Environmental chamber study of the photochemical reaction of ethyl methyl sulfide and NO_x

A series of experiments were conducted in a self-made smog chamber at （300 ＋ 1） K and 1.01 × 10^5 Pa to simulate the photochemical reaction of ethyl methyl sulfide （EMS） and NOx. The results showed that the higher the initial concentration of EMS, the more ozone was generated in the simulative reactions. It was found that the light intensity plays a very important role in the evaluation of ozone formation potential for EMS. The parameters of d（Oa-NO） and IR （incremental reactivity） were used to quantify the potential of EMS on ozone formation. The obtained maximum IR values in this article for the five simulative reactions were 1.55 × 10^-2, 0.99 × 10^-2, 1.36 × 10^-2, 2.47 × 10^-2, and 1.65 × 10^-2, respectively. A comparison between the results we obtained here and the results we obtained previously for di-tert-butyl peroxide and acetylene showed that the potential reactivity of EMS on ozone formation was at a relatively low level.

Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform

Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform under irradiation with light were studied. The reactions were separately carried out under air, oxygen, and nitrogen. The obtained results showed that this reaction belongs to the pseudo-first-order reaction with a rate constant kobs of 1.4×10?5 s?1 at room temperature. The presence or absence of air, oxygen, and nitrogen did not have obvious effects on the reaction rate under irradiation with light.

Photochemical reaction between magnesium tetraphenyl porphyrin and oxygen

The photochemical reaction of magnesium tetraphenyl porphyrin （MgTPP） with O2 was studied in CH2Cl2 by steady-state fluorescence, UV-vis absorption, FTIR and MALDI-TOF MS measurements. These spectra indicate that O2 can react with MgTPP excited by irradiation, forming the stable 1：1 coordinated adduct of MgTPP-O2. In the adduct, the oxygen atoms of O2 may insert in the Mg-N bonds in MgTPP and bind with the nitrogen atoms of MgTPP to form N-O-Mg bonds.

Photochemical reaction of magnesium tetraphenyl porphyrin with sulfur dioxide

The photochemical reaction of magnesium tetraphenyl porphyrin（MgTPP） with sulfur dioxide（SO_2） was investigated in dichloromethane（CH_2Cl_2） by steady-state fluorescence,UV-vis absorption,MS,and XRD spectroscopic techniques.These spectra showed that under irradiation MgTPP reacted with SO_2 to form 1：1 molecular adduct at first step.During the process of keeping irradiation and maintaining the flow of SO_2,SO_2 was reduced into S^（2-） by MgTPP and the results were detected using MS and XRD techniques.Understanding the photochemical reaction of MgTPP with SO_2 is of key interest in elucidating fundamental photochemical reaction mechanisms associated with this class of chlorophyll in the presence of SO_2.

Theoretical Study of the Photochemical Reaction Mechanism of Bicyclo[4.1.0]heptane

The photochemical reaction of bicyclo[4.1.0]heptane was studied at the complete active space SCF（CASSCF） level with a 6-31G^＊ basis set. A muhireference MP2 algorithm that has been implemented in the Gaussian program was used to correct the energetics for the dynamic correlation. Starting from the Franck-Condon excitation of bicyclo [ 4.1.0 ] heptane, the reaction is via two bonds＇ breakage to give rise to 1,6-heptdiene. One internal conversion （IC） and two intersystem crossing points（ISC） were located and are discussed separately. The reaction proceeds to its own characteristic product on the ground state.

THE SOLID STATE CONTROLLED PHOTOCHEMICAL REACTION OF NITROBENZALDEHYDE WITH INDOLE

The solid state photochemical reaction of nitrobenzaldehyde with indole was investigated. Seven hey products were identified by IR, MS,^(1)H HMR and elemental analysis.

THE PHOTOCHEMICAL SYNTHESIS OF THE PYRIDINE ADDUCT OF TETRAPHENYLPORPHYRINATORHODIUM(Ⅱ)AND THE MECHANISM OF PHOTOCHEMICAL REACTION

A new rhodium(Ⅱ)porphyrin complex was isolated by chromatography from the photochemical reac- tion of(μ—tetraphenylporphyrinato)bis[dicarbonylrhodium(Ⅰ)]with pyridine in benzene and has been charac- terized.From the results,the reaction mechanism is proposed.

