Understanding the unique characteristics of continuous-flow photochemistry will lead to a paradigm shift in the way we enhance sustainability and wellbeing.In this mini-review,we first provide a succinct overview of w...Understanding the unique characteristics of continuous-flow photochemistry will lead to a paradigm shift in the way we enhance sustainability and wellbeing.In this mini-review,we first provide a succinct overview of working principles of this technique and discuss several recent synthetic protocols.Then,emphasis is given to those representative examples which address environmental issues such as indoor air pollutants and water contamination.Finally,recent progress made using this technique to deal with rising CO2 emission,solar energy utilization and biomedical equipment is described.It is believed that this mini-review could inspire more chemists to utilize this technique in their research,either in the academic or industrial field.展开更多
Photochemical aging of volatile organic compounds(VOCs)in the atmosphere is an important source of secondary organic aerosol(SOA).To evaluate the formation potential of SOA at an urban site in Lyon(France),an outdoor ...Photochemical aging of volatile organic compounds(VOCs)in the atmosphere is an important source of secondary organic aerosol(SOA).To evaluate the formation potential of SOA at an urban site in Lyon(France),an outdoor experiment using a Potential Aerosol Mass(PAM)oxidation flow reactor(OFR)was conducted throughout entire days during JanuaryFebruary 2017.Diurnal variation of SOA formations and their correlation with OH radical exposure(OHexp),ambient pollutants(VOCs and particulate matters,PM),Relative Humidity(RH),and temperature were explored in this study.Ambient urban air was exposed to high concentration of OH radicals with OHexp in range of(0.2-1.2)×10^12 molecule/(cm^3·sec),corresponding to several days to weeks of equivalent atmospheric photochemical aging.The results informed that urban air at Lyon has high potency to contribute to SOA,and these SOA productions were favored from OH radical photochemical oxidation rather than via ozonolysis.Maximum SOA formation(36μg/m^3)was obtained at OHexp of about 7.4×10^11 molecule/(cm^3·sec),equivalent to approximately 5 days of atmospheric oxidation.The correlation between SOA formation and ambient environment conditions(RH&temperature,VOCs and PM)was observed.It was the first time to estimate SOA formation potential from ambient air over a long period in urban environment of Lyon.展开更多
Chiral photochemistry appears to be a highly challenging topic and still very much in its infancy, especially if comparing to its well-developed thermochemical counterpart.Significant efforts have been devoted in orde...Chiral photochemistry appears to be a highly challenging topic and still very much in its infancy, especially if comparing to its well-developed thermochemical counterpart.Significant efforts have been devoted in order to improve stereoselectivity of chiral photoreactions,among which,the supramolecular strategy proven the most promising.The present review,motivated by the rapid progress in the supramolecular chiral photochemistry,concentrates on advancements achieved mainly in the last decade.The features and advantages of supramolecular chiral photochemistry are exemplified by representative photoreactions in terms of the chiral hosts/assemblies.展开更多
Criegee intermediates(CIs),also known as carbonyl oxide,are reactive intermediates that play an important role in the atmospheric chemistry.Investigation on the structures and reactivity of CIs is of fundamental impor...Criegee intermediates(CIs),also known as carbonyl oxide,are reactive intermediates that play an important role in the atmospheric chemistry.Investigation on the structures and reactivity of CIs is of fundamental importance in understanding the underlying mechanism of their atmospheric reactions.In sharp contrast to the intensively studied parent molecule(CH_(2)OO)and the alkyl-substituted derivatives,the knowledge about the fluorinated analogue CF_(3)C(H)OO is scarce.By carefully heating the triplet carbene CF_(3)CH in an O2-doped Ar-matrix to 35 K,the elusive carbonyl oxide CF_(3)C(H)OO in syn-and anti-conformations has been generated and characterized with infrared(IR)and ultraviolet-visible(UV-vis)spectroscopy.The spectroscopic identification is supported by^(18)O-labeling experiments and quantum chemical calculations at the B3 LYP/6-311++G(3df,3pd)and MP2/6-311++G(2d,2p)levels.Upon the long-wavelength irradiation(λ>680 nm),both conformers of CF_(3)C(H)OO decompose to give trifluoroacetaldehyde CF_(3)C(H)O and simultaneously rearrange to the isomeric dioxirane,cyclic-CF_(3)CH(OO),which undergoes isomerization to the lowest-energy carboxylic acid CF_(3)C(O)OH upon UV-light excitation at 365 nm.The O_(2)-oxidation of CF_(3)CH via the intermediacy of CF_(3)C(H)OO and cyclic-CF_(3)CH(OO)might provide new insight into the mechanism for the degradation of hydro-chlorofluorocarbon CF_(3)CHCl_(2)(HCFC-123)in the atmosphere.展开更多
