the trans -UA photoisomerization action spectrum depends upon both the initial trans -UA concentration irradiated in an experiment and upon the irradiation dose used to determine the amount of cis -UA generated. This kinetic model can be used to explain current discrepancies between in vitro and in vivo photoisomerization action spectra reported in the literature. 相似文献
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E. Snellman C T. Jansén J. K. Laihia T. Milán L. Koulu K. Leszczynski P. Pasanen 《Photochemistry and photobiology》1997,65(5):862-865
Abstract— To investigate the relationship between erythemal sensitivity of the skin to U V radiation and epidermal urocanic acid (UCA) concentration, 45 healthy volunteers of anamnestic skin phototypes (ASP) I-IV were studied. In 16 of the subjects, we analyzed UCA photoisomerization after graded UVB exposures. The median and mean total UCA concentration in unirradiated skin was 22.4 and 35.3 nmol/cm2 , and no statistically significant difference in total UCA concentrations was detectable either between ASP I through II and III through IV or between the phototested skin type (PSP) groups 1 through 2 and 3 through 4. The relative amount of the cis -isomer varied between 3 and 35%, with median and mean values of 7 and 12%, respectively. No statistically significant difference in absolute or relative cis -UCA concentrations was detectable between ASP I through II and III through IV, but a significantly lower absolute ( P < 0.009) and relative ( P < 0.002) cis -UCA concentration in unirradiated skin was recorded in PSP groups 1 through 2, compared to types 3 through 4. In all tested subjects, an erythemally weighted dose of 1 mj/cm2 sufficed to cause trans - to cis -UCA isomerization. When comparing photosensitive (skin phototype I) and phototolerant (phototypes III and IV) individuals, who were irradiated with a reference 5 mJ/cm2 UV dose or with fractions of 0.1-1.0 of their individual minimal erythema dose values, no skin phototype-dependent difference in ability to photoisomerize was discernible. 相似文献
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Lindsay J. Webber Eugene Whang Edward C. De Fabo 《Photochemistry and photobiology》1997,66(4):484-492
Abstract— Ultraviolet B radiation (280-320 nm) can systemically suppress contact hypersensitivity (CHS), delayed type hypersensitivity (DTH) and tumor rejection responses in mice. Several models have been postulated for the initiation of this UVB-induced immune suppression and, although the complete mechanism is unclear, our early studies suggested that initiation is via the activation of a photoreceptor in the skin, identified as urocanic acid (UCA). Recent preliminary data from our laboratory and others indicated that UVA (320-400 nm)-emitting broadband sunlamps can also isomerize UCA but may not lead to immune suppression, in contrast to UVB-emitting sunlamps, which cause both effects. Although the reason for this inconsistency is unknown, the emission spectra of UVA lamps contain differing amounts of UVB, UVA-I (340-400 nm) and UVA-II (320-340 nm) from those of UVB sources. In this study we determined a detailed dose-response for the isomerization of UCA in mouse skin using the UVA-I, UVA-II and UVA-I+II wavelength ranges. The dose-response curves obtained were put on an equal energy basis by quantum correction and the possibility of wavelength interaction for this effect investigated. A simple additive wavelength interaction between UVA-I, UVA-II, and UVA-I+II was observed for trans-UCA photoisomerization. This result indicates that the failure of UVA-I, UVA-II or UVA-I+II radiation to induce immune suppression of the CHS response in an animal model is not due to complex wavelength interactions and/or the presence of an in vivo endogenous photosensitizer of UCA isomerization. Other factors, such as downstream blocking by UVA of the cis -UCA generated signal, may be involved. 相似文献
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Deborah L. Terrian C. Nicole Kuhll Irwin Tessman Harry Morrison 《Photochemistry and photobiology》1996,63(6):898-900
It has been reported that UV-induced immunosuppres-sion can be reversed by photoreactivation or exposure to T4 endonuclease V, two treatments that can repair cyclobutane pyrimidine dimers. These observations, together with the known role of urocanic acid (UA) in UV-induced immune suppression, prompted us to study the ability of DNA photolyase to repair UA-DNA cyclobutane photoadducts in single-stranded calf thymus DNA. We did not detect any release of UA, with a sensitivity implying that photolyase is at least 2900 times less active toward UA-DNA adducts than toward cis-syn thyminethymine dimers. This indicates that any reversal of photoimmunosuppression by photoreactivation cannot significantly involve cleavage of UA-DNA cyclobutane adducts. 相似文献
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Pekka Juusola Pentti Minkkinen Lasse Leino Jarmo K. Laihia 《Monatshefte für Chemie / Chemical Monthly》2007,138(10):951-965
Summary. (E)- and (Z)-Urocanic acids are endogenous chemicals in the normal mammalian skin. The first and the second thermodynamic dissociation
constants (pK
a1 and pK
a2) of urocanic acid isomers were determined using UV spectrophotometry in aqueous solutions. The values with standard deviation
(pK
a1 = 3.43 ± 0.12 and pK
a2 = 5.80 ± 0.04) and (pK
a1 = 2.7 ± 0.3 and pK
a2 = 6.65 ± 0.04) were obtained to (E)- and (Z)-urocanic acids, respectively. The second dissociations were studied also by potentiometric titration in aqueous sodium chloride
solutions up to the isotonic salt concentration (0.154 mol dm−3), and the second thermodynamic dissociation constants as well as activity parameters for both isomers were determined at
temperature 25°C and for (E)-urocanic acid also at 37°C. The obtained pK
a2 values were close to those found by UV spectrophotometry. The equations for the calculation of the second stoichiometric
dissociation constants of urocanic acid isomers on molality and molarity scale in aqueous sodium chloride solutions were derived.
