Photolysis of mono- through deca-chlorinated biphenyls by ultraviolet irradiation in n-hexane and quantitative structure-property relationship analysis

The photolysis of 16 polychlorinated biphenyls （PCBs） （including mono- through deca-chlorinated） in n-hexane was investigated under ultraviolet irradiation using a 500-W high-pressure mercury lamp. Photolysis of PCBs follows pseudo-first-order reaction kinetics, with photolysis rate constants ranging between 0.0011 s^-1 for PCB-52 and 0.0574 s^-1 for PCB-118. The degradation rates of PCBs by high-pressure mercury lamp irradiation were remarkably independent with respect to the degree of chlorination. Furthermore, partial least squares （PLS） models were developed to provide insight into which aspect of the molecular structure influenced PCB photolysis rate constants. It was found that the photolysis rates of PCBs increased with an increase in the net charge on the carbon atom （qc）, （ELUMO-EHOMO）^2, and the Y-axis dipole moment （μy） values, or the decrease in the energy of the second highest occupied molecular orbital （EHOMO-1）, energy of the lowest unoccupied molecular orbital （ELUMO）, ELUMO ＋ EHOMO, ELUMO - EHOMO, most positive atomic charge （q^＋）, and the twist angle of the chlorine atom （TA） values.

Photolysis pathway of nitroaromatic compounds in aqueous solutions in the UV/H_2O_2 process

Nitroaromatic compounds such as nitrobenzene and nitrophenols are largely synthesised and particularly often occur in water bodies as toxic pollutants. The degradation of these compounds in the environment via direct photolysis and by biological treatment is difficult and usually slow. In our two previous published papers, we have discussed the advanced oxidation of nitrobenzene and nitrophenols in aqueous solutions irradiated by direct photolysis using polychromatic light and by means of UV/H2O2 process. The experimental results suggested the UV/H2O2 process is an effective and efficient technology for complete mineralization of these organic compounds. Based on the results therein, comprehensive reaction mechanism for nitrobenzene photolysis was proposed with detailed discussions.

Direct photolysis of nitroaromatic compounds in aqueous solutions

The direct photolysis of nitrobenzene and nitrophenols in aqueous solutions irradiated by polychromatic light were investigated. Several aromatic intermediates were identified as three nitrophenol isomers, nitrohydroquinone, nitrosobenzene, nitrocatechol, catechol and phenol. Nitrite and nitrate ions were also detected in the irradiated solution indicating direct photolysis of nitrobenzene or nitrophenols. The degradation of nitrobenzene and nitrophenols and the formation of three nitrophenol isomers were observed to follow zero-order kinetics. The quantum yields for nitrobenzene and nitrophenols removal are about 10~ -3 and 10~ -3 —10~ -4 respectively. The mechanism for nitrobenzene degradation was suggested to follow mainly nitro-nitrite intramolecular arrangement.

Photochemistry of insecticide imidacloprid: direct and sensitized photolysis in aqueous medium

The direct and sensitized photodegradations of imidacloprid, 1-(6-chloro-3-pyridinylmethyl)-N-nitro-2-imidazolidinimine, were investigated in aqueous solution and with and without various photo-sensitizers. Results of the study revealed that the intensity of lamp-house and irradiation wavelength had significant effects on the photolysis of imidacloprid. Complete degradation of 20 mg/L imidacloprid in aqueous phase was observed in 40 min under ultraviolet(UV) irradiation system, suggesting the ultraviolet ray played significant role in direct photolysis of imidacloprid. The additions of various photo-sensitizers lead to improve the degradation efficiency of imidacloprid under the irradiation of black light fluorescent lamp. TiO 2 was the most efficient in the photo-catalytic degradation of imidacloprid among other photo-sensitizers in used this study. However, addition of acetone inhibited the photolysis of imidacloprid under the irradiation of UV, indicating the occurrence of competition between acetone and imidacloprid for photos. Mineralization of the imidacloprid was examined to clarify the final photochemical degradation products of the insecticide which were CO 2, Cl- and NO- 3. Complete photo-oxidation of nitrogen to NO- 3 occurred very slowly via the intermediate formation of NH+ 4 and NO- 2.