Solar energy is the primary driving force behind a planet’s climate system,and surface albedo plays a key role in determining the energy budget of the planet.Coupling the Snow,Ice,and Aerosol Radiation(SNICAR)with th...Solar energy is the primary driving force behind a planet’s climate system,and surface albedo plays a key role in determining the energy budget of the planet.Coupling the Snow,Ice,and Aerosol Radiation(SNICAR)with the Laboratoire de Météorologie Dynamique(LMD)Mars General Circulation Model(MGCM)to create a new coupled model leads to an approximately 4%drop in the net CO2 ice deposition on Mars.Newly simulated surface albedo affects the concentration of gaseous species in the Martian atmosphere(condensation-sublimation cycle).The new set-up also impacts the solar energy available in the atmosphere.These two effects together lead to subsequent and significant changes in other chemical species in the Martian atmosphere.Compared with results of the MGCM model alone,in the new coupled model CO2(gas)and O3 show a drop of about 1.17%and 8.59%in their respective concentrations,while H2O(vapor)and CO show an increase of about 13.63%and 0.56%in their respective concentrations.Among trace species,OH shows a maximum increase of about 29.44%,while the maximum drop of 11.5%is observed in the O concentration.Photochemically neutral species such as Ar and N2 remain unaffected by the albedo changes.展开更多
During the past few years,regulation and controlling of the two-dimension（2D） self-assembled supramolecular structure on surface have drawn increasing attention in nanoscience and technology.External stimuli have be...During the past few years,regulation and controlling of the two-dimension（2D） self-assembled supramolecular structure on surface have drawn increasing attention in nanoscience and technology.External stimuli have been widely used to regulate these 2D nanostructures.Among various external stimuli approaches,photo-regulation as one of the most outstanding means of regulation has been extensively studied because different wave bands can lead to molecular conformation variation and new bonds to gain new molecules.In this review,the photo-regulated self-assembled structure on solid surface as well as the photo-reactions of different molecules substituted with photo-sensitive groups are introduced to give us an insight into on-surface photochemistry,which plays an important role on the nano-devices fabrication.Notably,these photo-sensitive behaviors as well as the formed structures on surface were probed at sub-molecule level by unique scanning tunneling microscopy（STM） technique.展开更多
We have presented the synthesis and characterization of three new bromo substituted stilbene derivatives, p-3,4,5-trimethoxy-p′- 2,3,4,5,6-pentabromostilbene （C1）, p-N,N-dimethylamino-p′-2,3,4,5,6-pentabromostilbe...We have presented the synthesis and characterization of three new bromo substituted stilbene derivatives, p-3,4,5-trimethoxy-p′- 2,3,4,5,6-pentabromostilbene （C1）, p-N,N-dimethylamino-p′-2,3,4,5,6-pentabromostilbene （C2） and p-N,N-diphenylamino-p′- 2,3,4,5,6-pentabromostilbene （C3） in this letter. The UV/vis absorption and photoluminescence were investigated in various solvents. The maximal absorption wavelength of C1 exhibited blue-shift to those of C2 and C3 in different solvents. No florescence emission could be detected for these compounds at room temperature. Singlet oxygen could be efficiently produced with these sensitizers under near-ultraviolet and visible light irradiation.展开更多
Diphenylchlorin (DPC) and diphenylbacteriochlorin (DPBC) were synthesized for the first time from reduction of 5,10-diphenylporphyrin (DPP). As photosensitizers they have sizable absorption in the red region of the vi...Diphenylchlorin (DPC) and diphenylbacteriochlorin (DPBC) were synthesized for the first time from reduction of 5,10-diphenylporphyrin (DPP). As photosensitizers they have sizable absorption in the red region of the visible spectrum. The high yield of DPC.-photosensitized generation Of O-1(2), and the EPR studies in homogenerous solution showed that the photodynamic action of DPP-based photosensitizers may proceed via type I and type II machanisms.展开更多
Marine inorganic photochemistry, as one of the important branches of marine chemistry, is significantly connected with marine biology, marine ecology, marine geochemistry and marine environment, and plays an important...Marine inorganic photochemistry, as one of the important branches of marine chemistry, is significantly connected with marine biology, marine ecology, marine geochemistry and marine environment, and plays an important role in the development of marine sciences. To date, lots of investigations in the field have been conducted home and abroad. As for the following development of marine inorganic photochemistry, it is greatly of significance to summarize these research works. This paper detailedly summarizes the present research progress in the photochemistry of Fe, Mn and Cu, with an emphasis on investigations on photochemical processes which could affect existing forms of these metal elements in seawater. The problems and shortcomings in the study field are pointed out and some suggestions for the future study are put forward.展开更多
