Photooxidation stability of phytosterols with different relative spatial positions in different particles

The aim of this study was to investigate the effects of relative spatial position of stigmasterol on its photooxidation stability in different particles.Phytosterol oxidation products(POPs)from phytosterol oxidation were successfully isolated and studied using solid phase extraction(SPE)technology in conjunction with GC-MS.The photooxidation stability of stigmasterol in four particles was as follows:zein stabilized particles(ZPs)≈zein-pectin stabilized particles(ZPPs)>soy protein isolate(SPI)-pectin stabilized particles(SPPs)>SPI stabilized particles(SPs).7β-Hydroxy and 5β,6β-epoxy was the main POPs in the first and second oxidation stages,respectively,which reached 8,945±43μg/g and 6,010±289μg/g after 240 min UV light exposure treatment in SPs.When stigmasterol was hydrophobically adsorbed on the surface of SPs,the network gel generated by pectin outside SPPs prevented photooxidation of stigmasterol.When stigmasterol was encapsulated in the interior of ZPs,the blocking effect of pectin in ZPPs became insignificant.The study provided a feasible development direction for the storage and quality control of phytosterols as dietary supplements.

Effects of seed aerosols on the growth of secondary organic aerosols from the photooxidation of toluene

Hydroxyl radical （.OH）-initiated photooxidation reaction of toluene was carried out in a self-made smog chamber. Four individual seed aerosols such as ammonium sulfate, ammonium nitrate, sodium silicate and calcium chloride, were introduced into the chamber to assess their influence on the growth of secondary organic aerosols （SOA）. It was found that the low concentration of seed aerosols might lead to high concentration of SOA particles. Seed aerosols would promote rates of SOA formation at the start of the reaction and inhibit its formation rate with prolonging the reaction time. In the case of ca. 9000 pt/cm^3 seed aerosol load, the addition of sodium silicate induced a same effect on the SOA formation as ammonium nitrate. The influence of the four individual seed aerosols on the generation of SOA decreased in the order of calcium chloride〉sodium silicate and ammonium nitrate〉ammonium sulfate.

The Relationship Among Photoinhibition, Photooxidation and Early Aging at a Late Development Stage in Different Varieties with High Yield

Using six high yield varieties from different ecological districts in China the parameters of Chl fluorescence, the performance of membrane lipid peroxidation and the reduction of Chl content in flag leaf under natural condition at the later developmental stages (from heading stage to mature stage). The results showed that Fv/Fm , decreased gradually, the excessive light energy led to the accumulation of active oxygen O2-, H2O2 and the product of membrane-lipid peroxidation, MDA, which resulted in the reduction of Chl content and early aging due to photooxidation during the course of senescence of flag leaf. This phenomenon varied obviously in rice varieties. When comparina japonica tolerant to photooxidation, Fv/Fm in indica shanyou 63 susceptible to photoxidation decreased significantly. An increase of active oxygen and a sharp drop of Chl content, resulted in 'yellowish' early aging and influenced filling and setting of rice grain. The mechanism on early aging in indica was related to light and temperature conditions in filling stages. On a fine day (above 251), PS Ⅱ reaction center exhibited a dynamic change on revisable inactivation. Under strong midday light, PS Ⅱ function in indica exhibited obvious down-regulation and photoinhibition; Under strong light with low temperature, PS Ⅱ resulted in photodamage, showing early aging, which were related to the degradation of PSⅡ - D1 Protein and the inhibition of the endogenous protecting system such as Xanthophyll cycle and the enzymes of scavenging active oxygen. The results suggested that for a view of high-yield breeding, on the basis of a good type-plant, giving consideration to the utilization of heterosis and resistance to early aging, selecting japonica or a sterile line with japonice genotype as maternal was a breeding strategy worthy of being paid more attention.

