PHOTOREDUCTION OF THIONINE BY WATER

Abstract —The photoreduction of thionine by water has been studied, using a technique applied in earlier work on photoreduction of methylene blue. It is found for thionine as for methylene blue, that a long-lived excited intermediate is formed, and that two such intermediates react to produce a single reduced molecule, thus providing adequate energy for the reaction. The mechanism proposed for methylene blue photoreduction is shown to be applicable to thionine photoreduction as well, indicating the unimportance of the amine methyl groups. Although in previous work it was suggested that H₂O was the reducing agent, none of them, however, could determine the H₂O₂ formed. The formation of H₂O₂ is confirmed in this work, and the kinetics of its formation are shown to be in accordance with the mechanism.     

VISIBLE LIGHT PHOTOCHEMICAL RELEASE OF NITRIC OXIDE FROM S-NITROSOGLUTATHIONE: POTENTIAL PHOTOCHEMOTHERAPEUTIC APPLICATIONS

Abstract Some aspects of the physiological role of NO may be mediated by stable NO-carriers such as S -nitrosoglutathione and related S -nitrosothiols. In this report we show that irradiation of S-nitrosoglutathione at either absorption band (λ_max= 340 nm or 545 nm) results in the release of nitric oxide. Photolysis of S -nitrosoglutathione at 545 nm exhibited a quantum yield of 0.056 ± 0.002 and was best approximated by a first-order process with k _obs= 4.9 × 10⁻⁷± 0.3 × 10⁻⁷ s⁻¹. The photolytic release of NO from S -nitrosoglutathione resulted in an enhanced cytotoxic effect of S -nitrosoglutathione on HL-60 leukemia cells. That the cytotoxic effect of S -nitrosoglutathione was diminished by the addition of oxyhemoglobin strongly suggests that NO is the cytotoxic species. The finding that NO can be readily liberated from S -nitrosoglutathione by visible radiation indicates that the photochemical properties of this compound in the visible spectrum must be considered in order to obtain meaningful data as to its physiological role and the S -nitrosoglutathione and related compounds may find use as photochemotherapeutic agents.     

PHOTOOXIDATION OF 2-MERCAPTOETHANOL BY VARIOUS WATER-SOLUBLE PHTHALOCYANINES IN AQUEOUS ALKALINE SOLUTION UNDER IRRADIATION WITH VISIBLE LIGHT

Abstract A selection of charged water-soluble phthalocyanines was employed for the photocatalytic oxidation of 2-mercaptoethanol in aqueous alkaline solution in the presence of oppositely charged detergents. Most efficient are Zn(II) and Al(III) phthalocyaninetetrasulfonic acids, which oxidize the thiolate to the sulfonic acid and sulfate, whereas Co(II)phthalocyaninetetrasulfonic acid does not exhibit a photoeffect. During the photooxidation reactions, decomposition (photobleaching) of the zinc phthalocyanine derivatives occurs, whereas the analogous alumina chelates are more stable. Covalent binding of Zn(II)phthalocyanine derivatives to silica carriers results in photocatalytic activities even in the absence of detergents, since the immobilization of the complexes preserves the required monomeric state. Moreover, the photodecomposition (bleaching) of the heterogenized complexes is strongly retarded. For the photo-oxidations mainly the pathway via the sensitized formation of singlet oxygen with subsequent oxidation reactions is valid. Hydrogen peroxide as one reduction product of oxygen was found.     

STIMULATION OF Escherichia coli DIVISION BY LOW-INTENSITY MONOCHROMATIC VISIBLE LIGHT

Abstract— Bacterial suspensions in a phosphate buffer were irradiated at 364, 404, 434, 454, 484, 520, 560. 570, 599, 619, 630, 633, 640, 693, 730 and 750 nm, incubated in Hottinguer broth, and assayed for viability by the standard surface plating technique. When irradiated at 404, 454, 560, 619, and 750 nm, the cells started dividing more rapidly, the growth stimulation effect reaching170–180% 60 min after irradiation. The shape of the action spectrum and the reduced-minus-oxidized difference spectrum of the bacterial suspensions suggest that respiratory chain components of the bacterium such as dehydrogenases and cyt d might be the photoacceptors involved. The growth stimulation effect is believed to be due to the ability of the irradiation-activated respiratory chain to produce the necessary pH gradient more rapidly, thus enabling the cells to start dividing earlier.     

SELECTIVE INACTIVATION OF MICROSOMAL DRUG METABOLIZING PROTEINS BY VISIBLE LIGHT

Abstract— Rat liver microsomes treated with heterochromatic visible light (λ > 400 nm) and O₂ showed a preferential inactivation of NADPH-cytochrome P₄₅₀ reductase and cytochrome P₄₅₀, proteins involved in drug metabolism. Cytochrome P₄₅₀ destruction correlates with lipid peroxidation; both are oxygen dependent and affected to the same extent by antioxidants and radical scavengers. Under anaerobic conditions. NADPH-cytochrome P₄₅₀ reductase is the only component which is inactivated; this is accompanied by FMN loss and activity can be restored by reconstitution.     