Direct photolysis and quenching experiments with styrene oxide support the existence of an efficient triplet photochemical pathway to benzyl radical formation. Similar photolytic behavior for styrene glycol carbonate ...Direct photolysis and quenching experiments with styrene oxide support the existence of an efficient triplet photochemical pathway to benzyl radical formation. Similar photolytic behavior for styrene glycol carbonate strongly supports the 1,3-diradical, resulting from the scission of the benzylic C-O bond, as the geometric source of the triplet pathway. Primary photoproducts were determined by both NMR and HPLC analysis and we observed that toluene and bibenzyl were both primary photoproducts, not secondary photoproducts.展开更多
Heterocyclic compounds represent a pivotal class of organic molecules with a profound impact on daily life.In particular,thiazole and isothiazole stand out as fundamental scaffolds that are widely used in medicinal ch...Heterocyclic compounds represent a pivotal class of organic molecules with a profound impact on daily life.In particular,thiazole and isothiazole stand out as fundamental scaffolds that are widely used in medicinal chemistry,agrochemicals,and materials science(Figure 1a)[1].Despite their importance,the functionalization of these heterocycles,including alkylation,and amination,predominantly relies on cross-coupling reactions,which are often constrained by limited regioselectivity and harsh reaction conditions[2,3].展开更多
The photochemistry of organic contaminants present in ice is receiving growing attention,given the wide presence of ice during winter in temperate regions as well as Polar and mountain environments.Differences between...The photochemistry of organic contaminants present in ice is receiving growing attention,given the wide presence of ice during winter in temperate regions as well as Polar and mountain environments.Differences between ice photochemistry and aqueous photochemistry,however,influence the quanti-tative fate and transformation of organic chemicals present in freshwater,marine and ice-cap environ-ments and these differences need to be explored.Here we comparatively studied the ice and aqueous photochemistry of three antibiotics[levofloxacin(LVX),sulfamerazine(SM),and chlortetracycline(CTC)]under the same simulated sunlight(λ>290 nm).Their photodegradation in ice/water followed pseudo-first-order kinetics,whereby the photolytic rates of LVX in ice and water were found to be similar,SM photodegraded faster in ice,while CTC underwent slower photodegradation in ice.Whether individual antibiotics underwent faster photodegradation in ice or not depends on the specific concentration effect and cage effect coexisting in the ice compartment.In most cases,the fastest photodegradation occurred in freshwater ice or in fresh water,and the slowest photolysis occurred in pure-water ice or in pure water.This can be attributed to the effects of key photochemical reactive constituents of Cl^(-),HA,NO_(3)^(-)and Fe(Ⅲ),that exist in natural waters.These constituents at certain levels showed significant effects(P<0.1)on the photolysis,not only in ice but also in water.However,these individual constituents at a given concentration,serve to either enhance or suppress the photoreaction,depending on the specific antibiotic and the matrix type(e.g.,ice or aqueous solution).Furthermore,extrapolation of the laboratory findings to cold environments indicate that pharmaceuticals present in ice will have a different photofate compared to water.These results are of particular relevance for those regions that experience seasonal ice cover in fresh water and coastal marine systems.展开更多
