RADIATION CHEMISTRY OF AMINOALKYITHIOIS

Abstract

Radiation chemistry of aminoalkylthiols and some derivatives (aminoalkyl-S-thiophosphates and aminoalkyl-S-thiosulfates among which are most effective radioprotectors) in aqueous solutions has been studied in order to establish the relation between the structure of these compounds and their radiation-chemical properties. Increase in the number of methylene groups between the sulfur atom and nitrogen atom in the aminothiol molecule from 2 to 4 and substitution of the amino group hydrogene by an alkyl radical has been found to be without appreciable effect both on the “spectra” of radiolisis products and rate constants for interaction of H, e^? _aq and OH with aminothiols     

CORRELATION BETWEEN INTERFACIAL TENSIONS AND MICELLAR STRUCTURES

It is shown that results of surface and interfacial tension measurements can be used to predict the type of micelles and of liquid crystalline phases which are formed in binary and ternary surfactant solutions. In particular it is possible to predict the position of l.c. cubic phases in ternary systems consisting of surfactant, hydrocarbon and water. Data to demonstrate the conclusions were obtained on the surfactants Alkyltrimethylammoniumbromides, Alkyldimethylaminoxides and Alkyldimethylphosphinoxides. It was found that the interfacial tension of a dilute micellar solution against a reference hydrocarbon is a most sensitive and indicative parameter for the prediction of the different structures. Large changes of the interfacial tension were observed for the three systems having the same hydrocarbon chainlength. The value of the interfacial tension directly reflects also the amount of hydrocarbon which can be solubilized in the micellar solution. Interfacial tensions larger than 1mN/m are indicative of globular micelles while interfacial tensions between 0.1 and 1 mN/m indicate the formation of rods. Values below 0.1 mN/m indicate disclike micelles or lamellar phases.

The interfacial tension depends somewhat on the kind of hydrocarbon which is used for the measurements. It is observed that for several surfactant solutions the interfacial tension passes through a shallow minimum when the chainlength of the hydrocarbon is increased from six to sixteen.     

蒽环与苯环间的光化学Ⅰ.蒽环与苯环间分子内光致环加成反应

9 氯甲基蒽 ( 1 )与 3 ,5 二甲氧基苄醇 ( 2 )在相转移催化剂存在下反应生成 9 ( 3 ,5 二甲氧基苄基氧甲基 )蒽 ( 3 ) .( 3 )的苯溶液在紫外光照射下发生蒽环与苯环间的分子内 [4π + 4π]光致环加成反应 ,定量地生成多环化合物 ( 4 ) .( 4 )在热的作用下发生逆反应 ,定量地转化成原料 ( 3 ) .这种光致可逆反应可应用于制备光开关材料 .     

RELATIONS BETWEEN PHOTOCHEMISTRY AND FLUORESCENCE IN CELLS AND EXTRACTS OF PHOTOSYNTHETIC BACTERIA*

Abstract— Light-induced changes in the yield of bacteriochlorophyll fluorescence have been measured in cells and chromatophores of photosynthetic bacteria, and coordinated with light-induced absorbancy changes. Comparisons were drawn during transitions between dark and light steady states and also between steady states established at different light intensities. Aerobic cell suspensions of Rhodospirillum rubrum, Rhodopseudomonas spheroides, Chromatium and Rhodopseudomonas sp. NHTC 133 showed a strict correspondence between changes in the fluorescence yield and the bleaching of P870 (P985 in Rps. sp. NHTC 133), as reported by Vredenberg and Duysens for R. rubrum cells. The relationship shows that singlet excitation energy in bacteriochlorophyll is quenched by P870 at a rate proportional to the concentration of unbleached P870. This implies that the photosynthetic units are not independent with respect to energy transfer. In anaerobic cell suspensions the change in fluorescence did not follow the bleaching of P870 in the manner described by Vredenberg and Duysens. Here a change in fluorescence may have resulted from the reduction of a primary photochemical electron acceptor as well as from the oxidation (bleaching) of P870. In chromatophore preparations there were further deviations from the Vredenberg and Duysens relationship which could be attributed to changes in the rate constants for quenching of singlet excitation energy. Finally there was a light-induced increase in the fluorescence yield which was related to a band shift of bacteriochlorophyll and not to the bleaching of P870. Aerobic cell suspensions presented a limiting case in which these complications were absent. No change in the fluorescence was associated uniquely with the oxidation of cytochrome or band shifts of carotenoid pigments. These results, when coordinated with earlier findings about the fluorescence of bacteriochlorophyll and P870, indicate that the singlet excitation quantum is the only energy carrier linking the absorption of light with the initiation of photochemistry in bacterial photosynthesis.     

