The Photochemical Reaction of Pentachlorophenol

A herbicide, sodium pentachlorophenoxide (Na-PCP), used in Japan, is easily decomposed with sunlight after its application in the rice field. The photochemical reaction of Na-PCP in an aqueous solution on exposure to sunlight afforded numerous products which were mainly accompanied with chloranilic acid and a yellow compound (I). The chemical structure of the yellow compound I was established as being 3, 4, 5-trichloro-6-(2′-hydroxy-3′, 4′, 5′, 6′-tetrachlorophenoxy)-o-benzoquinone by chemical and spectroscopic evidences.

Minor decomposition products of sodium pentachlorophenoxide (Na-PCP) in an aqueous solution by sunlight have been isolated. Chemical structures of them are described, and infrared and ultraviolet spectra are presented in support of these stractures. These illustrate a new type of oxidative reaction of phenols.     

Photochemical Colorine Reaction of Sake

Coloring reaction of sake caused by exposure to sun-light was investigated. There is one of the coloring reactions in which deferri-ferrichrysin participate. The reaction was named Reaction I.

Deferri-ferrichrysin, tyrosine, Mn²⁺ and unknown nitrogenous compound named conveniently compound X were essential for Reaction I and citric acid was stimulative.

Compound X was purified by using Amberlite IR 120 (H type) column, active carbon column, silicic acid column and alumina column, and crystallized from methanol-water (1 : 1).

The crystals decomposed at 288~290°C. The ultraviolet and infrared spectra of the compound X were essentially identical with those of authentic kynurenic acid.

From these results the compound X was identified as kynurenic acid.

Since kynurenic acid alone did not cause the color development and riboflavin could be substituted for kynurenic acid in Reaction I, kynurenic acid may act as photosensitizer in Reaction I.     

Photochemical Reaction between Uridine and Sulfhydryl Compounds

Kinetics of photochemical reaction between uridine and sulfhydryl compounds were investigated in phosphate buffer (pH 7.0) and in unbuffered aqueous solution under aerobic condition. The results obtained clearly demonstrate that the photo-induced hydration or reduction of the uridine molecule was significantly influenced by the amount of sulfhydryl group present in the reaction medium. Reaction on uridine (1 mm) was observed to lead to photohydration with pseudo first order rates, independently of the presence of cysteine (1 mm or 2 mm), while in the presence of dithiothreitol (DTT, 1 mm to 10 mm) both photoreduction and photohydration of uridine were observed. The rate of photoreduction came to predominate as the amount of DTT increased. The reaction was discussed from the view point of food chemistry as well as reaction pathways.     

Characterization of the Photochemical Reaction Cycle of Proteorhodopsin

Absorption changes in the photocycle of the recently described retinal protein, proteorhodopsin, are analyzed. The transient spectra at pH 9.5, where it acts as a light-driven proton pump, reveal the existence of three spectrally different intermediates, K, M, and N, named in analogy with the photointermediates of bacteriorhodopsin. Model analysis based on time-dependent absorption kinetic signals at four wavelengths suggested the existence of two more spectrally silent intermediates and lead to a sequential reaction scheme with five intermediates, K, M₁, M₂, N, and PR′, before decay to the initial state PR. An L-like intermediate was not observed, probably for kinetic reasons. By measuring the light-generated electric signal of an oriented sample, the electrogenicity of each intermediate could be determined. The electrogenicities of the first three intermediates (K, M₁, and M₂) have small negative value, but the last three components, corresponding to the N and PR′ intermediates and PR, are positive and two-orders-of-magnitude larger. These states give the major contributions to the proton translocation across the membrane. The energetic scheme of the photocycle was calculated from the temperature-dependence of the absorption kinetic signals.     

紫细菌光合反应中心中细菌脱镁叶绿素被置换后的光化学活性

采用新型表面活性剂ＬＤＡＯ,结合ＤＥＡＥ纤维素层析法,我们提纯了紫细菌Ｒｈｏｄｏｂａｃｔｅｒｓｐｈａｅｒｏｉｄｅｓ６０１的光合反应中心。在一定温度和丙酮的协同作用下,外加的植物脱镁叶绿素ａ可取代反应中心细菌脱镁叶绿素,形成含有脱镁叶绿素ａ的紫细菌光合反应中心（ＰｈｅａＲＣ）。当协同作用１５ｍｉｎ和６０ｍｉｎ时,反应中心中的细菌脱镁叶绿素分别被替代了５０％和７１％。在ＰｈｅａＲＣ中,细菌脱镁叶绿素的ＱＸ（５３７ｎｍ）和ＱＹ（７５８ｎｍ）特征峰显著下降,而出现高等植物脱镁叶绿素的ＱＸ（５０９／５４２ｎｍ）和ＱＹ（６７４ｎｍ）特征峰。排除温度和丙酮的影响,替代时间为１５ｍｉｎ或６０ｍｉｎ的ＰｈｅａＲＣ的光化学活性分别为对照的７８％或７１％。     

