Abstract The insufficient exciton (e−-h+ pair) separation/transfer and sluggish two-electron water oxidation are two main factors limiting the H2O2 photosynthetic efficiency of covalent organic frameworks (COFs) photocatalysts. Herein, we present an alternative strategy to simultaneously facilitate exciton separation/transfer and reduce the energy barrier of two-electron water oxidation in COFs via a dicyano functionalization. The in situ characterization and theoretical calculations reveal that the dicyano functionalization improves the amount of charge transfer channels between donor and acceptor units from two in COF-0CN without cyano functionalization to three in COF-1CN with mono-cyano functionalization and four in COF-2CN with dicyano functionalization, leading to the highest separation/transfer efficiency in COF-2CN. More importantly, the dicyano group activates the neighbouring C atom to produce the key *OH intermediate for effectively reducing the energy barrier of rate-determining two-electron water oxidation in H2O2 photosynthesis. The simultaneously enhanced exciton separation/transfer and two-electron water oxidation in COF-2CN result in high H2O2 yield (1601 μmol g−1 h−1) from water and oxygen without using sacrificial reagent under visible-light irradiation. COF-2CN can effectively yield H2O2 in water with wide pH range, in different real water samples, in scaled-up reactor under natural sunlight irradiation, and in continuous-flow reactor for consecutively producing H2O2 solution for water decontamination.
Human occupants themselves constitute an important source of volatile organic compounds (VOCs) in indoor environments through breath and dermal emissions. In order to quantify VOC emissions from occupants under real-world settings, previous indoor observational studies often determined emission factors (i.e., average emission rates per person). However, the values obtained across these studies exhibited large variability, and the causes of this variability still need to be understood. Herein we report 10-day real-time VOC measurements in a university student office, using a proton transfer reaction-quadrupole interface-time-of-flight mass spectrometer. A method was developed to identify VOCs of primary human origin and to quantify the corresponding emission factors, accounting for the dynamically changing occupancy level and ventilation rate in the assessed office. We found that the emission factors of many dermally emitted VOCs strongly increased as the ozone concentration increased from <3 to 10–15 ppb. These VOCs include geranyl acetone, 6-methyl-5-hepten-2-one (6-MHO), and C10-C12 saturated aldehydes, which align with characteristic first-generation ozonolysis products of skin oil. The strongest increase occurred for 6-MHO, from 113 to 337 μg/h/p. In comparison, acetone and isoprene, which are primarily emitted from human breath, varied little with the ozone level. In light of this finding, we conducted an integrated analysis of emission factors reported in the literature for two frequently reported species, namely, 6-MHO and decanal. Ozone concentration alone can explain 94–97% of the variation in their emission factors across previous studies, and the best-estimated ozone dependence obtained using the literature data is consistent with those obtained in the current study. These results suggest that the ozone concentration is a key factor regulating emission factors of many dermally emitted VOCs in real indoor environments, which has to be considered when reporting or using the emission factors.
Quorum sensing (QS)-based manipulations emerge as a promising solution for biofilm reactors to overcome challenges from inefficient biofilm formation and lengthy start-ups. However, the ecological mechanisms underlying how QS regulates microbial behaviors and community assembly remain elusive. Herein, by introducing different levels of N-acyl-homoserine lactones, we manipulated the strength of QS during the start-up of moving bed biofilm reactors and compared the dynamics of bacterial communities. We found that enhanced QS elevated the fitness of fast-growing bacteria with high ribosomal RNA operon (rrn) copy numbers in their genomes in both the sludge and biofilm communities. This led to notably increased extracellular substance production, as evidenced by strong positive correlations between community-level rrn copy numbers and extracellular proteins and polysaccharides (Pearson's r = 0.529−0.830, P < 0.001). Network analyses demonstrated that enhanced QS significantly promoted the ecological interactions among taxa, particularly cooperative interactions. Bacterial taxa with higher network degrees were more strongly correlated with extracellular substances, suggesting their crucial roles as public goods in regulating bacterial interactions and shaping network structures. However, the assembly of more cooperative communities in QS-enhanced reactors came at the cost of decreased network stability and modularity. Null model and dissimilarity-overlap curve analysis revealed that enhanced QS strengthened stochastic processes in community assembly and rendered the universal population dynamics more convergent. Additionally, these shaping effects were consistent for both the sludge and biofilm communities, underpinning the planktonic-to-biofilm transition. This work highlights that QS manipulations efficiently drive community assembly and confer specialized functional traits to communities by recruiting taxa with specific life strategies and regulating interspecific interactions. These ecological insights deepen our understanding of the rules governing microbial societies and provide guidance for managing engineering ecosystems.
