A flow photochemical reaction system for a π-Lewis acidic metal-catalyzed cyclization/radical addition sequence was developed, which utilizes in situ-generated 2-benzopyrylium intermediates as the photoredox catalyst and electrophilic substrates. The key 2-benzopyrylium intermediates were generated in the flow reaction system through the intramolecular cyclization of ortho-carbonyl alkynylbenzene derivatives by the π-Lewis acidic metal catalyst AgNTf2 and the subsequent proto-demetalation with trifluoroacetic acid. The 2-benzopyrylium intermediates underwent further photoreactions with benzyltrimethylsilane derivatives as the donor molecule in the flow photoreactor to provide 1H-isochromene derivatives in higher yields in most cases than the batch reaction system.

The surface photochemical activity of goethite, which occurs widely in surface soils and sediments, plays a crucial role in the environmental transformation of various pollutants and natural organic matter. This study systemically investigated the mechanism of different types of surface hydroxyl groups on goethite in generating reactive oxygen species (ROSs) and Fe(III) reduction under sunlight irradiation. Surface hydroxyl groups were found to induce photoreductive dissolution of Fe(III) at the goethite-water interface to produce Fe2+(aq), while promoting the production of ROSs. Substitution of the surface hydroxyl groups on goethite by fluoride significantly inhibited the photochemical activity of goethite, demonstrating their important role in photochemical activation of goethite. The results showed that the surface hydroxyl groups (especially the terminating hydroxyl groups, ≡FeOH) led to the formation of Fe(III)-hydroxyl complexes via ligand-metal charge transfer on the goethite surface upon photoexcitation, facilitating the production of Fe2+(aq) and •OH. The bridging hydroxyl groups (≡Fe2OH) were shown to mainly catalyze the production of H2O2, leading to the subsequent light-driven Fenton reaction to produce •OH. These findings provide important insights into the activation of molecular oxygen on the goethite surface driven by sunlight in the environment, and the corresponding degradation of anthropogenic and natural organic compounds caused by the generated ROSs.

Atmospheric aerosols have a serious impact on altering the radiation balance of the vulnerable Himalayan atmosphere. Organic aerosol (OA), one of the least resolved aerosol fractions in the Himalayas, constrain our competence to assess their climate impacts on the region. Here we investigate water-soluble OA molecules in PM10 samples collected from March to May 2019 at Lachung (27.4°N and 88.4°E), a high-altitude location (2700 m a.s.l.) in the eastern Himalaya, to elucidate their origin and formation process. The dominance of oxalic acid (C2) reveals that water-soluble OA in the eastern Himalaya are atmospherically processed. Backward air mass trajectories and mass concentration ratios of organic tracers as well as relationships with inorganic species (K+, SO42-, NH4+) suggest an anthropogenic origin of water-soluble OA with significant atmospheric processing during long-range transport to the eastern Himalayan region. We used the thermodynamic prediction of aerosol liquid water (ALW) to examine the formation mechanism of secondary OA (SOA) such as oxalic acid. Correlations of ALW with SO42- and water-soluble organic matter show that ALW is sensitive to both anthropogenic sulfate and water-soluble organic compounds in Himalayan aerosols. A strong positive relationship of C2 acid with predicted ALW provides evidence of extensive SOA formation from precursors via aqueous phase photochemical processes. This inference is supported by positive correlations of C2 acid relative abundance with diagnostic mass concentration ratios of C2 acid to precursor molecules. Our findings underscore the importance of anthropogenic sources and ALW in SOA formation through aqueous phase processes in the eastern Himalaya.

The sensitivity analysis of ozone generation in key ozone-polluted regions and cities is an important basis for the prevention and control of near-surface ozone （O3） pollution. Based on the five-year data of ozone, VOCs, and NOx from three typical stations in Shanghai, namely Dianshan Lake Station （suburban area）, Pudong Station （urban area）, and Xinlian Station （industrial area） from 2016 to 2020, the nonlinear relationship between ozone and precursors （VOCs and NOx） during the high-ozone season in the five years was quantitatively analyzed using an observation model. The results showed that the peak months of near-surface ozone in Shanghai were from April to September during 2016 to 2020, with the highest values appearing from June to August. The volume fraction of VOCs and NO2 concentration had a strong indicative significance for the O3 concentration at Pudong Station. The O3 concentration at Dianshan Lake Station was mainly influenced by regional environment, meteorological factors, and cross-regional transmission. The ozone concentration at Xinlian Station was a combination of environmental background concentration and industrial area photochemical pollution. Pudong Station and Dianshan Lake Station were in the VOCs control zone. Xinlian Station was gradually closer to the NOx control zone from 2016 to 2019, transitioning to the VOCs control zone since 2020. The L·OH of Pudong Station, Dianshan Lake Station, and Xinlian Station were： NOx control area>collaborative control area>VOCs control area.

Herein, we describe a visible light-induced C(sp2)-H arylation method for quinoxalin-2(1H)-ones and coumarins using iodonium ylides without the need for external photocatalysts. The protocol demonstrates a broad substrate scope, enabling the arylation of diverse heterocycles through a simple and mild procedure. Furthermore, the photochemical reaction showcases its applicability in the efficient synthesis of biologically active molecules. Computational investigations at the CASPT2//CASSCF/PCM level of theory revealed that the excited state of quinoxalin-2(1H)-one facilitates electron transfer from its π bond to the antibonding orbital of the C-I bond in the iodonium ylide, ultimately leading to the formation of an aryl radical, which subsequently participates in the C-H arylation process. In addition, our calculations reveal that during the single-electron transfer (SET) process, the C-I bond cleavage in iodonium ylide and new C-C bond formation between resultant aryl radical and cationic quinoxaline species take place in a concerned manner. This enables the arylation reaction to efficiently proceed along an energy-efficient route.