Characterization of products from photooxidation of toluene

Photooxidation reaction of toluene in smog chamber systems was initiated by the UV radiation of tolucne/CH5ONO/NOx mixtures. The products of the photooxidation reaction of toluene and its subsequent reactions were analyzed directly utilizing Fourier transform infrared spectrometer （FTIR）. Detailed assignments to FTIR spectrum of gas-phase products were given. The information of some important functional groups in the products, such as, carbonyl groups （C-O）, hydroxyl groups （-OH）, carboxylic acid （- COOH）, C-C bonding, N O bonding and C-H bonding （C H）, was got from this analysis. These results were compared to those analyzed by aerosol time of flight mass spectrometer （ATOFMS）. It was found that there are some differcnccs between FTIR analysis of gas-phase products and that of particle-phase, for example, the products with carbonyl groups, which were connected to unsaturated chemical bonds, was relatively higher in the gas phase, while kctoncs, aldehydes, carboxylic acid and organonitrates were the dominant functional groups in the aerosol-phase reaction products. The possible reaction pathways of some important products in the gas phase were also discussed.

Photooxidation of hydrochlorofluocarbons and hydrofluorocarbons initiated by OH radicals

Under simulated atmospheric condition, photoomdation for HCFC-22 + H2O2, HCFC-22 + H2O2+O2, HFC-134A + H2O2 and HFC-134A + H2O2+ O2 systems were studied.H2O2 was irradiated by low pressure mercury lamp and produced OH radicals. The OH radicals can initiate photooxidation of HCFC-22 and 134A. The products of photooxidation were determined by a Fourier Transform infrared Spectroscopy with a 20ml long path cell. The products were COF2,CO2, HCI, H2O and HF for HCFC-22 + H2O2 system, HO, CO2, HCI and HF for HCFC-22 +H2O2 +O2 system, HCOF, CF3OOCF3,CO2, H2O and HF for HFC-134A +H2O2 system, HCOF, CO2, H2O, and HF for HFC-134A + H2O2+ O2 system. Based on those results, the mechanisms of photooxidation were suggested.

Photooxidation of Furfural with Phthalocyanine-sensitized TiO_2 Particle Under Xenon Lamp

Copper phthalocyanine was selected as the photosensitizer to sensitize TiO2 in this experiment with furfural as the target pollutant. The composite catalysts（TiO2/CuPC） obtained showed a great activity under a xenon lamp. By experiments, the optimal preparation conditions of the composite catalysts were set as follows ： the CuPC loading mass fraction was 1.5%, the mass fraction of acetylacetone was 0. 3% , and the stirring time was 10 h. UV-Vis diffuse reflectance spectra, XRD, and BET were used to characterize the properties of the composite catalysts, which showed that after loading CuPC on TiO2, the composite catalyst retained the same crystal structure as pure TiO2 and the wavelength range of its absorption spectrum was broadened to 600-700 nm while its surface area was smaller than that of the pure TiO2. Under the optimal conditions, 20 mg/L furfural solution was degraded by nearly 90% and TOC by about 70%. When the catalyst was reused 6 times, the activity of the catalyst was still retained by about 75%.

The Effects of Accelerated Photooxidation on Molecular Weight and Thermal and Mechanical Properties of PHBV/Cloisite 30B Bionanocomposites

The effects of accelerated photooxidation on the molecular weight and thermal and mechanical properties of Cast PHBV and PHBV/Cloisite 30B(3 wt%)bionanocomposites are investigated herein.Through size exclusion chromatography(SEC)analysis,a significant decrease in both weight and number average molecular weights was observed for all irradiated samples over time,resulting from the chain scission mechanism.Differential scanning calorimetry(DSC)data indicated a decrease in degree of crystallinity and melting temperature after UV exposure,with the appearance of double melting peaks related to the changes in the crystal structure of PHBV.Thermal stability,tensile and thermo-mechanical properties were also reduced consecutively in photooxidation,being more pronounced for Cast PHBV.This study shows that the incorporation of Cloisite 30B in PHBV provides a better resistance to photooxidation in comparison with the neat polymer.