Chlorinated paraffins (CPs), mainly short-chain CPs (SCCPs) and medium-chain CPs (MCCPs), are currently the most produced and used industrial chemicals related to persistent organic pollutants (POPs) globally. These chemicals are widely detected in the environment and in the human body. As the release of SCCPs and MCCPs from products represents only a small fraction of their stock in products, the potential long-term release of CPs from a large variety of products at the waste stage has become an issue of great concern. The results of this study showed that, by 2050, SCCPs and MCCPs used between 2000 and 2021 will cumulatively generate 226.49 Mt of CP-containing wastes, comprising 8610.13 kt of SCCPs and MCCPs. Approximately 79.72 Mt of CP-containing wastes is predicted to be generated abroad through the international trade of products using SCCPs and MCCPs. The magnitude, distribution, and growth of CP-containing wastes subject to environmentally sound disposal will depend largely on the relevant provisions of the Stockholm and Basel Conventions and the forthcoming global plastic treaty. According to multiple scenarios synthesizing the provisions of the three conventions, 26.6–101.1 Mt of CP-containing wastes will be subject to environmentally sound disposal as POP wastes, which would pose a great challenge to the waste disposal capacity of China, as well as for countries importing CP-containing products. The additional 5-year exemption period for MCCPs is expected to see an additional 10 Mt of CP-containing wastes subject to environmentally sound disposal. Thus, there is an urgent need to strengthen the Stockholm and Basel Conventions and the global plastic treaty.
Tryptophan (Trp) plays a critical role in the regulation of protein structure, interactions and functions through its π system and indole N–H group. A generalizable method for blocking and rescuing Trp interactions would enable the gain-of-function manipulation of various Trp-containing proteins in vivo, but generating such a platform remains challenging. Here we develop a genetically encoded N1-vinyl-caged Trp capable of rapid and bioorthogonal decaging through an optimized inverse electron-demand Diels–Alder reaction, allowing site-specific activation of Trp on a protein of interest in living cells. This chemical activation of a genetically encoded caged-tryptophan (Trp-CAGE) strategy enables precise activation of the Trp of interest underlying diverse important molecular interactions. We demonstrate the utility of Trp-CAGE across various protein families, such as catalase-peroxidases and kinases, as translation initiators and posttranslational modification readers, allowing the modulation of epigenetic signalling in a temporally controlled manner. Coupled with computer-aided prediction, our strategy paves the way for bioorthogonal Trp activation on more than 28,000 candidate proteins within their native cellular settings.
The heterogeneous coprecipitation of nanocrystals with metals on substrates plays a significant role in both natural and engineered systems. Due to the small dimensions and thereby the large specific surface area, nanocrystal coprecipitation with metals, which is ubiquitous in natural settings, exerts drastic effects on the biogeochemical cycling of metals on the earth’s crust. Meanwhile, the controlled synthesis of nanocrystals with metal doping to achieve tunable size/composition enables their broad applications as adsorbents and catalysts in many engineered settings. Despite their importance, complex interactions among aqueous ions/polymers, nanocrystals, substrates, and metals are far from being well-understood, leaving the controlling mechanisms for nanocrystal formation with metals on substrates uncovered.