Photochemical reaction of particle-bound 1-nitropyrene under simulated atmospheric condition

Photoreaction of particle-bound 1-nitropyrehe (1-NP) under simulated atmospheric condition has been studied. When 1-NP coated on the surface of silica gel was suspended in a stream of nitrogen, oxygen or air, respectively, and exposed to intensive light of xenon lamp, photochemical reaction took place. The result of kinetic study showed it to be of the second order. The photoreaction products were identified by off-line HPLC/MS as 1,6-pyrenequinone, 1,8-pyrenequinone, trinitro-hydroxypyrene, dinitrohydroxypyrene, 6,6'- dipyrenenone, etc. The mutagenicity of photochemical reaction products is higher in oxygen and air, and lower in nitrogen than that of the precursor 1-NP, as detected by the Ames Bioassay.

Photochemical Reaction of 9,10-Anthraquinone Labeled Bovine Serum Albumin Conjugate

Bovine serum albumin (BSA) was labeled with 9,10-anthraquinone and the photochemical fluorimetric reactivity of the covalently conjugated 9,10-anthraquinone was remarkably improved. The mechanism for the enhancement in the photochemical reactivity of conjugated 9,10-anthraquinone with BSA was discussed.

Photochemical Reactions of Microcystin-LR Following Irradiation with UV Light

Photochemical reactions of microcystin-LR, a toxic compound produced by some blue green algae, were investigated. Ultraviolet absorption of microcystin-LR was assessed. Time-dependent density functional theory (TDDFT) calculations indicated that absorption peak at 238 nm was mainly due to excitation of electrons from the linear chain structure Adda of microcystin-LR. Irradiation of microcystin-LR with UV light resulted in the reduction of the 238 nm absorption peak and the appearance of a new peak at 300 nm. Density functional theory (DFT) and TDDFT calculations with a model molecule suggested that this 300 nm peak was due to tricyclo-Adda microcystin-LR, an intermediate in photochemical reactions of microcystin-LR. Analysis of the rate of this photochemical reaction showed that it was a first order reaction.

Photochemical reactions as synthetic tool for pharmaceutical industries

In the quest for new agrochemicals and pharmaceuticals,chemists seek access to reliable and mild synthetic techniques to allow for the systematic modification of chemical structures,exploration of unexplored chemical space,and facilitation of practical synthesis in their search for novel agrochemicals and pharmaceuticals.In this regard,photocatalytic reactions enabled the synthesis of intricate and more functionalized compounds.This review overviews the developed synthetic methodologies and their utility in the chemical synthesis of pharmaceuticals.This review also offers in-depth insights into contemporary photoredox reactions such as allylic additions,cyclization,reductive cross-coupling,C–H activation,ring opening,oxidative cross-coupling,dehydrogenation,desulphonation,and decarboxylation.It provides a positive outlook for the promising future of this field.

Enhanced secondary organic aerosol formation during dust episodes by photochemical reactions in the winter in Wuhan

To investigate the effect of frequently occurring mineral dust on the formation of secondary organic aerosol(SOA),106 volatile organic compounds(VOCs),trace gas pollutants and chemical components of PM_(2.5) were measured continuously in January 2021 in Wuhan,Central China.The observation period was divided into two stages that included a haze period and a following dust period,based on the ratio of PM_(2.5) and PM_(10) concentrations.The average ratio of secondary organic carbon(SOC)to elemental carbon(EC)was 1.98 during the dust period,which was higher than that during the haze period(0.69).The contribution of SOA to PM_(2.5) also increased from 2.75% to 8.64%.The analysis of the relationships between the SOA and relative humidity(RH)and the odd oxygen(e.g.,O_(X)=O_(3)+NO_(2))levels suggested that photochemical reactions played a more important role in the enhancement of SOA production during the dust period than the aqueous-phase reactions.The heterogeneous photochemical production of OH radicals in the presence of metal oxides during the dust period was believed to be enhanced.Meanwhile,the ratios of trans-2-butene to cis-2-butene and m-/p-xylene to ethylbenzene(X/E)dropped significantly,confirming that stronger photochemical reactions occurred and SOA precursors formed efficiently.These results verified the laboratory findings that metal oxides in mineral dust could catalyse the oxidation of VOCs and induce higher SOA production.