Syntheses and Photosensitive Effects of Rare Earth Carboxylate Complexes

Six kinds of cerium carboxylate (CeCar(3)) and rare earth carboxylate (RECar(3), RE=La+Ce+Pr) complexes were synthesized, and the compositions and characters of these complexes were studied by elementary analysis, thermo-gravimetric and differential thermal analysis (TG-DTA), infrared (IR) spectroscopy and ultra violet (UV) spectroscopy. The carbonyl indexes (CI) of law density polyethylene (LDPE) films containing CeCar(3) or RECar(3) during UV photooxidation were determined by IR spectroscopy. The effects of CeCar(3) or RECar(3) on the UV photooxidation rates, viscosity and average molecular weights (M(n)) of LDPE films were studied by using CI, and their mechanisms in sensitizing photooxidation degradation of LDPE films are discussed. Results show that the lifetime of LDPE films can be controlled by adding 0.1 wt%similar to 0.3 wt% CeCar(3) complexes to LDPE films.

Kinetic Characteristic of Photooxidation of Cypermethrin by Organic Peroxy Radical

The kinetic characteristic of photolysis of cypermethrin (CPM) sensitized by acetophenone (AP) and the effect of probe substance 2,6-Di-tert-butyl-4-methylphenol and tetralin is studied in this report. It showed that the photolysis rate of CPM increases slightly with the increase of AP concentration; photolysis rate of CPM has no relationship with [CPM] itself; The more dipolar moment the solvent has, the more the interaction between radical and solvent has, and the slower the photolysis of CPM is. The addition of radical probe substance confirms that ROO·is more than RO·. The steady-state concentration of ROO·is about 10?8 mol·L?1.

Photodegradation of bisphenol A in Fe(Ⅲ)-oxalate complexes solution

The aqueous photodegradation of bisphenol A （BPA） in the presence of Fe（Ⅲ）-oxalate complexes （Fe（Ⅲ）-Ox）, which are common compositions of natural water, was investigated in this study. BPA underwent rapid indirect photolysis in Fe（Ⅲ）-Ox solution under simulated solar irradiation, proceeding pseudo-first-order kinetics. The photolysis rate increased with decreasing pH or initial BPA level and increasing Fe（Ⅲ）/oxalate concentration ratio. Hydroxyl radicals （·OH）, which were generated from the photochemical processes of Fe（Ⅲ）-Ox complexes and contributed to the photooxidation of BPA, were determined by molecular probe and electron spin resonance （ESR） methods with the steady-state concentration of 2.56 × 10^-14 mol/L. Superoxide anion radical （O2^·-） was considered as the precursor of. OH and qualitatively determined by adding nitro blue tetrazolium as well as ESR experiments. Based on the structural analysis of the intermediate photoproducts of BPA in Fe（Ⅲ）-Ox complexes solution, the possible degradation pathways of BPA were proposed, involving ·OH addition, alkyl scission and alky oxidation. The results indicate that the photochemical reactivity of Fe（Ⅲ） may affect the environmental fate of BPA in natural water significantly.

Decolorization and kinetics of photo oxidizing cationic blue X-GRL by UV/H_2O_2 system

Azo dye cationic blue X GRL, which is non biodegradable toxic organic compound, is decolorized and subsequently mineralized by UV/H 2O 2/N 2 or UV/H 2O 2/air (O 2) system. The effects of initial solution concentration, initial solution pH, and some ions produced during the degradation on the rate of decolorization of cationic blue X GRL were investigated. The photodegradation of cationic blue X GRL approximately follows first order kinetics. The regression curve of the natural logarithm of concentration verus reaction time becomes less linear with initial concentration increasing. Oxygen and appropriate OH\+· generator can accelerate reaction rate. The effect of reaction atmosphere, initial concentration, light intensity on the optimal dosage of H 2O 2 were studied. It was found that the optimal H 2O 2 dosage was determined by UV light intensity. These intermediates of cationic blue X GRL decolorization are biodegradable.

The Role of Tripiet State of Oligophenylenevinylenes (OPVs) in their Photooxidative Degradation

Results of triplet-triplet energy transfer from biacetyl to OPVs and OPV tripiet state quenching by 1, 4-diazabicyclo[2.2.2] octane (DABCO) suggested that tripiet state of oligophenylenevinylenes(OPVs) directly takes part in their photooxidative degradation instead of just generating singlet oxygen.