PHOTOCHEMISTRY OF DNA USING 193 nm EXCIMER LASER RADIATION

Photoproducts in double-stranded DNA induced by 193 nm radiation have been investigated. Double-stranded, supercoiled pBR322 DNA in buffered aqueous solution was exposed to varying fluences of 193 nm radiation from an ArF excimer laser. The quantum yields for formation of cyclobutylpyrimidine dimers, frank strand breaks and alkali labile sites were calculated from the conversion of supercoiled (Form I) DNA to relaxed (Form II) DNA after treatment with Micrococcus luteus dimer-specific endonuclease, no treatment, or treatment with alkali and heat, respectively. The quantum yields were 1.65 (+/- 0.03) X 10(-3) for pyrimidine dimers, 9.4 (+/- 3.2) X 10(-5) for frank strand breaks and 9.6 (+/- 3.6) X 10(-5) for alkali labile sites. The quantum yields for pyrimidine dimers and strand breaks and alkali labile sites were not affected by 10 nM mannitol. The relative quantum yields for these DNA photoproducts induced by 193 nm radiation differed markedly from those produced by 254 nm radiation.     

QUANTITATIVE CORRELATION BETWEEN SPECTROPHOTOMETRIC PHYTOCHROME ASSAY AND PHYSIOLOGICAL RESPONSE

Abstract— Apparent synthesis* of the enzyme lipoxygenase in the cotyledons of the mustard seedling (Sinapis alba L.) is controlled by phytochrome (P_{fr ground state})? through a threshold (all-or-none) mechanism. This response was used to determine physiologically the photostationary states, Λ that is, the [P_fr]/[P_tot] ratios established by different wavelengths in the red and far-red range of the spectrum, including the standard red and far-red sources used in this laboratory (Mohr, 1966). Under the premises (for which justification has been given on previous occasions) that the [P_fr]/[P_tot] ratio for standard red light is 0.8, and that the decay of P_fr is a first-order process with a half-life of 45 min, the [P_fr]/[P_tot] ratios determined physiologically by means of the lipoxygenase response agree with the [P_fr]/[P_tot] ratios determined spectrophotometrically by Hartmann and Spruit (cf. Fig. 9 in Hanke et al., 1969) in hypocotyl hooks of mustard seedlings. In the hook the _fr, that is, the [P_fr]/[P_tot] ratio for standard far-red, is found to be 0.023. In the cotyledons, this ratio is several times higher (Schafer et al., 1972). The conclusion that apparent lipoxygenase synthesis in the cotyledons is controlled by phytochrome located in the hook has been substantiated by further spectrophotometric (Schäfer et al., 1973) and physiological experiments (H. Oelze-Karow and H. Mohr, in preparation). The minimum steepness of the threshold was determined. An increase of the P_fr level from 118 (relative units) to 130 leads to an instantaneous and total suppression of apparent lipoxygenase synthesis; a corresponding decrease from 130 (relative units) to 118 leads to an immediate resumption of apparent LOG synthesis at full speed. It is concluded that an explanation of the experimental facts requires a cooperative effect on the level of P_fr, a high degree of synchrony on the cellular and organismic level and rapid communication between the hypocotyl hook and the cotyledons. *The term ‘apparent synthesis’ is used operationally in the present paper to denote any increase of enzyme activity, although de novo synthesis of lipoxygenase has not so far been rigorously demonstrated. The usual inhibitor experiments (cf. Oelze-Karow et al., 1970) have led to the conclusion that intact RNA and protein synthesis is required for an increase of lipoxygenase activity.     