To reveal and quantify the interactive effects of drought stresses and elevated CO2 concentration [CO2] on photochemistry efficiency of cucumber seedlings, the portable chlorophyll meter was used to measure the chloro...To reveal and quantify the interactive effects of drought stresses and elevated CO2 concentration [CO2] on photochemistry efficiency of cucumber seedlings, the portable chlorophyll meter was used to measure the chlorophyll content, and the Imaging-PAM was used to image the chlorophyll fluorescence parameters and rapid light response curves （RLC） of leaves in two adjacent greenhouses. The results showed that chlorophyll content of leaves was reduced significantly with drought stress aggravated. Minimal fluorescence （Fo） was increased while maximal quantum yield of PSII （Fv/Fm） decreased significantly by severe drought stress. The significant decrease of effective quantum yield of PSII （Y（Ⅱ）） accompanied by the significant increase of quantum yield of regulated energy dissipation （Y（NPQ）） was observed under severe drought stress condition, but there was no change of quantum yield of nonregulated energy dissipation （Y（NO））. We detected that the coefficient of photochemical quenching （qP） decreased, and non-photochemical quenching （NPQ） increased significantly under severe drought stress. Furthermore, we found that maximum apparent electron transport rate （ETRmax） and saturating photosynthetically active radiation （PPFDsat） decreased significantly with drought stress aggravated. However, elevated [CO2] significantly increased FvlFm, qP and PPFDsat, and decreased NPQ under all water conditions, although there were no significant effects on chlorophyll content, Fo, Y（Ⅱ）, Y（NPQ）, Y（NO） and ETRmax. Therefore, it is concluded that CO2-fertilized greenhouses or elevated atmospheric [CO2] in the future could be favorable for cucumber growth and development, and beneficial to alleviate the negative effects of drought stresses to a certain extent.展开更多
The effect of diabatic process due to the photochemical heating and cooling on the gravity wave propagation in middle atmosphere is studied. A linear gravity wave model which considers the diabatic process is establis...The effect of diabatic process due to the photochemical heating and cooling on the gravity wave propagation in middle atmosphere is studied. A linear gravity wave model which considers the diabatic process is established. The unstable region and the growth rate of the gravity wave caused by photochemistry are calculated. And the comparison between the model and the adiabatic gravity wave theory of pure dynamics is made. The results indicate that the photochemical heating process can induce the instability of gravity wave at mesopause. The intensity of the instability becomes stronger as the temperature decreases. The temperature feature and the altitude characteristics of the instability are consistent with the observation. Therefore, the instability of the gravity wave induced by photochemistry may be an important mechanism in polar mesopause region in summer.展开更多
Hypocrellins are novel photosensitizers from China, which are demonstrated to have significant anti-tumor and anti-virus activity and to be potential photo-dynamic therapy (PDT) agents. As compared with hemato-porphyr...Hypocrellins are novel photosensitizers from China, which are demonstrated to have significant anti-tumor and anti-virus activity and to be potential photo-dynamic therapy (PDT) agents. As compared with hemato-porphyrin, the only approved photosensitizer, hypocrellins have several advantages, such as easy preparation and easy purification, high triplet quantum yield, high singlet-oxygen quantum yield, high phototoxicity but low dark toxicity, and rapid clearance from normal issues. This article reviews briefly the photophysics, photochemistry and photobiology of hypocrellins on the basis of the domestic and international research results.展开更多
Metal–metal cooperativity effects have been extensively explored in olefin polymerization,along with the design and preparation of many binuclear transition metal catalysts.However,their synthesis and the tuning of m...Metal–metal cooperativity effects have been extensively explored in olefin polymerization,along with the design and preparation of many binuclear transition metal catalysts.However,their synthesis and the tuning of metal–metal distance are complicated and time-consuming.In this contribution,a supramolecular chemistry strategy was used to construct multinuclear olefin polymerization catalysts.Urea functional groups were installed into severalα-diimine palladium catalysts to enable hydrogenbonding-induced self-assembly.展开更多
基金Financial support from the National Natural Science Foundation of China(No.21771088)Zhejiang Provincial Natural Science Foundation of China(No.LY20B010005)the open research funds of JLU(2020-9)&FJIRSM,CAS(No.20170034)。
文摘Understanding the unique characteristics of continuous-flow photochemistry will lead to a paradigm shift in the way we enhance sustainability and wellbeing.In this mini-review,we first provide a succinct overview of working principles of this technique and discuss several recent synthetic protocols.Then,emphasis is given to those representative examples which address environmental issues such as indoor air pollutants and water contamination.Finally,recent progress made using this technique to deal with rising CO2 emission,solar energy utilization and biomedical equipment is described.It is believed that this mini-review could inspire more chemists to utilize this technique in their research,either in the academic or industrial field.