EFFECT OF PHOTOOXIDATION ON PHOTOLUMINESCENCE OF N, N'-DIPHENYL-N, N'-DI(M-TOLYL)-BENZIDINE AND RUBRENE CODOPED PMMA THIN FILMS

In this paper, the PMMA films doped with N,N'-diphenyl-N,N'-di(m-tolyl)-benzidine and rubrene were fabricated by spin coating, and the effect of photooxidation on the photoluminescence of the doped PMMA thin films was investigated. The results showed that under the irradiation of 350nm UV light, N,N'-diphenyl-N,N'-di(m-tolyl)-benzidine can sensitized rubrene and results in the enhancement in the photooxidation of rubrene. The effect of photooxidation on the photoluminescence from rubrene was more obvious. Both lifetime measurement and in situ measurement of photoluminescence showed that rubrene molecules exist in two chemical surroundings.

Study on the Direct Photooxidation of Near-Infrared Absorbing Benzothiazolone Cyanine Dye

In this paper, direct photooxidation of benzothiazolone cyanine dye: in acetonitrile was studied. The photoproducts had been identified by (HNMR)-H-1 and fast atom bombardment (FAB) mass spectrometry. The results showed that the N-ethylbenzothiazolone (I), the ionic acid (II), and ionic aldehyde (III) are the principal photoproducts.

Immobilizing Triphenylamine with Photoredox Inert Sr^(2+)Forming Sr-MOF with Controlled Electron Migration for Photocatalytic Oxidation of Thiols to Disulfides

The photocatalytic oxidative coupling of thiols is one of the most popular methods to synthesize the disulfides.Triphenylamine and its derivatives(TPAs)are promising for the above reaction,but suffer from the easy polymerization and difficult separation.To overcome these obstacles while controlling the photogenerated electrons transfer directly to target substrates,herein,we constructed one TPA-based metal-organic framework(MOF),(Me_(2)NH_(2))[Sr(TCBPA)]·DMA·3H_(2)O(1),by direct self-assembly of tris(4′-carboxybiphenyl)amine(H_(3)TCBPA)and photoredox inert strontium ion(Sr^(2+)).DFT calculations revealed that the valence band maximum(VBM)and the conduction band minimum(CBM)are mainly located on TCBPA^(3-),successfully inhibiting the undesirable electron migration to metal nodes.Experimental results indicated that 1 displays superior performance than homogeneous H_(3)TCBPA,which may result from the abundant π…π and C—H…π interactions between the well-arranged TCBPA^(3-)and the build-in electric field between the anionic framework and the Me_(2)NH^(2+).This work highlights that immobilizing TPAs into MOFs is one promising approach to designing heterogeneous photocatalysts for the synthesis of disulfides by oxidative coupling of thiols.

Effects of NO_(2) and SO_(2) on the secondary organic aerosol formation fromβ-pinene photooxidation

Elucidating the effects of anthropogenic pollutants on the photooxidation of biogenic volatile organic compounds is crucial to understanding the fundamental mechanisms of secondary organic aerosol(SOA)formation.Here,the impacts of NO_(2)and SO_(2)on SOA formation from the photooxidation of a representative monoterpene,β-pinene,were investigated by a number of laboratory studies.The results indicated NO_(2)enhanced the SOA mass concentrations and particle number concentrations under both low and highβ-pinene conditions.This could be rationalized that the increased O_(3)concentrations upon the NO_(x)photolysis was helpful for the generation of more amounts of O_(3)-oxidized products,which accelerated the SOA nucleation and growth.Combing with NO_(2),the promotion of the SOA yield by SO_(2)was mainly reflected in the increase of mass concentration,which might be due to the elimination of the newly formed particles by the initially formed particles.The observed low oxidation degree of SOA might be attributed to the fast growth of SOA,resulting in the uptake of less oxygenated gas-phase species onto the particle phase.The present findings have important implications for SOA formation affected by anthropogenic–biogenic interactions in the ambient atmosphere.