Correlation of Vascular Endothelial Growth Factor Production with Photochemical Reaction-induced Retinal Edema

Background： Retinal edema is the major complication of retinal vein occlusion and diabetic retinopathy; it can damage visual function by influencing macular region. This study was to establish a rat retinal edema model and explore the related VEGF expression and observe the responses to anti-VEGF drugs in this model. Methods： A rat retinal edema model was established by inducing photochemical reaction using a 532 nm laser after the intravenous injection of Erythrosin B. Immediately after the laser treatment, models were given intravitreal injections of Ranibizumab or Conbercept to inhibit VEGF expression, and the changes of retinal thickness were measured. Retinal edema was observed using fundus photography （FP）, optical coherence tomography （OCT）, and fluoresce in fundus angiography （FFA） at 0, 1, 2, 4, 7 and 14 days after intervention. The retinal VEGF expression was measured using enzyme-linked immunosorbent assay （ELISA） and western blotting at each time point. The rat retinal edema model was also used to verify the function of anti-VEGF polypeptide ZY1. Results： Both retinal edema and vascular leakage were clearly observed at 1, 2 and 4 days after photochemical induction and the retinal thickness increased notably over the same period. The retinal VEGF expression peaked at day 1 and retina became thickening simultaneously. After the interventions, the VEGF expression of the Ranibizumab and Conbercept groups decreased at each time point compared to the edema group （26.90 ± 3.57 vs. 40.29 ± 6.68, F = 31.269 on day 1 and 22.36 ± 1.12 vs. 29.92 ± 0.93 F = 163.789 on day 2, both P 〈 0.01）; the mean RT （278 ± 4 vs. 288 ± 3, F = 134.190 on day 1 and 274 ± 7 vs. 284 ± 6, F = 64.367 on day 2, both P 〈 0.05） and vascular leakage in these groups also decreased. The same results were observed in the ZY1 group, particularly at day 2 （P 〈 0.05）. Conclusions： This retinal edema model induced by a photochemical reaction is reliable and repeatable. Induced edema increases expression of VEGF. This model can be used to test new drugs.

Review of heterogeneous photochemical reactions of NOy on aerosol-A possible daytime source of nitrous acid (HONO) in the atmosphere

As an important precursor of hydroxyl radical, nitrous acid （HONO） plays a key role in the chemistry of the lower atmosphere. Recent atmospheric measurements and model calculations show strong enhancement for HONO formation during daytime, while they are inconsistent with the known sources in the atmosphere, suggesting that current models are lacking important sources for HONO. In this article, heterogeneous photochemical reactions of nitric acid/nitrate anion and nitrogen oxide on various aerosols were reviewed and their potential contribution to HONO formation was also discussed. It is demonstrated that HONO can be formed by photochemical reaction on surfaces with deposited HNO3 , by photocatalytic reaction of NO2 on TiO2 or TiO2 -containing materials, and by photochemical reaction of NO2 on soot, humic acids or other photosensitized organic surfaces. Although significant uncertainties still exist in the exact mechanisms and the yield of HONO, these additional sources might explain daytime observations in the atmosphere.

Successive construction of cucurbit[8]uril-based covalent organic frameworks from a supramolecular organic framework through photochemical reactions in water

Functional framework materials have been developed for many applications including adsorption, asymmetric catalysis, sensing,drug delivery, optical device, and so on. Here, we report the successive construction of two cucurbit[8]uril-based covalent organic frameworks(COFs) including tetraphenylethene-based COF(COF-1) and phenanthrene-based COF(COF-2) from a two-dimensional(2D) periodic cucurbit[8]uril-based supramolecular organic framework(SOF-1) as the prearranged structure via the intermolecular photocycloaddition of the coumarin units and the intramolecular photocyclization of the tetraphenylethene(TPE) units under ultraviolet(UV) irradiation(365 nm) in water. In this case, oxygen(O_(2)) plays an important role in the photocyclization of the TPE units into the phenanthrene units in the transform process from SOF-1 or COF-1 to COF-2. As the TPE units further form phenanthrenes after UV-irradiation, COF-2 exhibits aggregation-caused quenching effect and weak green emission, while COF-1 displays a strong yellow emission due to the aggregation-induced emission. Besides, the adaptive chirality of cationic COF-1 as a biomolecular sensor can be efficiently induced by chiral anionic biomolecules including adenosine-5′-triphosphate(ATP) and adenosine-5′-diphosphate(ADP) to exhibit sensitive negative circular dichroism responses in water. This supramolecular approach to construct COF from SOF via photochemical reactions may open a new opportunity for the construction and application of the water-soluble COFs with well structural controllability, unique photophysical properties,and favorable biocompatibility.