In this Account, we discuss our systematic investigation over the past 10 years of the heterogeneous formation of representative nanocrystals with metals on typical substrates. We chose Fe(OH)3 and BaSO4 as representative nanocrystals. Mechanisms for varied metal coprecipitation were also investigated for both types of nanocrystals (i.e., Fe, Al, Cr, Cu, and Pb)(OH)3 and (Ba, Sr)(SO4, SeO4, and SeO3)). Bare SiO2 and Al2O3, as well as those coated with varied organics, were selected as geologically or synthetically representative substrates. Through the integration of state-of-the-art nanoscale interfacial characterization techniques with theoretical calculations, the complex interactions during nanocrystal formation at interfaces were probed and the controlling mechanisms were identified.
For BaSO4 and Fe(OH)3 formation on substrates, the local supersaturation levels near substrates were controlled by Ba2+ adsorption and the electrostatic attraction of Fe(OH)3 monomer/polymer to substrates, respectively. Meanwhile, substrate hydrophobicity controlled the interfacial energy for the nucleation of both nanocrystals on (in)organic substrates. Metal ions’ (i.e., Cr/Al/Cu/Pb) hydrolysis constants and substrates’ dielectric constants controlled metal ion adsorption onto substrates, which altered the surface charges of substrates, thus controlling heterogeneous Fe(OH)3 nanocrystal formation on substrates by electrostatic interactions. The sizes and compositions of heterogeneous (Fe, Cr)(OH)3 and (Ba, Sr)(SO4, SeO4, SeO3) formed on substrates were found to be distinct from those of homogeneous precipitates formed in solution. The substrate (de)protonation could alter the local solution’s pH and the substrates’ surface charge; substrates could also adsorb cations, affecting local Fe/Cr/Ba/Sr ion concentrations at solid–water interfaces, thus controlling the amount/size/composition of nanocrystals by tuning their nucleation/growth/deposition on substrates. From slightly supersaturated solution, homogeneous coprecipitates of microsized (Ba, Sr)(SO4, SeO4, SeO3) formed through growth, with little Sr/Se(VI) incorporation due to higher solubilities of SrSO4 and BaSeO4 over BaSO4. While cation enrichment near substrates made the local solution highly supersaturated, nanosized coprecipitates formed on substrates through nucleation, with more Sr/Se(VI) incorporation due to lower interfacial energies of SrSO4 and BaSeO4 over BaSO4. The new insights gained advanced our understanding of the biogeochemical cycling of varied elements at solid–water interfaces and of the controlled synthesis of functional nanocrystals.
Microplastics are found in various human tissues and are considered harmful, raising concerns about human exposure to microplastics in the environment. Existing research has analyzed indoor and occupational scenarios, but long-term monitoring of ambient atmospheric microplastics (AMPs), especially in highly polluted urban regions, needs to be further investigated. This study estimated human environmental exposure to AMPs by considering inhalation, dust ingestion, and dermal exposure in three urban functional zones within a megacity. The annual exposure quantity was 7.37 * 104 items for children and 1.06 * 105 items for adults, comparable with the human microplastic consumption from food and water. Significant spatiotemporal differences were observed in the characteristics of AMPs that humans were exposed to, with wind speed and rainfall frequency mainly driving these changes. The annual human AMP exposure quantity in urban green land spaces, which were recognized as relatively low polluted zones, was comparable with that in public service zones and residential zones. Notably, significant positive correlations between the AMP characteristics and the pathogenicity of the airborne bacterial community were discovered. AMP size and immune-mediated disease risks brought by atmospheric microbes showed the most significant relationship, where Sphingomonas might act as the potential key mediator.
Atmospheric organic peroxides (POs) play a key role in the formation of O3 and secondary organic aerosol (SOA), impacting both air quality and human health. However, there still remain technical challenges in investigating the reactivity of POs in ambient aerosols due to the instability and lack of standards for POs, impeding accurate evaluation of their environmental impacts. In the present study, we conducted the first attempt to categorize and quantify POs in ambient PM2.5 through hydrolysis, which is an important transformation pathway for POs, thus revealing the reactivities of various POs. POs were generally categorized into hydrolyzable POs (HPO) and unhydrolyzable POs (UPO). HPO were further categorized into three groups: short-lifetime HPO (S-HPO), intermediate-lifetime HPO (I-HPO), and long-lifetime HPO (L-HPO). S-HPO and L-HPO are typically formed from Criegee intermediate (CI) and RO2 radical reactions, respectively. Results show that L-HPO are the most abundant HPO, indicating the dominant role of RO2 pathway in HPO formation. Despite their lower concentration compared to L-HPO, S-HPO make a major contribution to the HPO hydrolysis rate due to their faster rate constants. The hydrolysis of PM2.5 POs accounts for 19% of the nighttime gas-phase H2O2 growth during the summer observation, constituting a noteworthy source of gas-phase H2O2 and contributing to the atmospheric oxidation capacity. Seasonal and weather conditions significantly impact the composition of POs, with HPO concentrations in summer being significantly higher than those in winter and elevated under rainy and nighttime conditions. POs are mainly composed of HPO in summer, while in winter, POs are dominated by UPO.