Hydrolysis and Photolysis of Herbicide Clomazone in Aqueous Solutions and Natural Water Under Abiotic Conditions

The hydrolysis and photolysis of clomazone in aqueous solutions and natural water were assessed under natural and controlled conditions. Kinetics of hydrolysis and photolysis of clomazone were determined by HPLC-DAD. Photoproducts were identiifed by HPLC-MS. No noticeable hydrolysis occurred in aqueous buffer solutions （（25±2）°C, pH （4.5±0.1）, pH （7.4±0.1）, pH （9.0±0.1）;（50±2）°C, pH （4.5±0.1）, pH （7.4±0.1）） or in natural water up to 90 d. At pH （9.0±0.1） and （50±2）°C the half-life of clomazone was 50.2 d. Clomazone photodecomposition rate in aqueous solutions under UV radiation and natural sunlight followed ifrst-order kinetics. Degradation rates were faster under UV light （half-life of 51-59 min） compared to sunlight （half-life of 87-136 d）. Under UV light, four major photoproducts were detected and tentatively identiifed according to HPLC-MS spectral information such as 2-chlorobenzamide, N-hydroxy-（2-benzyl）-2-methylpropan-amide, 2-[2-phenol]-4,4-dimethyl-3-isoxazolidinone and 2-[（4,6-dihydroxyl-2-chlorine phenol）]-4,4-dimethyl-3-isoxazolidinone. These results suggested that clomazone photodegradation proceeds via several reaction pathways：1） dehalogenation;2） substitution of chlorine group by hydroxyl;3） cleavage of the side chain. Photosensitizers, such as H2O2 and ribolfavin, could enhance photolysis of clomazone in natural sunlight. In summary, we found that photoreaction is an important dissipation pathway of clomazone in natural water systems.

DYE-SENSITIZED PHOTOLYSIS OF o-Cl-HEXAARYLBIIMIDAZOLE AND PHOTOPOLYMERIZATION KINETICS STUDY OF THE LONG WAVE-LENGTH DYE/HEXAARYLBIIMIDAZOLE SYSTEMS

o-Chloro-hexaarylbiimidazole (o-Cl-HABI) can be sensitized efficiently by the dyes 1-ethyl-3'-methyl thiacyanine bromide (C1), 3,3'-diethyl thiacarbocyanine iodide (C2), and cyclopentanone 2,5-bis[2-(1,3 -dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)ethylidene] (C3) through electron transfer proceses. When exposed to a xenon lamp (filtered by Pyrex glass), the photosensitive systems composed of o-Cl-HABI and the above dyes can produce free radicals which initiate the polymerization of MMA. The photopolymerization kinetics equation was obtained for the o-Cl-HABI/C2 system, R-p = K [C2](0.75)[o-Cl-HABI](0.44)[MTA](0.12)[MMA](1.0). A comparison of the influence of different dyes on the conversion of MMA photopolymerization was conducted.

UV Spectral Analysis of the Chemical Modification and Photolysis of Acetylacetone Modified Alumina Aqueous Solution

Acetylacetone was firstly introduced into the aqueous media with the presence of aluminum sec-butoxide and pep-tizator. It was confirmed that the UV (ultraviolet) absorption band of acetylacetone underwent 14 nm of red-shift due to the formation of the six-membered ring of the complex between alumina and acetylacetone in the aqueous solution. It was also found that the chemical modification can be dissociated by the UV irradiation with a wavelength shorter than 286 nm as a result of the excitation of π-π* transition in the complex.

Theoretical Study on the Triplet-sensitized Photolysis of 2,5-Dimethylfuran

In the present work, the triplet-sensitized photolysis of 2,5-dimethylfuran has been investigated with the complete active space SCF （CASSCF） molecular orbital method. Two different reaction routes through diradical and carbene intermediates respectively have been systematically studied, and the reaction via carbene intermediate is the major part well compatible with experiment. Geometries of minima and transition states on S0T1 surface were fully optimized at the CAS level with a 6-31G^＊ basis set. A multireference MP2 algorithm that has been implemented in Gaussian was used to correct the energetics for dynamic correlation. Four intersystem crossing points have been located and discussed, and two of them are efficient. Our computation indicates that the reaction must occur on the triplet-excited state.

pH Dependence of Photochemical Kinetics of Thioxanthen-9-one from Nanosecond Time-resolved Laser Flash Photolysis

pH dependent uorescence emission of a thioxanthone-based probe has been re-ported recently.The potential deter-minant factors of pH dependence may provide important clues to design novel thioxanthone-based probes in the fu-ture.pH dependence of photochemical kinetics of thioxanthone itself was inves-tigated in this work using nanosecond time-resolved laser ash photolysis.The nanosecond time-resolved transient absorption spectra and kinetics of TX in aqueous acetonitrile were recorded,as well as for a model reaction system including TX with diphenylamine(DPA)as a co-initiator.Besides the well-known absorption peak of ^(3)TX*,other peaks at 417,518,673 and 780 nm,have been reliably attributed to major intermediates in the overall reaction between TX and DPA with photolysis,which has been con rmed to occur along a multistep process.In the strong acidic solution(pH≈3.0),TX and protonated TX ions(TXH^(+))coexist due to protonated equilibrium.Consequently,high proton concentration promotes the predominant decay pathway after photolysis from electron transfer to proton affnity.Subsequently,the di erent primary products,^(3)TXH^(+*)or TX^(·-),proceed di erent secondary reaction channels.In addition,within the wide pH range from weak acid(pH=5.0)to alkaline solution(pH=13.0),the overall reaction mechanism and rates do not show visible changes.