Currently, microplastics (MPs) have ubiquitously distributed in different aquatic environments. Due to the unique physicochemical properties, MPs exhibit a variety of environmental effects with the coexisted contaminants. MPs can not only alter the migration of contaminants via vector effect, but also affect the transformation process and fate of contaminants via environmental persistent free radicals (EPFRs). The aging processes may enhance the interaction between MPs and co-existed contaminants. Thus, it is of great significance to review the aging mechanism of MPs and the influence of coexisted substances, the formation mechanism of EPFRs, environmental effects of MPs and relevant mechanism. Moreover, microplastic-derived dissolved organic matter (MP-DOM) may also influence the elemental biogeochemical cycles and the relevant environmental processes. However, the environmental implications of MP-DOM are rarely outlined. Finally, the knowledge gaps on environmental effects of MPs were proposed.

We have established a facile and efficient protocol for the generation of germyl radicals by employing photo-excited electron transfer (ET) in an electron donor-acceptor (EDA) complex to drive hydrogen-atom transfer (HAT) from germyl hydride (R3GeH). Using a catalytic amount of EDA complex of commercially available thiol and benzophenone derivatives, the ET-HAT cycle smoothly proceeds simply upon blue-light irradiation without any transition metal or photocatalyst. This protocol also affords silyl radical from silyl hydride.

Activated sludge extracellular polymeric substances (ASEPSs) comprise most dissolved organic matters (DOMs) in the tail water. However, the understanding of the link between the photolysis of antibiotic and the photo-reactivity/photo-persistence of ASEPS components is limited. This study first investigated the photochemical behaviors of ASEPS\'s components (humic acids (HA), hydrophobic substances (HOS) and hydrophilic substances (HIS)) separated from municipal sludge\'s EPS (M-EPS) and nitrification sludge\'s EPS (N-EPS) in the photolysis of sulfadiazine (SDZ). The results showed that 60% of SDZ was removed by the M-EPS, but the effect in the separated components was weakened, and only 24% - 39% was degraded. However, 58% of SDZ was cleaned by HOS in N-EPS, which was 23% higher than full N-EPS. M-EPS components had lower steady-state concentrations of triplet intermediates (3EPS*), hydroxyl radicals (·OH) and singlet oxygen (1O2) than M-EPS, but N-EPS components had the highest concentrations (5.96 ×10-15, 8.44 ×10-18, 4.56 ×10-13 M, respectively). The changes of CO, C-O and O-CO groups in HA and HOS potentially correspond to reactive specie\'s generation. These groups change little in HIS, which may make it have radiation resistance. HCO-3 and NO-3 decreased the indirect photolysis of SDZ, and its by-product N-(2-Pyrimidinyl)1,4-benzenediamine presents high environmental risk.

To develop advanced optical systems, many scientists have endeavored to create smart optical materials which can tune their photophysical properties by changing molecular states. However, optical multi-states are obtained usually by mixing many dyes or stacking multi-layered structures. Here, multiple molecular states are tried to be generated with a single dye. In order to achieve the goal, a diacetylene-functionalized cyanostilbene luminogen (DACSM) is newly synthesized by covalently connecting diacetylene and cyanostilbene molecular functions. Photochemical reaction of cyanostilbene and topochemical polymerization of diacetylene can change the molecular state of DACSM. By thermal stimulations and the photochemical reaction, the conformation of polymerized DACSM is further tuned. The synergetic molecular cooperation of cyanostilbene and diacetylene generates multiple molecular states of DACSM. Utilizing the optical multi-states achieved from the newly developed DACSM, switchable optical patterns and smart secret codes are successfully demonstrated.

To investigate disparities in VOCs pollution characteristics, O3 generation activity, and source apportionment outcomes resulting from photooxidation, online monitoring of 106 VOCs was conducted in Jinshan District, Shanghai from April to October 2020. The observed VOCs concentrations (VOCs-obs) were 47.1 ppbv and 59.2 ppbv for clear days (CD) and O3-polluted days (OPD), respectively. The increase in daytime concentrations of alkenes is a significant factor contributing to the enhanced atmospheric photochemical activity during the OPD period, corroborated by VOCs-loss, ozone formation potential (OFP), propy-equiv concentration, and LOH. The sensitivity analysis of O3-NOx-VOCs indicated that O3 formation was in a transitional regime towards NOx-limited conditions. The results of positive matrix factorization (PMF) demonstrated that refining and petrochemicals (20.8-25.0 %), along with oil and gas evaporation (15.6-16.7 %) were the main sources of VOCs concentrations. Notably, source apportionment based on VOCs-obs underestimated the contributions from sources of reactive components. It is worth highlighting that the sunlight impact & background source was identified as the major contributor to LOH (21.6 %) and OFP (25.3 %), signifying its significant role in O3 formation. This study reiterates the importance of controlling reactive VOC components to mitigate O3 pollution and provides a scientific foundation for air quality management, with emphasis on priority species and controlling sources.