The obtained pK
a1 and pK
a2 values for (Z)-urocanic acid appear to be essentially lower than some previously reported values in literature.
An erratum to this article is available at . 相似文献
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Pekka Juusola Pentti Minkkinen Lasse Leino Jarmo K. Laihia 《Monatshefte für Chemie / Chemical Monthly》2007,38(11):951-965
(E)- and (Z)-Urocanic acids are endogenous chemicals in the normal mammalian skin. The first and the second thermodynamic dissociation
constants (pK
a1 and pK
a2) of urocanic acid isomers were determined using UV spectrophotometry in aqueous solutions. The values with standard deviation
(pK
a1 = 3.43 ± 0.12 and pK
a2 = 5.80 ± 0.04) and (pK
a1 = 2.7 ± 0.3 and pK
a2 = 6.65 ± 0.04) were obtained to (E)- and (Z)-urocanic acids, respectively. The second dissociations were studied also by potentiometric titration in aqueous sodium chloride
solutions up to the isotonic salt concentration (0.154 mol dm−3), and the second thermodynamic dissociation constants as well as activity parameters for both isomers were determined at
temperature 25°C and for (E)-urocanic acid also at 37°C. The obtained pK
a2 values were close to those found by UV spectrophotometry. The equations for the calculation of the second stoichiometric
dissociation constants of urocanic acid isomers on molality and molarity scale in aqueous sodium chloride solutions were derived.
The obtained pK
a1 and pK
a2 values for (Z)-urocanic acid appear to be essentially lower than some previously reported values in literature. 相似文献
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H. de Vries S. Encinas M. A. Miranda J. V. Castell G. M. J. Beijersbergen van Henegouwen 《Photochemistry and photobiology》1997,66(4):432-435
Abstract— The photoreactivity of the photosensitizing nonsteroidal anti-inflammatory drug tiaprofenic acid (TA) and its photoproduct decarboxytiaprofenic acid (DTA) was studied both in the presence and in the absence of bovine serum albumin (BSA). The photoproduct DTA was found to be photostable in buffered aqueous solution at pH 7.4, but photodecomposed when BSA was present in the reaction medium. Both TA and DTA underwent irreversible photobinding to BSA in an almost quantitative way, as evidenced by radioactivity measurements using labeled (3H) compounds. In the case of TA, it has been proven that photobinding is mainly attributable to the phototoreactivity of in situ -generated DTA. The photo-degradation and photobinding of TA were also investigated in the epidermis in vivo. Rats were exposed to UVA after application of TA to their shaven dorsal skin. During the initial periods of irradiation, the amount of TA decreased sharply, and the yield of the corresponding photoproduct (DTA) reached a maximum. Prolonged irradiation led to photodegradation of DTA. In vivo photobinding was studied using 3H-TA. Photobinding took place slowly at the beginning, but its rate increased sharply after complete photoconversion of TA, when the photoproduct DTA reached the maximum concentration. Thereafter, the decrease of DTA was more pronounced than that of TA. This indicates thatalso in vivoDTA rather than TA is responsible for the photobinding to biomacromolecules in the viable layer of the epidermis. Overall, the above results suggest that irradiation of TA in buffered aqueous solution, in the presence of proteins, is a reasonable model system to study the photodegradation and photobinding behavior of this drug in vivo. From the qualitative point of view, the main conclusion is that DTA plays a key role both in vivo and in vitro: it is the major photoproduct, it undergoes further photodegradation upon prolonged irradiation, and it appears to be responsible for the photobinding process. 相似文献
10.