Pentachlorophenol

Pentachlorophenol (PCP) is a substance whose widespread use, mainly in wood protection and pulp and paper mills, has led to a substantial environmental contamination. This in turn accounts for a significant exposure of the general human population, with rather high exposure levels being attained in occupational settings. Investigations on the genotoxic activity of PCP have given rise to divergent results which would seem to make an evaluation difficult. By grouping them into 3 categories a somewhat clearer picture, allowing finally an (admittedly tentative) assessment, can be obtained. PCP does seem to be at most a weak inducer of DNA damage: it produces neither DNA-strand breaks nor clear differential toxicity to bacteria in rec-assays in the absence of metabolic activation. Also in SCE induction no increase can be observed in vivo, while PCP is found marginally active in a single in vitro experiment. Metabolic activation, however, leads to prophage induction and to DNA strand breaks in human lymphocytes, presumably through the formation of oxygen radicals. A possible further exception in this area might be the positive results in the yeast recombination tests, although their inadequate reporting makes a full evaluation difficult. PCP does not seem to induce gene (point) mutations, as most bacterial assays, the Drosophila sex-linked recessive lethal test and in vitro assays with mammalian cells did not demonstrate any effects. Marginally positive results were obtained in the mammalian spot test in vivo and in one bacterial test; the positive result in the yeast assay for cycloheximide resistance is fraught somewhat with its questionable genetic basis. PCP does, however, induce chromosomal aberrations in mammalian cells in vitro and in lymphocytes of exposed persons in vivo. Those in vivo results that were unable to provide evidence of chromosomal damage are hampered either by methodological inadequacies or by too low exposure levels. The (rodent) metabolite tetrachlorohydroquinone might be a real genotoxic agent, capable of binding to DNA and producing DNA strand breaks; this activity is probably due to semiquinone radical formation and partly mediated through active oxygen species. Since this compound has not been tested in the common bacterial and mammalian mutagenicity assays, the few ancillary results on this substance cannot be used in a meaningful human risk assessment of PCP. Furthermore, this metabolite has only been produced by human liver microsomes in vitro, but has not been detected in exposed humans in vivo.(ABSTRACT TRUNCATED AT 400 WORDS)     

Pentachlorophenol

Pentachlorophenol (PCP) is a substance whose widespread use, mainly in wood protection and pulp and paper mills, has led to a substantial environmental contamination. This in turn accounts for a significant exposure of the general human population, with rather high exposure levels being attained in occupational settings.Investigations on the genotoxic activity of PCP have given rise to divergent results which would seem to make an evaluation difficult. By grouping them into 3 categories a somewhat clearer picture, allowing finally an (admittedly tentative) assessment, can be obtained.PCP does seem to be at most a weak inducer of DNA damage: it produces neither DNA-strand breaks nor clear differential toxicity to bacteria in rec-assays in the absence of metabolic activation. Also in SCE induction no increase can be observed in vivo, while PCP is found marginally active in a single in vitro experiment. Metabolic activation, however, leads to prophage induction and to DNA strand breaks in. human lymphocytes, presumably through the formation of oxygen radicals. A possible further exception in this area might be the positive results in the yeast recombination tests, although their inadequate reporting makes a full evaluation difficult.PCP does not seem to induce gene (point) mutations, as most bacterial assays, the Drosophila sex-linked recessive lethal test and in vitro assays with mammalian cells did not demonstrate any effects. Marginally positive results were obtained in the mammalian spot test in vivo and in one bacterial test; the positive result in the yeast assay for cycloheximide resistance is fraught somewhat with its questionable genetic basis.PCP does, however, induce chromosomal aberrations in mammalian cells in vitro and in lymphocytes of exposed persons in vivo. Those in vivo results that were unable to provide evidence of chromosomal damage are hampered either by methodological inadequacies or by too low exposure levels.The (rodent) metabolite tetrachlorohydroquinone might be a real genotoxic agent, capable of binding to DNA and producing DNA strand breaks; this activity is probably due to semiquinone radical formation and partly mediated through active oxygen species. Since this compound has not been tested in the common bacterial and mammalian mutagenicity assays, the few ancillary results on this substance cannot be used in a meaningful human risk assessment of PCP. Furthermore, this metabolite has only been produced by human liver microsomes in vitro, but has not been detected in exposed humans in vivo. Its formation in mutagenicity test systems and its activity involving radicals might, however, help to explain some of the divergencies in the genotoxicity results.The review concludes that PCP is a weak human clastogen which may lack other genotoxic properties, although it may add somewhat to the normal oxidative damage.     