STUDIES ON LYSOZYME: EFFECT OF VISIBLE LIGHT ON THE CONFORMATION OF THE ENZYME IN THE PRESENCE OF METHYLENE BLUE

Abstract— Lysozyme undergoes conformational changes when exposed to visible light in the presence of methylene blue. Ultracentrifugation, gel filtration and end group analysis showed that no peptide bond was cleaved. About 30 per cent of the tryptophan residues were, however, modified. The enzymic activity decreased by 50 per cent. The sedimentation coefficient and helical content decreased; the extinction in the u.v. region between 185 to 210 nm increased. The photooxidized enzyme was more susceptible to trypsinolysis than the native enzyme.     

VISIBLE LIGHT ANAEROBIC PHOTOCONVERSION OF TYROSINE SENSITIZED BY RIBOFLAVIN. CYTOTOXICITY ON MOUSE TUMORAL CELLS

The anaerobic phototransformation of tyrosine under visible light sensitized by riboflavin is reported. The cytotoxicity of the anaerobic photoproducts on in vitro-cultured myeloid mouse tumoral cells was demonstrated. A radical mechanism is proposed. Dityrosine was identified as one of the main anaerobic photoproducts by using absorption, emission and ¹H-NMR spectra.     

樟脑酮/过氧化物复合体系引发丙烯酸酯可见光聚合反应

采用差热扫描方法（ＤＳＣ）研究了樟脑酮（ＣＱ）／过氧化物（ＰＯ）复合体系引发三缩乙二醇双甲基丙烯酸酯（ＴＥＧＤＭ）的可见光聚合．与ＣＱ单一引发体系相比,ＣＱ和ＰＯ组成的复合体系更为有效．实验结果指出,加入过氧化物,如ＤＣＰＯ和ＤＢＰＯ,使聚合速率显著增加,最大速率到达时间明显缩短,然而它们对应的过氧化氢化合物,如ＴＢＨＰ、ＣＭＨＰ却效果不佳,复合体系的增效作用表明,激发态ＣＱ通过能量传递机制,使过氧化物发生有效的光解生成活性自由基,同时发现在含氧的条件下聚合反应速率得到增加．     

锌—镉法测定天然水中硝酸盐的盐误差及其解决方法

研究了锌-镉法测定天然水中硝酸盐的盐误差,发现水中含盐量对还原率有重大影响,但在盐度为1%以后还原率基本不变;加入人工海盐(1.5g/50ml水样)可消除盐误差.由此建立了没有盐误差的新的锌-镉法.方法相对标准偏差小于3%,回收率为98%～102%,与镉-铜法对比,两种方法的相对偏差小于8%.     

ACTION OF VISIBLE LIGHT ON ENZYMES IN CELL ENVELOPES OF MICROCOCCUS ROSEUS

Abstract— Envelopes were isolated from the carotenogenic bacterium Micrococcus roseus , which is subject to photodynamic killing in the presence of a photosensitizing dye but not in the absence of such a dye. Envelope preparations contained 88 per cent of the total cellular carotenoids, 20% of the NADH oxidase, 100 per cent of the ATPase and 30% of the succinic dehydrogenase activity. NADH oxidase activity in envelopes was stimulated 2–5-fold by light in the presence of dye; this was followed by inactivation. In the presence of dye, ATPase was inactivated by light and 25 per cent of the succinic dehydrogenase activity was lost. In the absence of dye, responses were extended over a longer period of time, but similar patterns were observed for the three enzymes, indicating that envelopes contain an endogenous photosensitizer(s). Carotenoid-deficient cells were obtained after growth in medium containing diphenylamine. But all three enzymes showed evidence of instability in envelope preparations, indicating that diphenylamine affects membrane structure in addition to inhibiting synthesis of colored carotenoids.     

FLASH PHOTOLYSIS OF SEVERAL AROMATICS BY ULTRAVIOLET LIGHT AND VISIBLE LIGHT IN THE PRESENCE OF EOSIN Y*

Abstract— A flash photolysis investigation was made of the photo-oxidation of aqueous aniline, resorcinol, βnaphthol, p-sulfanilic acid, and p-bromophenol induced by ultraviolet and visible light irradiation in the presence of eosin Y. The transient spectra show that u.v. irradiation generates the hydrated electron (except in p-bromophenol) and the radical products of one-electron oxidation. The initial products of the eosin-sensitized oxidations are the dye semi-quinone and aromatic radicals which coincide with the u.v. photolysis products in at least several cases. The investigation of the reaction kinetics by rapid spectrophotometry with analog computer analysis shows that the aromatics quench the triplet state of eosin and also react with it in a slower electron-transfer process, in competition with ‘dye-dye’ quenching and electron-transfer reactions. The u.v. and dye-sensitized oxidations are discussed in terms of their energetics.     