基金the Institute for Research on Catalysis and the Environment of Lyon(IRCELYON)supported by the"Investissement d’Avenir"PEPS Program Project(ASTRAL)of the University of Lyon and French National center for Scientific Research(French:center national de la recherche scientifique,CNRS)as part of the ANR-11-IDEX-0007 programby the European Research Council under the Horizon 2020 Research and Innovation Program Project of the European Union under Convention N°690958(MARSU)。
文摘Photochemical aging of volatile organic compounds(VOCs)in the atmosphere is an important source of secondary organic aerosol(SOA).To evaluate the formation potential of SOA at an urban site in Lyon(France),an outdoor experiment using a Potential Aerosol Mass(PAM)oxidation flow reactor(OFR)was conducted throughout entire days during JanuaryFebruary 2017.Diurnal variation of SOA formations and their correlation with OH radical exposure(OHexp),ambient pollutants(VOCs and particulate matters,PM),Relative Humidity(RH),and temperature were explored in this study.Ambient urban air was exposed to high concentration of OH radicals with OHexp in range of(0.2-1.2)×10^12 molecule/(cm^3·sec),corresponding to several days to weeks of equivalent atmospheric photochemical aging.The results informed that urban air at Lyon has high potency to contribute to SOA,and these SOA productions were favored from OH radical photochemical oxidation rather than via ozonolysis.Maximum SOA formation(36μg/m^3)was obtained at OHexp of about 7.4×10^11 molecule/(cm^3·sec),equivalent to approximately 5 days of atmospheric oxidation.The correlation between SOA formation and ambient environment conditions(RH&temperature,VOCs and PM)was observed.It was the first time to estimate SOA formation potential from ambient air over a long period in urban environment of Lyon.
文摘Chiral photochemistry appears to be a highly challenging topic and still very much in its infancy, especially if comparing to its well-developed thermochemical counterpart.Significant efforts have been devoted in order to improve stereoselectivity of chiral photoreactions,among which,the supramolecular strategy proven the most promising.The present review,motivated by the rapid progress in the supramolecular chiral photochemistry,concentrates on advancements achieved mainly in the last decade.The features and advantages of supramolecular chiral photochemistry are exemplified by representative photoreactions in terms of the chiral hosts/assemblies.