Remote Excitation Polarization-Dependent Surface Photochemical Reaction by Plasmonic Waveguide

For the first time, we report remote excitation polarization-dependent surface photochemical reaction by plasmonic waveguide. Remote excitation polarization-dependent surface-enhanced Raman scattering (SERS) spectra indicate a surface photochemical reaction that p-aminothiophenol is converted to p,p′-dimercaptoazobenzene (DMAB) induced by the plasmonic waveguide. Surface plasmon polaritons generated at the end of a silver nanowire can propagate efficiently along the nanowire, and be coupled by nanoparticles near the nanowire as a nanoantenna. Massive electromagnetic enhancement is generated in the nanogap between the nanowire and the nanoparticles. The remote excitation polarization-dependent SERS spectra can be obtained experimentally in the nanogaps; furthermore, the remote excitation polarization-dependent SERS spectra of DMAB reveal the occurrence of this surface catalytic reaction. Theoretical simulations using finite-difference time-domain methods strongly support our experimental results.     

光化学反应诱导大鼠视网膜水肿模型

目的:通过静脉注射光敏剂Erythrosin B联合激光照射诱导大鼠视网膜水肿模型,并观察该模型中大鼠视网膜及血管形态改变.方法:大鼠尾静脉注射光敏剂Erythrosin B后,使用532nm Nd:YAG激光(1.95±0.05 mw)照射大鼠视网膜8分钟.分别于建模后第1、2、3、5、7及14天进行眼底照相、眼底荧光造影(FFA)及视网膜光学相干断层扫描(OCT)检查.并在OCT图像上测量大鼠视网膜厚度(RT).结果:眼底照相、FFA及OCT结果显示大鼠视网膜在激光照射后可立即出现血管损伤及视网膜厚度增加,但未发现视网膜血管栓塞.激光照射前RT为219±2 μm,激光照射后第1天RT即增加至283±6μm,并在第2天到达顶峰(302±7μm),之后开始下降,至第5天恢复到激光照射前水平(234±9 μm),到第14天时视网膜发生明显萎缩,RT较激光处理前减小(198±6μm).结论:这一通过光化学反应诱导的视网膜水肿模型具有可靠及可重复性,可被运用于视网膜水肿的病理学及动力学研究.     

Inactivation of Escherichia coli by Photochemical Reaction of Ferrioxalate at Slightly Acidic and Near-Neutral pHs

Fenton chemistry, which is known to play an effective role in degrading toxic chemicals, is difficult to apply to disinfection in water treatment, since its reaction is effective only at the acidic pH of 3. The presence of oxalate ions and UV-visible light, which is known as a photoferrioxalate system, allows the Fe(III) to be dissolved at slightly acidic and near-neutral pHs and maintains the catalytic reaction of iron. This study indicates that the main oxidizing species in the photoferrioxalate system responsible for microorganism inactivation is OH radical. Escherichia coli was used as an indicator microorganism. The CT value (OH radical concentration × contact time; used to indicate the effect of the combination of the concentration of the disinfectant and the contact time on inactivation) for a 2-log inactivation of E. coli was approximately 1.5 × 10⁻⁵ mg/liter/min, which is approximately 2,700 times lower than that of ozone as estimated by the delayed Chick-Watson model. Since the light emitted by the black light blue lamp is similar to sunlight in the specific wavelength range of 300 to 420 nm, the photoferrioxalate system, which can have a dual function, treating water for both organic pollutants and microorganisms simultaneously, shows promise for the treatment of water or wastewater in remote or rural sites. However, the photoferrioxalate disinfection system is slower in inactivating microorganisms than conventional disinfectants are.     

Decomposition of Pentachlorophenol in Paddy Soil

The herbicide, pentachlorophenol decomposes within a few weeks after its application in rice fields. A reductive dechloronation was revealed as one of its decomposition pathways, in which some microorganisms play a dominant role and other soil chemical factors in a reduced condition are relatively of little importance. The stable decomposition products found in the paddy soil were 2,3,4,5-, 2,3,5,6- and 2,3,4,6-tetrachlorophenol, 2,4,5- and 2,3,5-trichlorophenol, 3,4- and 3,5-dichlorophenol, and 3-chlorophenol.     