Electron Transfer Reaction Between Desoxyadenosine and Triplet 2-Methyl-1,4-naphthaquinone:A Laser Photolysis Study

Introduction Electron transfer oxidation of DNA by triplet artificial photonuclease reveals a bright prospect of its application in biology and medicine. Both molecular orbital calculation and laser experiments have indicated that the homo guanine sequence should be the final localization site of photoexcited hole via long range migration within DNA. However, the direct observation of the produced ion pairs of biomolecules especially the stabilized radical cation DNA or its components is hampered by the overwhelming transient absorption of protonated radical anion of photosensitizers, such as 2-methyl-1,4-naphthaguinonel （MQ）.

Temperature-dependent Kinetics on Laser Induced Photolysis of Aqueous CS_2-HONO Solutions

A laser photolysis/transient absorption technique has been employed to investigate the photolysis kinetics of aqueous CS2-HONO solutions at 355 nm. Spectral analysis shows that CS2OH will react with HONO to form CS2OH-HONO. Temperature dependent rate coefficients for the reaction are reported for the first time. The following Arrhenius expressions adequately summarize the kinetic data obtained over the temperature range 273-313 K （units are L·mol^-1·s^-1）： In k = （31.6±0.6）-{（4.1±0.2）×10^3/T}, and the activation energy in unit of kJ.molA is 32.47 with the temperature accuracy 0.2 K.

TIME-RESOLVED IR STUDIES OF UV LASER FLASH PHOTOLYSIS OF W(CO)_6 IN C_6H_(12)-CCl_4 AND CCl_4 SOLUTION

Time-resolved IR absorption spectroscopy has been used to atudy the photochemistry of W(CO)_6 in cyclohexane, carbon tetrachloride, and the mixture of carbon tetrachloride and cyelohexane. The reastion of photolytically generated W(CO)_5. C_6H_(12) with CCl_4 was investigated. An intermediate with a lifetime of about 0.5ms, presumably attributed as W(GO)_5.CCl_4, was first observed.

Electrochemical Studies on the Photolysis of Iron-Arene Complex Photoinitiator

Iron-arene complex was first introduced by researchers in Ciba-Geigy as an effective photoinitiator for the photocuring of epoxy resin. The photolysis of these complexes has been studied by some authors. The electrochemical study reported in this note provides further evidence for the photolysis process which is crucial for the understanding of the photoinitiation mechanism.

Destruction of H_2S Gas with a Combined Plasma Photolysis(CPP) Reactor

A combined plasma photolysis （CPP） reactor that utilized the dielectric barrier discharge （DBD） plasma together with DBD-driven KrI^＊ excimer ultraviolet emission was applied to the decomposition of H2S gas. The effects of applied voltage, input current, gas flow velocity, original concentration as well as the ratio of Kr/I2 mixture on H2S removal efficiency were investigated. Gas streams containing H2S were separately treated with single DBD and CPP reactor under the same conditions. In comparison to DBD, CPP could greatly enhance the H2S removal efficiency at the same applied voltage, inlet gas concentration and gas flow velocity. In addition, the reaction mechanism was also discussed in this paper.

Photolysis studies on HCOOH and HCOO^- in presence of TiO_2 photocatalyst as suspension in aqueous medium