基金supported by the National Natural Science Foundation of China(Nos.22003010 and 22025301)
文摘Criegee intermediates(CIs),also known as carbonyl oxide,are reactive intermediates that play an important role in the atmospheric chemistry.Investigation on the structures and reactivity of CIs is of fundamental importance in understanding the underlying mechanism of their atmospheric reactions.In sharp contrast to the intensively studied parent molecule(CH_(2)OO)and the alkyl-substituted derivatives,the knowledge about the fluorinated analogue CF_(3)C(H)OO is scarce.By carefully heating the triplet carbene CF_(3)CH in an O2-doped Ar-matrix to 35 K,the elusive carbonyl oxide CF_(3)C(H)OO in syn-and anti-conformations has been generated and characterized with infrared(IR)and ultraviolet-visible(UV-vis)spectroscopy.The spectroscopic identification is supported by^(18)O-labeling experiments and quantum chemical calculations at the B3 LYP/6-311++G(3df,3pd)and MP2/6-311++G(2d,2p)levels.Upon the long-wavelength irradiation(λ>680 nm),both conformers of CF_(3)C(H)OO decompose to give trifluoroacetaldehyde CF_(3)C(H)O and simultaneously rearrange to the isomeric dioxirane,cyclic-CF_(3)CH(OO),which undergoes isomerization to the lowest-energy carboxylic acid CF_(3)C(O)OH upon UV-light excitation at 365 nm.The O_(2)-oxidation of CF_(3)CH via the intermediacy of CF_(3)C(H)OO and cyclic-CF_(3)CH(OO)might provide new insight into the mechanism for the degradation of hydro-chlorofluorocarbon CF_(3)CHCl_(2)(HCFC-123)in the atmosphere.
基金partially supported by DST-INSPIRE Faculty Award。
文摘Solar energy is the primary driving force behind a planet’s climate system,and surface albedo plays a key role in determining the energy budget of the planet.Coupling the Snow,Ice,and Aerosol Radiation(SNICAR)with the Laboratoire de Météorologie Dynamique(LMD)Mars General Circulation Model(MGCM)to create a new coupled model leads to an approximately 4%drop in the net CO2 ice deposition on Mars.Newly simulated surface albedo affects the concentration of gaseous species in the Martian atmosphere(condensation-sublimation cycle).The new set-up also impacts the solar energy available in the atmosphere.These two effects together lead to subsequent and significant changes in other chemical species in the Martian atmosphere.Compared with results of the MGCM model alone,in the new coupled model CO2(gas)and O3 show a drop of about 1.17%and 8.59%in their respective concentrations,while H2O(vapor)and CO show an increase of about 13.63%and 0.56%in their respective concentrations.Among trace species,OH shows a maximum increase of about 29.44%,while the maximum drop of 11.5%is observed in the O concentration.Photochemically neutral species such as Ar and N2 remain unaffected by the albedo changes.
基金The financial support from the National Key Basic Research Program of China(Nos.2016YFA0200700,2013CB934203)the National Natural Science Foundation of China(No.21472029)
文摘During the past few years,regulation and controlling of the two-dimension（2D） self-assembled supramolecular structure on surface have drawn increasing attention in nanoscience and technology.External stimuli have been widely used to regulate these 2D nanostructures.Among various external stimuli approaches,photo-regulation as one of the most outstanding means of regulation has been extensively studied because different wave bands can lead to molecular conformation variation and new bonds to gain new molecules.In this review,the photo-regulated self-assembled structure on solid surface as well as the photo-reactions of different molecules substituted with photo-sensitive groups are introduced to give us an insight into on-surface photochemistry,which plays an important role on the nano-devices fabrication.Notably,these photo-sensitive behaviors as well as the formed structures on surface were probed at sub-molecule level by unique scanning tunneling microscopy（STM） technique.
基金support from National Natural Science Foundation of China(Nos. 20776165,20702065,20872184)Key Foundation of Chongqing Science and Technology Commission"(No.CSTC 2008BA4020)+1 种基金"A Foundation for the Author of National Excellent Doctoral Dissertation of PR China(200735)"for financial supportsponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry as well(Nos.20071108-1, 20071108-5).
文摘We have presented the synthesis and characterization of three new bromo substituted stilbene derivatives, p-3,4,5-trimethoxy-p′- 2,3,4,5,6-pentabromostilbene （C1）, p-N,N-dimethylamino-p′-2,3,4,5,6-pentabromostilbene （C2） and p-N,N-diphenylamino-p′- 2,3,4,5,6-pentabromostilbene （C3） in this letter. The UV/vis absorption and photoluminescence were investigated in various solvents. The maximal absorption wavelength of C1 exhibited blue-shift to those of C2 and C3 in different solvents. No florescence emission could be detected for these compounds at room temperature. Singlet oxygen could be efficiently produced with these sensitizers under near-ultraviolet and visible light irradiation.