“Steric Armor”Strategy of Blue Fluorescent Emitters against Photooxidation-Induced Degradation

Stability against oxygen is an important factor affecting the performance of organic semiconductor devices.Improving photooxidation stability can prolong the service life of the device and maintain the mechanical and photoelectric properties of the device.Generally,various encapsulation methods from molecular structure to macroscopic device level are used to improve photooxidation stability.Here,we adopted a crystallization strategy to allow 14H-spiro[dibenzo[c,h]acridine-7,9′-fluorene](SFDBA)to pack tightly to resist fluorescence decay caused by oxidation.In this case,the inert group of SFDBA acts as a“steric armor”,protecting the photosensitive group from being attacked by oxygen.Therefore,compared with the fluorescence quenching of SFDBA powder under 2 h of sunlight,SFDBA crystal can maintain its fluorescence emission for more than 8 h under the same conditions.Furthermore,the photoluminescence quantum yields(PLQYs)of the crystalline film is 327%higher than that of the amorphous film.It shows that the crystallization strategy is an effective method to resist oxidation.

Fabrication of MXene-Bi_(2)WO_(6)heterojunction by Bi_(2)Ti_(2)O_(7)hinge for extraordinary LED-light-driven photocatalytic performance

Heterojunction composites with intimate interfaces can shorten the diffusion distance,which leads to a shorter path for photogenerated carriers,thereby increasing photocatalytic activity.Herein,we report the fabrication of Ti_(3)C_(2)-Bi_(2)WO_(6)(TC-BW)heterojunctions hinged by Bi_(2)Ti_(2)O_(7)joints via an in situ hydrothermal reaction of Ti_(3)C_(2)in the presence of Na_(2)WO_(4)and Bi(NO_(3))_(3).The TC-BW was characterized using X-ray diffraction(XRD),scanning transmission electron microscopy(STEM),and Raman spectroscopy.TC-BW showed superior photocatalytic activity(productivity over 15TC-WB reaches up to 5.0 mmolreacted BA·gcat.^(−1)·h^(−1))in the oxidation of benzyl alcohol using light-emitting diode(LED)light,arising from the surface defects and intimate heterojunction interface between the Ti_(3)C_(2)MXene and Bi_(2)WO_(6)nanosheets.TC-BW heterojunctions provide an enhanced separation efficiency of photogenerated charges,which in turn yields superior photocatalytic activity.Furthermore,it is well substantiated by density functional theory(DFT)calculations.In summary,this study elucidates the preparation of heterojunction composites with intimate interfaces for highly efficient photooxidation.

Preparation of Perovskite Solar Cells in the Air:Degradation Mechanism and Prospects on Large-Area Fabrication

The preparation of perovskite solar cells(PsCs)in the air environment has attracted the attention of numerous experimenters due to its low preparation cost and the possibility of commercialization.Although the power conversion efficiency(PCE)of PSCs has increased rapidly and exceeded 25%,which is comparable to commercial polysilicon solar cells,most certified or reported high-efficiency perovskite solar cells are still confined to glove boxes or relatively small active areas in the air environment due to moisture,oxygen,high temperature,and ultraviolet(UV)factors.In this review.

Interface boosted highly efficient selective photooxidation in Bi_(3)O_(4)Br/ Bi_(2)O_(3) heterojunctions

Selective photooxidation of amines to biologically important imines is in great demand for industrial applications.The conversion efficiency and selectivity of the process are strongly dependent on the activation of photocatalytic molecular oxygen(O_(2))into reactive oxygen species.Here,we propose the construction of rich interfaces to boost photocatalytic O_(2) activation by facilitating the transfer of photocarriers.Taking Bi_(3)O_(4)Br/Bi_(2)O_(3) heterojunctions as an example,rich interfaces facilitate electron transfer to adsorbed O_(2) for superoxide(O_(2)⋅^(-))generation,thus achieving≥98%conversion efficiency and selectivity for benzylamine and benzylamine derivatives.This study offers a valid method to design advanced photocatalysts for selective oxidation reactions.