LACK OF CORRELATION BETWEEN SUPPRESSION OF CONTACT HYPERSENSITIVITY BY UV RADIATION AND PHOTOISOMERIZATION OF EPIDERMAL UROCANIC ACID IN THE HAIRLESS MOUSE

Abstract The immunological consequences of exposure to UVA (320–400 nm) radiation are unclear. This study describes the relationship between the generation of epidermal cis -urocanic acid and the ability to respond to a contact-sensitizing agent, in hairless mice exposed to different UV radiation sources, which incorporate successively greater short-wavelength cutoff by filtration of the radiation from fluorescent UV tubes. Mice were exposed to these radiation sources at doses systematically varying in UVB radiation content but supplying increasing proportions of UVA radiation. All radiation sources were found to generate approximately 35% cis -urocanic acid in the epidermis, thus normalizing the sources for cis -urocanic acid production. However, only those sources richest in short-wavelength UVB resulted in suppression of the systemic contact hypersensitivity response. These sources also induced the greatest erythema reaction, measured as its edema component, in the exposed skin. A strong correlation was thus demonstrated between the induction of edema and the suppression of contact hypersensitivity, but there appeared to be no correlation between the generation of epidermal cis-urocanic acid and suppression of contact hypersensitivity. The sources richest in UVA content did not result in suppression of contact hypersensitivity: furthermore mice previously irradiated with such UVA-rich sources were refractory to the immunosuppressive action of exogenous cis-urocanic acid. A protective effect of the increased UVA content thus appeared to be inhibiting immunosuppression by the available endogenously generated or exogenously applied cⁱs-urocanic acid.     

INTERACTION BETWEEN TYROSINE AND DIVALENT SULFUR IN FLUORESCENCE QUENCHING AND IN THE PHOTOCHEMISTRY OF RIBONUCLEASE

Abstract— –Ribonuclease is inactivated in aqueous solution by u.v. light through different mechanisms according to whether divalent sulfur or aromatic amino acids are the primary light absorbers. At 284 nm, absorbed mainly by tyrosine, the presence of O₂ inhibits photoinactivation and H₂S formation, but does less so at 254 or 313 nm. Based on data with model substances containing disulfide groups a mechanism is indicated in which excited tyrosine is quenched through electron transfer to adjacent divalent sulfur within the protein. Disulfide compounds are shown to be very efficient quenchers of tyrosine fluorescence.     

影像科学与光化学

<正>本刊刊登以下研究领域的创新成果:光化学、影像科学与技术、光电化学及光电子技术(包括光电转换及储存材料、电光材料、非线性光学材料、纳米材料、电致发光材料及器件)、信息科学及信息材料(包括遥感、信息存储和记录、图像信息处理、信息显示材料等)、光生物、光医学、环境光化学等。Imaging Science and Photochemistrypublishes the results of studies on all aspects of photo-     

影像科学与光化学

正本刊刊登以下研究领域的创新成果:光化学、影像科学与技术、光电化学及光电子技术(包括光电转换及储存材料、电光材料、非线性光学材料、纳米材料、电致发光材料及器件)、信息科学及信息材料(包括遥感、信息存储和记录、图像信息处理、信息显示材料等)、光生物、光医学、环境光化学等。"Imaging Science and Photochemistry"publishes the results of studies on all aspects of photochemistry and imaging science/technology.The scope includes photo/electro-chemistry and opto-electronic technology,as well     

影像科学与光化学

正本刊刊登以下研究领域的创新成果:光化学、影像科学与技术、光电化学及光电子技术(包括光电转换及储存材料、电光材料、非线性光学材料、纳米材料、电致发光材料及器件)、信息科学及信息材料(包括遥感、信息存储和记录、图像信息处理、信息显示材料等)、光生物、光医学、环境光化学等。     

影像科学与光化学

正本刊刊登以下研究领域的创新成果:光化学、影像科学与技术、光电化学及光电子技术(包括光电转换及储存材料、电光材料、非线性光学材料、纳米材料、电致发光材料及器件)、信息科学及信息材料(包括遥感、信息存储和记录、图像信息处理、信息显示材料等)、光生物、光医学、环境光化学等。     