Summary. Photodiastereomerization of urocanic acid and its human serum albumin complex (its binding constant was estimated to amount 4.1·10–4dm3·mol–1) was investigated. It was found that although the photodiastereomerization rates were similar, the photoequilibrium positions differed significantly ((E):(Z)=33:77 for free urocanic acid, and 50:50 for the complex). This is thought to be due to a different stabilization of the corresponding orthogonal excited states. The thermal barrier of diastereomerization was estimated to amount to more than 250kJ·mol–1 making it a very unlikely process under physiological and photodiastereomerization conditions. The various prototropic species of the two diastereomers at various pH values were analyzed by means of a mathematical model and from these results a novel photoinduced pH-jump methodology allowing for fast, persistent, diffusion controlled, and bidirectional jumps is proposed. 相似文献
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在pH 为0.91 的HCl-NaOAc 缓冲介质中, 盐酸巴马汀与硅钨酸通过静电相互作用导致共振光散射信号显著增强,最大散射波长为297 nm, 增强的散射信号强度与盐酸巴马汀浓度在0.09~3.2 μg/mL 范围内呈线性关系, 据此建立了盐酸巴马汀的共振光散射分析方法, 检测限为9.1 ng/mL. 实验考察了pH、离子强度对体系的影响, 研究了体系紫外吸收光谱及荧光光谱, 讨论了共振光散射增强机理. 该方法用于黄藤素片、黄藤素胶囊及血清样品中盐酸巴马汀含量测定,RSD≤4.2%. 相似文献
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某些蒽环类抗癌药物与刚果红相互作用的吸收、荧光和共振瑞利散射光谱研究 总被引:8,自引:0,他引:8
在pH 2.5左右的酸性介质中, 刚果红与表柔比星、柔红霉素和米托蒽醌等蒽环类抗生素反应形成离子缔合物时, 仅能引起吸收光谱和荧光光谱的微小变化, 但却能导致共振瑞利散射(RRS)的显著增强并产生新的RRS光谱, 与此同时也观察到二级散射(SOS)和倍频散射(FDS)的增强. 最大RRS峰位于370 nm附近, 并在280 nm附近有另一散射峰. 而它们的SOS峰均在530 nm附近, 最大FDS峰均位于353 nm处. 其中RRS法灵敏度最高, 它对表柔比星、柔红霉素和米托蒽醌的检出限分别为0.054, 0.058和0.033 μg/mL, 而其线性范围分别为0.05~12.0, 0.05~12.0和0.04~7.5 μg/mL. 文中研究了反应产物的吸收、荧光和RRS光谱特征, 适宜的反应条件及分析化学性质, 据此发展了一种用RRS技术灵敏、简便、快速测定蒽环类抗癌药物的新方法. 相似文献
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Kuvichkin VV 《Bioelectrochemistry (Amsterdam, Netherlands)》2002,58(1):3-12
The data on lipid-nucleic interactions and their role in vitro and in vivo are presented. The results of study of DNA-lipid complexes in absence and in presence of divalent metal cations (triple complexes) are discussed. The triple complexes represent the generation of cellular structures such as pore complexes of eucaryotes and "Bayer's junctions" of procaryotes. The participation of triple complexes in the formation of structure of bacterial and eucaryotic nucleoid and nuclear matrix is analysed. A model of formation of triple complexes and cellular structures and their role in DNA-lipid interactions are discussed. 相似文献
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This review of Photochemistry and Photobiology summarizes articles published in 2010, and highlights progress in the area of photosensitization. The synthesis of conjugated photosensitizers is an area of interest where increasing water solubility has been a goal. Targeting infrared sensitizer absorption has been another goal, and relates to the practical need of deep tissue absorption of light. Photodynamic techniques for inactivating microbes and destroying tumors have been particularly successful. Biologically, singlet oxygen [(1)O(2)((1)Δ(g))] is an integral species in many of these reactions, although photosensitized oxidations tuned to electron and hydrogen transfer (Type I) give rise to other reactive species, such as superoxide and hydrogen peroxide. How photoprotection against yellowing, oxygenation and degradation occurs was also an area of topical interest. 相似文献