The Photochemical Reaction Cycle and Photoinduced Proton Transfer of Sensory Rhodopsin II (Phoborhodopsin) from Halobacterium salinarum

Sensory rhodopsin II (HsSRII, also called phoborhodopsin) is a negative phototaxis receptor of Halobacterium salinarum, a bacterium that avoids blue-green light. In this study, we expressed the protein in Escherichia coli cells, and reconstituted the purified protein with phosphatidylcholine. The reconstituted HsSRII was stable. We examined the photocycle by flash-photolysis spectroscopy in the time range of milliseconds to seconds, and measured proton uptake/release using a transparent indium-tin oxide electrode. The pKa of the counterion of the Schiff base, Asp⁷³, was 3.0. Below pH 3, the depleted band was observed on flash illumination, but the positive band in the difference spectra was not found. Above pH 3, the basic photocycle was HsSRII (490) → M (350) → O (520) → Y (490) → HsSRII, where the numbers in parentheses are the maximum wavelengths. The decay rate of O-intermediate and Y-intermediate were pH-independent, whereas the M-intermediate decay was pH-dependent. For 3 < pH < 4.5, the M-decay was one phase, and the rate decreased with an increase in pH. For 4.5 < pH < 6.5, the decay was one phase with pH-independent rates, and azide markedly accelerated the M-decay. These findings suggest the existence of a protonated amino acid residue (X-H) that may serve as a proton relay to reprotonate the Schiff base. Above pH 6.5, the M-decay showed two phases. The fast M-decay was pH-independent and originated from the molecule having a protonated X-H, and the slow M-decay originated from the molecule having a deprotonated X, in which the proton came directly from the outside. The analysis yielded a value of 7.5 for the pKa of X-H. The proton uptake and release occurred during M-decay and O-decay, respectively.     

Industrial Pentachlorophenol Poisoning in Winnipeg

Enquiry into the occupational history of a patient presenting with stupor, hyperpyrexia and profuse sweating, and dying at a Winnipeg hospital a few hours later in coma, finally led to the identification of pentachlorophenol-a substance widely used as a wood preservative-as the cause of death of this worker and the cause of non-fatal intoxication in four other workers engaged by wood-processing plants. In these latter four cases the prominent clinical symptoms were sweating, weight loss and gastrointestinal complaints. A review of the literature revealed that pentachlorophenol exerts its toxicity following cutaneous absorption or inhalation by interference with oxidative phosphorylation, resulting in excessive release of heat. This substance has been the cause of several deaths in other countries. Observance of simple precautionary measures that ensure adequate ventilation and skin protection should suffice in making this industrially useful product safe.     

Pentachlorophenol degradation by Pseudomonas aeruginosa

Five Pseudomonas species were tested for ability to degrade pentachlorophenol (PCP). Pseudomonas aeruginosa completely degraded PCP up to 800 mg/l in 6 days with glucose as co-substrate. With 1000 mg PCP/l, 53% was degraded. NH₄ ⁺ salts were better at enhancing degradation than organic nitrogen sources and shake-cultures promoted PCP degradation compared with surface cultures. Degradation was maximal at pH 7.6 to 8.0 and at 30 to 37°C. Only PCP induced enzymes that degraded PCP and chloramphenicol inhibited this process. The PCP was degraded to CO₂, with release of Cl^-.The authors are with the Bacteriology Laboratory, Central Leather Research Institute, Madras-600 020, India.     

Photochemical Reaction Dynamics of the Primary Event of Vision Studied by Means of a Hybrid Molecular Simulation

The photoisomerization reaction dynamics of a retinal chromophore in the visual receptor rhodopsin was investigated by means of hybrid quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations. The photoisomerization reaction of retinal constitutes the primary step of vision and is known as one of the fastest reactions in nature. To elucidate the molecular mechanism of the high efficiency of the reaction, we carried out hybrid ab initio QM/MM MD simulations of the complete reaction process from the vertically excited state to the photoproduct via electronic transition in the entire chromophore-protein complex. An ensemble of reaction trajectories reveal that the excited-state dynamics is dynamically homogeneous and synchronous even in the presence of thermal fluctuation of the protein, giving rise to the very fast formation of the photoproduct. The synchronous nature of the reaction dynamics in rhodopsin is found to originate from weak perturbation of the protein surroundings and from dynamic regulation of volume-conserving motions of the chromophore. The simulations also provide a detailed view of time-dependent modulations of hydrogen-out-of-plane vibrations during the reaction process, and identify molecular motions underlying the experimentally observed dynamic spectral modulations.     

Microbial Treatment of Soil to Remove Pentachlorophenol

Direct inoculation of bacteria capable of degrading pentachlorophenol (PCP) into PCP-contaminated soil was investigated as a prophylactic measure to reduce the hazards of runoffs when spills occur or when wooden poles freshly treated with PCP-containing preservatives are located near streams and lakes. In laboratory tests at 30°C, the direct addition of 10⁶ PCP-utilizing Arthrobacter cells per g of dry soil reduced the half-life of the pesticide from 2 weeks to <1 day. Soil inoculation also was shown to be an effective way to increase the PCP disappearance rate in a test conducted in an outdoor shed.