影像科学与光化学

正本刊刊登以下研究领域的创新成果:光化学、影像科学与技术、光电化学及光电子技术(包括光电转换及储存材料、电光材料、非线性光学材料、纳米材料、电致发光材料及器件)、信息科学及信息材料(包括遥感、信息存储和记录、图像信息处理、信息显示材料等)、光生物、光医学、环境光化学等。Imaging Science and Photochemistrypublishes the results of studies on all aspects of photo-     

影像科学与光化学

<正>本刊刊登以下研究领域的创新成果:光化学、影像科学与技术、光电化学及光电子技术(包括光电转换及储存材料、电光材料、非线性光学材料、纳米材料、电致发光材料及器件)、信息科学及信息材料(包括遥感、信息存储和记录、图像信息处理、信息显示材料等)、光生物、光医学、环境光化学等。     

影像科学与光化学

<正>http:∥www.yxkxyghx.org本刊刊登领域:影像科学与技术、生物与医学成像、数字成像及图像信息处理、光化学、光医学等。     

影像科学与光化学

<正>本刊刊登以下研究领域的创新成果:光化学、影像科学与技术、光电化学及光电子技术(包括光电转换及储存材料、电光材料、非线性光学材料、纳米材料、电致发光材料及器件)、信息科学及信息材料(包括遥感、信息存储和记录、图像信息处理、信息显示材料等)、光生物、光医学、环境光化学等。"Imaging Science and Photochemistry"publishes the results of studies on all aspects of photochemistry and imaging science/technology.The scope includes photo/electro-chemistry and optoelectronic technology,as well as photo-electrochemical conversion and storage materials,electro-optical     

CORRELATION BETWEEN ENDOGENOUS GLUTATHIONE CONTENT AND SENSITIVITY OF CULTURED HUMAN SKIN CELLS TO RADIATION AT DEFINED WAVELENGTHS IN THE SOLAR ULTRAVIOLET RANGE

Abstract— Glutathione depletion of cultured human skin fibroblasts by treatment with buthionine-S,R-sulfoximine (BSO) sensitises them to radiation at a series of defined wavelengths throughout the solar UV range. We now show that there is a close quantitative correlation between cellular glutathione content (as depleted by BSO) and sensitivity to radiation at 365 nm. A weaker correlation is observed when cells are depleted of glutathione using diethylmaleimide. Both fibroblasts and epidermal keratinocytes derived from the same foreskin biopsy are sensitised to radiation at 313 nm by glutathione depletion. However, the keratinocytes are sensitised to a much lesser extent, an observation which agrees quantitatively with the higher residual levels of cellular glutathione remaining after maximum depletion by BSO (approximately 25% for the keratinocytes vs less than 5% for the fibroblasts). At low to intermediate fluence levels, 10 mM cysteamine present during irradiation at 302 nm is able to almost completely reverse the sensitising effects of glutathione depletion suggesting that the endogenous thiol protects against radiation at this wavelength by a free radical scavenging mechanism. At 313 nm, the sensitisation is not reversed by cysteamine suggesting that glutathione plays a more specific role in protection against radiation at longer wavelengths. Xeroderma pigmentosum group A fibroblasts (excision deficient) are also sensitised to radiation at 313 and 365 nm by depletion of glutathione but since the sensitization is less than that observed for the normal strain, we cannot conclude that glutathione protects against a sector of DNA damage susceptible to excision repair. The results provide further evidence that endogenous glutathione is involved in protecting human skin cells against a wide range of solar radiation damage and suggest that while free radical scavenging is involved at the shortest wavelength (302 nm) tested, a more specific role of glutathione is involved in protection against radiation at longer wavelengths.     

单轴取向PET薄膜的α松弛与力学行为的相关性

本文用动态力学方法研究了在不同温度和速度下单轴自由辐拉伸的聚对苯二甲酸乙二酯薄膜的非晶区状态,表明从熔体骤冷的非晶态试片在不同热拉伸条件下拉伸,可以得到非晶状态有显著差别的单轴取向薄膜。它们的非晶状态可以用动态力学温度谱的α峰的高度,形状和位置来表征。具有不同非晶状态的试样的储能模量E′(25℃)、屈服应力、负荷-伸长曲线与α松弛的参数以及其他结构参数间有很好的相关性。在一定的条件下热拉伸温度和速度存在Arrhenius型的速度-温度变换关系。