PHOTOCHEMICAL REACTIONS IN RIGID MEDIA-I. THE EFFECT OF GELATIN ON THE AEROBIC PHOTOCHEMISTRY OF RIBOFLAVIN IN AQUEOUS SOLUTION

Abstract— The addition of potassium iodide to dilute aqueous solutions of riboflavin reduced both the rate of the aerobic photolysis and the fluorescence quantum yield of riboflavin in the same proportions. This indicated that under these conditions the photolysis proceeded from the singlet excited state. The addition of gelatin to aqueous solutions of riboflavin also reduced the rate of the aerobic photolysis but increased slightly the quantum yield of fluorescence. The rates and the fluorescence of solutions of riboflavin to which gelatin had been added were also reduced by the addition of potassium iodide but in this case the effect on the rate was proportionately greater than the effect on the fluorescence. The data suggests that in the presence of gelatin the mechanism of the reaction is changed and that the triplet state becomes more important.     

SrTiO_3粉末在可见光照射下光氧化水产氧的研究

SrTiO_3粉末在FeCl_3水溶液里的悬浮体([Fe~(3+)]=1.0×10~(-3)mol/L,pH2.8,SrTiO_3含量1.25g/L)能在λ>400 nm的可见光照射下光氧化水产氧。在相同条件下SrTiO_3和WO_3粉末的混合悬浮体(SrTiO_3与WO_3含量均为1.25g/L)产氧的速率为两者单独存在时的速率之和。光声光谱实验显示SrTiO_3粉末在从溶液里吸附Fe~(3+)后对可见光的吸收大大增强,使它能在可见光下光氧化水产氧。     

INVESTIGATIONS ON BIOLOGICAL EFFECT OF POLARIZED LIGHT

Abstract— The biological effects of single and 4-time irradiation of primary human embryo fibroblasts with 4 J/cm² polarized light emitted by a halogen light source were investigated. The functional state of the plasma membrane was examined by means of lectin-binding and polycationized ferritin-binding techniques. It was established that the Con A binding of the cells did not change, whereas the number of negatively charged binding sites increased to a significant degree in relation to the untreated (control) samples and cell cultures exposed to diffuse (non-polarized) light. The micromorphological examinations showed no ultrastructural deviations. The quantitative increase of negative surface charges may be regarded as an indication of the biological effect of polarized light exerted on the cell membrane. The modifying effect of polarized light on the survival of E. coli exposed to the ionizing radiation was manifested in decreased anoxic radiation response.     

PHOTOCHEMICAL REDUCTION OF 5-BROMOURACIL BY CYSTEINE DERIVATIVES AND COUPLING OF 5-BROMOURACIL TO CYSTINE DERIVATIVES

Irradiation of pH 7, aqueous solutions of 5-bromouracil (BU) in the presence of cysteine peptide-like derivatives at 308 nm using a XeCl excimer laser yielded initial formation of only uracil (U) and the corresponding cystine derivative. Continued irradiation yielded an S-uracilylcysteinyl adduct as well as additional U and cystine derivative. Similar irradiation of a solution of BU and a cystine derivative yielded initial formation of U and the S-uracilylcysteinyl adduct. Formation of these products as well as secondary products of uracil photochemistry was observed upon irradiation of the respective solutions with 254 nm light. With 308 nm laser excitation, U-Cys adduct formation and reduction of BU to U are proposed to occur via initial electron transfer from the disulfide of the cystine derivative to triplet BU. The quantum yield of BU destruction with 308 nm excitation in the presence of cystine derivative is 1.1 X 10(-3). Reaction of triplet BU with the cysteine derivative does not yield U-Cys adduct but U and cystine derivative. A possible byproduct of reduction of triplet BU to U by a cysteinyl residue in a protein BU-DNA complex is a sulphenyl bromide which might yield a protein-DNA crosslink via nucleophilic substitution on sulfur by a nucleophilic site in DNA.     

两亲性梳形共聚物PASP-Na-g-DDA的合成及接枝率对其水溶液胶束性质的影响

天冬氨酸自身缩聚产物聚琥珀酰亚胺(PSI)与十二胺(DDA)发生氨解反应,该氨解产物在碱性条件下水解,制得了一种两亲性梳形共聚物PASP-Na-g-DDA.通过改变DDA与PSI的比例,合成了一系列不同接枝率的两亲性梳形共聚物.用核磁共振(1H-NMR)及凝胶渗透色谱(GPC)对共聚物的结构进行了表征.随着疏水链段DD...     

建筑用梳形共聚物分散剂溶液行为的光散射研究

采用激光光散射研究了一种主链为聚丙烯酸侧链为聚乙二醇的梳形共聚物分散剂的一些溶液行为.从静态光散射得出了较为合理的表观重均分子量、均方旋转半径等参数.动态光散射给出了流体力学半径分布及其角度和浓度依赖性.结合静态和动态光散射,上述梳形共聚物分散剂在溶液中的构象也得到初步的表征.通过与描述梳形聚合物的Gay-Raphae模型进行比较表明,这类梳形共聚物溶液在低盐离子和低pH值条件下存在聚集行为,形成以PAA主链为核PEG为壳层的类胶束聚集.