文摘Diphenylchlorin (DPC) and diphenylbacteriochlorin (DPBC) were synthesized for the first time from reduction of 5,10-diphenylporphyrin (DPP). As photosensitizers they have sizable absorption in the red region of the visible spectrum. The high yield of DPC.-photosensitized generation Of O-1(2), and the EPR studies in homogenerous solution showed that the photodynamic action of DPP-based photosensitizers may proceed via type I and type II machanisms.
基金supported by the National Natural Science Foundation of China(No.40176023).
文摘Marine inorganic photochemistry, as one of the important branches of marine chemistry, is significantly connected with marine biology, marine ecology, marine geochemistry and marine environment, and plays an important role in the development of marine sciences. To date, lots of investigations in the field have been conducted home and abroad. As for the following development of marine inorganic photochemistry, it is greatly of significance to summarize these research works. This paper detailedly summarizes the present research progress in the photochemistry of Fe, Mn and Cu, with an emphasis on investigations on photochemical processes which could affect existing forms of these metal elements in seawater. The problems and shortcomings in the study field are pointed out and some suggestions for the future study are put forward.
文摘Direct photolysis and quenching experiments with styrene oxide support the existence of an efficient triplet photochemical pathway to benzyl radical formation. Similar photolytic behavior for styrene glycol carbonate strongly supports the 1,3-diradical, resulting from the scission of the benzylic C-O bond, as the geometric source of the triplet pathway. Primary photoproducts were determined by both NMR and HPLC analysis and we observed that toluene and bibenzyl were both primary photoproducts, not secondary photoproducts.
文摘Heterocyclic compounds represent a pivotal class of organic molecules with a profound impact on daily life.In particular,thiazole and isothiazole stand out as fundamental scaffolds that are widely used in medicinal chemistry,agrochemicals,and materials science(Figure 1a)[1].Despite their importance,the functionalization of these heterocycles,including alkylation,and amination,predominantly relies on cross-coupling reactions,which are often constrained by limited regioselectivity and harsh reaction conditions[2,3].
基金supported by the National Natural Science Foundation of China(21976045 and 22076112)China Scholarship Council(CSC)Scholarship(202308610123,202208610125)+1 种基金the Key Research and Development Program of Shaanxi Province(No.2024SF-YBXM-567)the Shaanxi Key Laboratory for Environmental Monitoring and Forewarning of Trace Pollutants(SHJKFJJ202318).
文摘The photochemistry of organic contaminants present in ice is receiving growing attention,given the wide presence of ice during winter in temperate regions as well as Polar and mountain environments.Differences between ice photochemistry and aqueous photochemistry,however,influence the quanti-tative fate and transformation of organic chemicals present in freshwater,marine and ice-cap environ-ments and these differences need to be explored.Here we comparatively studied the ice and aqueous photochemistry of three antibiotics[levofloxacin(LVX),sulfamerazine(SM),and chlortetracycline(CTC)]under the same simulated sunlight(λ>290 nm).Their photodegradation in ice/water followed pseudo-first-order kinetics,whereby the photolytic rates of LVX in ice and water were found to be similar,SM photodegraded faster in ice,while CTC underwent slower photodegradation in ice.Whether individual antibiotics underwent faster photodegradation in ice or not depends on the specific concentration effect and cage effect coexisting in the ice compartment.In most cases,the fastest photodegradation occurred in freshwater ice or in fresh water,and the slowest photolysis occurred in pure-water ice or in pure water.This can be attributed to the effects of key photochemical reactive constituents of Cl^(-),HA,NO_(3)^(-)and Fe(Ⅲ),that exist in natural waters.These constituents at certain levels showed significant effects(P<0.1)on the photolysis,not only in ice but also in water.However,these individual constituents at a given concentration,serve to either enhance or suppress the photoreaction,depending on the specific antibiotic and the matrix type(e.g.,ice or aqueous solution).Furthermore,extrapolation of the laboratory findings to cold environments indicate that pharmaceuticals present in ice will have a different photofate compared to water.These results are of particular relevance for those regions that experience seasonal ice cover in fresh water and coastal marine systems.