A comprehensive and accurate assessment of the policy effect of national tourism days is of great significance to further promote urban inbound tourism. Based on the panel data of 59 cities in China from 2000 to 2017, this paper evaluates the local and spatial spillover effects of the China Tourism Day policy on urban inbound tourism using a spatial difference-in-differences model based on the establishment of the China Tourism Day as a quasi-natural experiment. The study found that the China Tourism Day policy significantly increased the number of foreign tourists in cities but significantly reduced their average length of stay, with a positive spatial spillover effect on inbound tourism in surrounding cities.
The low commercialization rate of academic patents is a common challenge for developing countries. This study evaluates the impact of provincial policies on the commercialization of academic patents using spatial regression models and propensity score matching methods. It also provides a reference for optimizing university patent management. Considering provincial patent policies enacted in China in 2016 as the treatment, the results show no significant effect of provincial patent policies on rights definition and implementation economics on the commercialization of academic patents. However, promotion standard policies have a significant positive effect on the commercialization of academic patents. A significant negative spatial spillover effect is observed on the commercialization of academic patents among universities with similar innovation capabilities. Furthermore, non-geographic distances, such as innovation distance, positively affect competition among universities and their commercialization of academic patents. Therefore, local governments should consider the needs of academic inventors for title promotion when designing and introducing patent incentive policies for universities.
In the context of the rapid growth of corporate green investment and the rapid dissemination of information brought about by Internet technology, it is important to explore the relationship between investor attention and corporate environmental responsibility. Unfortunately, an in-depth research on the relationship between investor attention and firms' environment, society, and governance (ESG) performance remains unexplored. The results show a mutual inhibition between investor attention and firms’ ESG performance. Each 1% increase in investor attention decreases ESG performance by 0.252%, while each 1% increase in ESG performance decreases investor attention by 2.296%. Thus, ESG performance dominates this mutual influence. Moreover, ESG performance positively affects ESG performance and investor attention of neighboring firms. Each 1% increase in ESG performance increases ESG performance and investor attention of neighboring firms by 0.371% and 0.983%, respectively. Investor attention negatively affects investor attention and ESG performance of neighboring firms. Each 1% increase in investor attention decreases ESG performance and investor attention of neighboring firms by 0.04% and 0.104%, respectively. Further research reveals significant regional and organizational heterogeneity in the relationship between investor attention and ESG performance. The findings provide theoretical and empirical insights for further improvement of the ESG system and continued strengthening of investor guidance by regulators.
Although tourism is often treated as one of the crucial industries for the construction of low-carbon cities (LCCs), there is no systematic evidence on whether there is a causal relationship. This research aims to explore and empirically test the causal link between LCC initiatives and inbound tourism of cities using a spatial difference-in-differences approach with balanced panel data of 59 Chinese major tourism cities from 2000 to 2017. The results show that urban tourism by foreign tourists exhibits significant spatial spillover effects. Compared to non-LCCs, the number of foreign tourists on LCCs increased by 4.7 percentage points and the average length of stay of foreign tourists increased by 3.6 percentage points. The direct impact of the LCC initiative on foreign tourists was significant, while the indirect impact was insignificant. The findings of the study not only deepen the researchon sustainable tourism behavior of inbound tourists, but also provide valuable references for cities to participate in the competition in the international tourism market through low-carbon development.