Photochemical reaction of azobenzene in solvent-swollen Nafion membranes

The photochemical reactions of azobenzene (AB) incorporated into different solvent-swollen Nafion membranes were investigated. The location of azobenzene in water-swollen Nafion membranes was different from that in methanol-swollen Nafion membranes, which was responsible for the different photochemical reactions of AB. In methanol-swollen Nafion membranes only trans<->cis isomerization took place, while in water-swollen Nafion membranes photochemical cyclization of AB occurred after rapid trans<->cis isomerization. The relation between the relative quantum yields and the light intensity showed that the cyclization was a two-photo process. The numbers of AB molecules per cluster (n(AB)/cluster) in Nafion membranes with different AB concentrations and different water contents were calculated. Under the experimental condition two competitive photocyclization mechanisms were suggested by n(AB)/cluster in Nafion membranes, relative quantum yields of the cyclization, and the change of the ratio of benzidine to benzo[c]cinnoline.

THE ELECTRON SPIN RESONANCE STUDY ON PRIMARY PHOTOCHEMICAL REACTION OF HEMATOPORPHYRIN DERIVATIVE

The rate of oxygen consumption and the yield of free radical anion of hematoporphyrin derivative (HPD) in aqueous solutions of HPD and pyrocatechol were measured by the probe 2,2,6,6-tetramethyl4-piperidone-1-oxyl.It has been found that both singlet oxygen and free radical mechanisms exist simultaneously in primary photochemical reactions, and there is a competition between both mechanisms. When the oxygen concentration in solutions comes down to 12-14% of the stanting level, the predominant mechanism can be changed from the singlet oxygen to the free radical.Whether HPD exists in aggregation state is very important to photosensitization mechanisms.In the presence of the aggregation state of HPD, the predominant mechanism is the free radical,and photosensitization effects of HPD are all the better.

Magnetic field effects on photochemical reaction--III. Mechanistic study of the photodecarboxylation of arylmethyl esters in micellar solutions

Photolysis of benzyl phenylacetate (ACO_2A), benzyl p-methylphenylacetate (BCO_2A) and 1-naphthyl phenylacetate (ACO_2Np) in homogeneous and micellar solutions results in products typical of radical coupling reactions and loss of carbon dioxide. The cage effects upon direct photolysis of these esters in acetonitrile are significantly greater than zero and those in SDS or HDTBr micellar solutions are even greater. In the triplet sensitization reaction of ACO_2 Np in micellar solutions the cage effects are smaller than those obtained upon direct irradiation. However, the application of a 0.05 or 0.2 T external magnetic field in the photolysis in micellar solutions decreases the cage effects dramatically. All these results suggest that the photoextrusions of carbon dioxide from these esters proceed via radical intermediates, and upon direct photolysis the reactive states for the cleavage re- action involve both singlet and triplet excited states.

The Photochemical Study of HSA and BSA with Resonance Light Scattering and Fluorescence Spectra

The resonance light-scattering (RLS) of human serum albumin (HSA) and bovine serum albumin (BSA) is reported for the first time, and applied to study photochemical reaction of HSA and BSA. The fact of photocrosslinking self-association effect in HSA and BSA solutions is identified by the enhancement of RLS. The fluorescence quenching at about 350 nm and 700 nm proves that tryptophan (Trp) residues are one of the photochemical activity sites in HSA and BSA molecules. The Rayleigh scattering (RS) spectra of HSA and BSA that were neglected in fluorescence spectra before are found at about 296 nm, 592 nm and 888 nm for the first time, and are of adventageous to studying the aggregation of HSA or BSA. The possible photochemical reaction mechanism is also proposed.

Photochemical kinetics for holographic grating formation in phenanthrenequinone doped poly (methyl methacrylate) photopolymer

The photochemical kinetics of phenanthrenequinone （PQ） doped poly （methyl methacrylate） photopolymer in holographic recording was studied theoretically and experimentally. The diffusion of PQ molecules during holographic recording was negligible because of its small diffusion coefficient at room temperature. A photochemical reaction kinetics model of PQ/PMMA was established. The analytical expressions for the temporal variations of transmittance and diffraction efficiency were derived. By fitting the experimental curves, some parameters related with the polymer components were obtained by the proposed model, which can be used to analyze the photochemical process and will be helpful to the optimization of material preparation.