Photolysis studies on formic acid （HCOOH） and formate ion （HCOO-） in presence of TiO2, a photocatalyst, as suspension in water were carried out separately using 350 nm ultraviolet light. The products, such as H2, CO, CO2 and CH4, generated during the experiments were monitored with varying the ambient, light exposure time, and the concentration of HCOOH/HCOO-. The yields of CO in all these systems increased with light exposure time. In aerated systems, CO yields were higher in contrast to the deoxygenated （Ar-purged） systems under identical conditions. It is proposed apparently that the formation of CO is taking place during the chemical reduction of in-situ generated CO2, a photo-mineralized product of HCOOH/HCOO-, but not through the direct photodecomposition or photodehydration （CO＋H2O） of solute molecules. The rates of CO formation during 1.3 M HCOOH photolysis in presence of TiO2 photocatalyst were evaluated to be 0.21 and 0.13 μl/min in aerated and Ar-purged systems, respectively. As compared with HCOOH systems, the CO yields are lower when 0.2 M HCOONa was exposed to light under identical conditions. The CO growth rates were evaluated to be 0.07 and 0.046 μl/min^-1 for aerated and deoxygenated HCOONa systems, respectively; moreover, the trend is quite similar to that of the HCOOH system. Under these conditions, the emission of H2 was also observed, and its yield was significantly higher in Ar-purged system as compared with the CO yields. However, in aerated system, the yields of these products were just opposite. The formation of low yield of methane was observed during photolysis of HCOOH/HCOO ions. In CO2 ambient, the yields of CO and H2 varied drastically with time.

A Slow and Clean Fluorine Atom Beam Source Based on Ultraviolet Laser Photolysis

A slow and clean uorine atom beam source is one of the essential components for the low-collision energy scattering experiment involving uorine atom.In this work,we describe a simple but ef-fective photolysis uorine atom beam source based on ultraviolet laser photolysis,the performance of which was demonstrated by high-resolution time-of-ight spectra from the reactive scattering of F+HD.This beam source paved the way for stud-ies of low energy collisions with uorine atoms.

Time-resolved laser flash photolysis study on transient reaction between excited triplet state of anthraquinone derivatives (AQS) and 2-deoxythymidine

The transient absorption spectra and kinetics of excited triplet state of anthraquinone derivatives 2-anthraquinonesulfonatesodium (AQS) and 2-deoxythymidine (dT) have been investigated in CH3CN-H2O (97:3) using the time-resolved laser flash photolysis technique (KrF, 248 nm). The absorption spectra of dT radical cation and the radical anion of AQS have been observed. From dynamic and thermodyrnamic analysis, the mechanism of this transient reaction has been initially analysed.

Matrix Isolation and Computational Study on the Photolysis of CHCl₂COCl

UV light photolysis of dichloroacetyl chloride (CHCl2COCl) has been investigated by infrared spectroscopy in cryogenic Ar, Kr, Xe, and O2 matrices. The formation of CHCl3 and CO was found to be the dominant process over the ketene formation. The C-C bond cleaved products CHCl2 and COCl were also observed. As the number of the chlorine atom substitution to methyl group of acetyl chloride increased, the C-C bond cleaved product yield in the triplet state increased, which can be attributed to an internal heavy-atom effect where the intersystem crossing rate was enhanced.

Attempt to Polymerize <i>Cucurbita pepo</i>Oil by Temperature Action and Photolysis

The study of the polymerization of a vegetable oil has a double interest;industrial but especially food. Industrial because polymers based on vegetable oil are in line with sustainable development;food because an oil which polymerizes easily is a danger for human consumption. Three situations of Cucurbita pepo oil polymerization are carried out in the course of time, the factor retained being temperature. A monitoring of the evolution of the enthalpy by temperature variation by the DSC method allows to report the polymerization of this oil. It happens that a polymerization is triggered in the oil matrix but it seems to fade very quickly, this behavior is general because after sweeping a temperature range of 80°C;100°C and 150°C adding different amounts of Irgacure: the Cucurbita pepo oil resists polymerization through its antioxidant compounds. However, a photolysis of this oil carried out over 8 days shows that it effectively polymerizes after 144 hours, which proves the great capacity of antioxidant compounds to protect this oil. The analyses carried out at 25°C aim to simulate the behavior of the oil at room temperature. The results reveal good resistance to both thermochemical and photochemical polymerization, which opens up great prospects for its development in the food industry and in nutrition.

Theoretical insights of the pharmaceutical compound fluoxetine in water:Role in direct photolysis and indirect photolysis by free radicals

The frequent detection of pharmaceutical compounds in the environment has led to a growing awareness,which may pose a major threat to the aquatic environment.In this study,photodegradation(direct and indirect photolysis)of two different dissociation states of fluoxetine(FLU)was investigated in water,mainly including the determination of photolytic transition states and products,and the mechanisms of indirect photodegradation with·OH,CO_(3)^(*-)and NO_(3)^(*).The main direct photolysis pathways are defluorination and C–C bond cleavage.In addition,the indirect photodegradation of FLU in water is mainly through the reactions with·OH and NO_(3)^(*),and the photodegradation reaction with CO_(3)^(*-)is relatively difficult to occur in the water environment.Our results provide a theoretical basis for understanding the phototransformation process of FLU in the water environment and assessing its potential risk.