基金Supported by the National Key Project of Scientific and Technical Supporting Programs from Ministry of Science & Technology of China (2006BAD28B07-5)the Hi-Tech Research and Development (863) Program of China(2001AA247012)the Innovation in Graduate Education Plan of Northwest A&F University (05YCH013).
文摘To reveal and quantify the interactive effects of drought stresses and elevated CO2 concentration [CO2] on photochemistry efficiency of cucumber seedlings, the portable chlorophyll meter was used to measure the chlorophyll content, and the Imaging-PAM was used to image the chlorophyll fluorescence parameters and rapid light response curves （RLC） of leaves in two adjacent greenhouses. The results showed that chlorophyll content of leaves was reduced significantly with drought stress aggravated. Minimal fluorescence （Fo） was increased while maximal quantum yield of PSII （Fv/Fm） decreased significantly by severe drought stress. The significant decrease of effective quantum yield of PSII （Y（Ⅱ）） accompanied by the significant increase of quantum yield of regulated energy dissipation （Y（NPQ）） was observed under severe drought stress condition, but there was no change of quantum yield of nonregulated energy dissipation （Y（NO））. We detected that the coefficient of photochemical quenching （qP） decreased, and non-photochemical quenching （NPQ） increased significantly under severe drought stress. Furthermore, we found that maximum apparent electron transport rate （ETRmax） and saturating photosynthetically active radiation （PPFDsat） decreased significantly with drought stress aggravated. However, elevated [CO2] significantly increased FvlFm, qP and PPFDsat, and decreased NPQ under all water conditions, although there were no significant effects on chlorophyll content, Fo, Y（Ⅱ）, Y（NPQ）, Y（NO） and ETRmax. Therefore, it is concluded that CO2-fertilized greenhouses or elevated atmospheric [CO2] in the future could be favorable for cucumber growth and development, and beneficial to alleviate the negative effects of drought stresses to a certain extent.
文摘The effect of diabatic process due to the photochemical heating and cooling on the gravity wave propagation in middle atmosphere is studied. A linear gravity wave model which considers the diabatic process is established. The unstable region and the growth rate of the gravity wave caused by photochemistry are calculated. And the comparison between the model and the adiabatic gravity wave theory of pure dynamics is made. The results indicate that the photochemical heating process can induce the instability of gravity wave at mesopause. The intensity of the instability becomes stronger as the temperature decreases. The temperature feature and the altitude characteristics of the instability are consistent with the observation. Therefore, the instability of the gravity wave induced by photochemistry may be an important mechanism in polar mesopause region in summer.
文摘Hypocrellins are novel photosensitizers from China, which are demonstrated to have significant anti-tumor and anti-virus activity and to be potential photo-dynamic therapy (PDT) agents. As compared with hemato-porphyrin, the only approved photosensitizer, hypocrellins have several advantages, such as easy preparation and easy purification, high triplet quantum yield, high singlet-oxygen quantum yield, high phototoxicity but low dark toxicity, and rapid clearance from normal issues. This article reviews briefly the photophysics, photochemistry and photobiology of hypocrellins on the basis of the domestic and international research results.
基金supported by the National Natural Science Foundation of China(grant nos.21690071,21871242,U19B6001,and U1904212)the K.C.Wong Education Foundation,and the Fundamental Research Funds for the Central Universities.
文摘Metal–metal cooperativity effects have been extensively explored in olefin polymerization,along with the design and preparation of many binuclear transition metal catalysts.However,their synthesis and the tuning of metal–metal distance are complicated and time-consuming.In this contribution,a supramolecular chemistry strategy was used to construct multinuclear olefin polymerization catalysts.Urea functional groups were installed into severalα-diimine palladium catalysts to enable hydrogenbonding-induced self-assembly.
