Electron Spin Resonance Analyse on the Production of Hydroxyl Radicals by Ozone Photolysis

<Abstract>In order to explore the production of hydroxyl radical(·OH)in a confined space,a novel ozone-light irradiation system is constructed in this study,and the·OH radical is measured by spin-trapping electron spin resonance(ESR)method in which 5,5-dimethyl-1-pyrroline-N-oxide(DMPO)is selected as the spin-trap.Several influence factors including the light intensity,the irradiation time and DMPO mass concentration are discussed. The results show that in this experimental system,with DMPO mass concentration of 1g/L and the irradiation time of 30 min,the·OH radical can be best captured.Besides,both wavelength and intensity of the irradiation light could effect the generation of·OH radical.These results are of great importance to further study the sterilization effect of·OH radical in confined space.

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.

Study on the synthesis of spin labeled poly(styrene-co-maleic acid)s and their segmental motion

Study of the segmental mobility of polymer chains is important when the polymer is used as drag reduction agents of crude oil.Electron spin resonance(ESR)spectroscopy can provide important information about segmental dynamics of polymer chains,which is related to their microenvironment.In this article,we employed an amphiphilic polymer to study the effect of hydrophilic/hydrophobic balance of the polymers on the segmental motion of polymer chains.Poly(styrene-co-maleic acid)(PSMA)was spin labeled with 4-amino TEMPO radicals by increasing the concentration of radical moiety on the polymer chains.The PSMA and spin labeled-PSMAs(SL-PSMAs)were characterized by nuclear magnetic resonance(NMR),Fourier transform infrared(FT-IR)spectroscopy,Cyclic voltammetry(CV)and ESR techniques.Inter-polymer complexes(IPCs)of SL-PSMA-2 were prepared by employing polyethylene glycols(PEGs)of varying molecular weights.The results showed that the increased hydrophobic interactions of nitroxide radicals on the SLPSMAs’chains reduced the rotational mobility of spin labels and the random coil-toglobular transition of polymer chains occurred at higher pH value for SL-PSMAs,which showed a slow motion component in the ESR spectra of SL-PSMAs.Further,by increasing the molecular weight of PEGs in IPCs the complexation was increased,which also reduced the rotational motion of spin labels due to interpolymer hydrogen bonding causing a slow motion component in the ESR spectra.©2021 The Authors.

Optical nuclear spin polarization in quantum dots

Hyperfine interaction between electron spin and randomly oriented nuclear spins is a key issue of electron coherence for quantum information/computation. We propose an efficient way to establish high polarization of nuclear spins and reduce the intrinsic nuclear spin fluctuations. Here, we polarize the nuclear spins in semiconductor quantum dot(QD) by the coherent population trapping(CPT) and the electric dipole spin resonance(EDSR) induced by optical fields and ac electric fields. By tuning the optical fields, we can obtain a powerful cooling background based on CPT for nuclear spin polarization. The EDSR can enhance the spin flip–flop rate which may increase the cooling efficiency. With the help of CPT and EDSR, an enhancement of 1300 times of the electron coherence time can be obtained after a 10-ns preparation time.

The Contribution of dα-Tocopherol and dγ-Tocopherol to the Antioxidant Capacity of Several Edible Plant Oils

Many oils from plants are important components of our food chain and maintaining their oxidative stability (OS) is economically and nutritionally important. OS is dependent in part on antioxidant capacity (AC) arising from the electron donating ability of endogenous compounds in the oils. Attention has focused on the contribution to AC of phenolic compounds in oils as many have bioactivities in vitro. However, the relevance of such phenolics to healthy nutrition remains unclear. In contrast, many plant-derived oils also contain tocopherol homologs, which as vitamin E are dietary-essential, lipid-soluble antioxidants. We have determined the AC of twelve “off the shelf” edible oils by assessing their ability to quench galvinoxyl, a stable free radical species. The stochiometric reactivity of vitamin E with galvinoxyl indicates that the combined dα-tocopherol and dγ-tocopherol homologs contribute between 20% (olive) and 85% (soya) to AC depending on type of oil. Tocopherols are important contributors to the AC of several vegetable oils. Breeding and photo mixotrophic programmes to enhance content in edible oil crops of this important vitamin may have a positive impact not only on oil stability during storage but also in contributing to provision of optimum dietary intakes for health.

Living Bacteria-Mediated Aerobic Photoinduced Radical Polymerization for in Situ Bacterial Encapsulation and Differentiation

Conventional polymerizations mediated by living cells typically require synthetic transition-metal complexes or photoredox catalysts.Herein,we report an alternative photoinduced polymerization strategy for preparing functional polymer hydrogels through bacteria-initiated radical polymerization of acrylamides in ordinary culture media.Upon light irradiation under ambient conditions,polyacrylamides were obtained with molecular weights of over 150 kDa using various bacteria.

Formation mechanism of solid product produced from co-pyrolysis of Pingdingshan lean coal with organic matter in Huadian oil shale

A mixture of Pingdingshan lean coal and acid-treated Huadian oil shale was co-pyrolyzed in a drop-tube fixed-bed reactor in the temperature range of 300℃–450℃.To reveal the formation mechanism of the solid co-pyrolysis product,changes in some physicochemical properties were investigated,using analysis by X-ray diffraction,X-ray photoelectron spectroscopy,scanning electron microscopy,pore analysis,thermogravimetry,and electron spin resonance.X-ray diffraction showed that the lattice plane spacing for the co-pyrolyzed mixture decreased from 0.357 nm to 0.346 nm and the average stacking height increased from 1.509 nm to 1.980 nm in the temperature range of 300°C–450°C,suggesting that pyrolysis treatment increased its degree of metamorphism.The amount of oxygen-containing functional groups and pore volume decreased with increasing temperature.Thermogravimetry and electron spin resonance results showed that synergistic effects occurred during the co-pyrolysis process.A formation mechanism for the solid product was proposed.Hydrogen-rich radicals generated from the pyrolysis of the oil shale were trapped by hydrogen-poor macromolecular radicals of the intermediate metaplast produced from coal pyrolysis,thereby increasing the yield of solid product.

Formation mechanisms of reactive carbonyl species from fatty acids in dry-cured fi sh during storage in the presence of free radicals

This study aimed to better understand the changes of fatty acids in dry-cured fish during storage,and to analyze the reactive carbonyl species(RCS)formation mechanism primarily from the standpoint of oxygen-derived free radical reactions interactions.Oleic acid and linoleic acid were the predominant unsaturated fatty acids in dry-cured fish.The content of unsaturated fatty acids in dry-cured fish increased over time at 4℃,while decreased at 25℃.Singlet oxygen,superoxide anion and hydroxyl-alkyl radical levels increased with time,and more free radicals were yielded in the samples held at 25℃.Redundancy analysis revealed that hydroxyl-alkyl radicals had the greatest influence on the oxidation of lipids.Hydroxyl-alkyl radicals and singlet oxygen levels were positively correlated with 4-hydroxy-2-nonenal(HNE),malondialdehyde(MDA),peroxide value and acid value levels,but adversely to 4-hydroxy-2-hexenal(HHE)and fatty acids levels.Moreover,HNE and MDA were both inversely linked with fatty acids contents.It is possible that the intermediates of lipid oxidation undergo oxidation,cleavage and other reactions due to free radical activity,resulting in the generation of aldehyde precursors.These findings help us further characterize the lipid oxidation and RCS formation mechanism in dry-cured fish during storage.