Sulfate radical (SO4•–)-based heterogonous advanced oxidation processes (AOPs) show promising potential to degrade emerging contaminants, however, regulating the electron structure of a catalyst to promote its catalytic activity is challenging. Herein, a hybrid that consists of Co3O4−x nanocrystals decorated on urchin-like WO2.72 (Co3O4−x/WO2.72) with high-valence W and rich oxygen vacancies (OVs) used to modulate the electronic structure of Co-3d was prepared. The Co3O4−x/WO2.72 that developed exhibited high catalytic activity, activating peroxymonosulfate (PMS), and degrading sulfamerazine (SMR). With the use of Co3O4−x/WO2.72, 100 % degradation of SMR was achieved within 2 min, at a pH of 7, with the reaction rate constant k1 = 3.09 min−1. Both characterizations and density functional theory (DFT) calculations confirmed the formation of OVs and the promotion of catalytic activity. The introduction of WO2.72 greatly regulated the electronic structure of Co3O4−x. Specifically, the introduction of high-valence W enabled the Co-3d band centre to be closer to the Fermi level and enhanced electrons (e–) transfer ability, while the introduction of OVs-Co in Co3O4−x promoted the activity of electrons in the Co-3d orbital and the subsequent catalytic reaction. The reactive oxygen species (ROS) were identified as •OH, SO4•–, and singlet oxygen (1O2) by quenching experiments and electron spin resonance (EPR) analysis. The DFT calculation using the Fukui index indicated the reactive sites in SMR were available for an electrophilic attack, and three degradation pathways were proposed.
Abstract Climate projection requires an accurate understanding for soil organic carbon (SOC) decomposition and its response to warming. An emergent view considers that environmental constraints rather than chemical structure alone control SOC turnover and its temperature sensitivity (i.e., Q10), but direct long-term evidence is lacking. Here, using compound-specific radiocarbon analysis of soil profiles along a 3300-km grassland transect, we provide direct evidence for the rapid turnover of lignin-derived phenols compared with slower-cycling molecular components of SOC (i.e., long-chain lipids and black carbon). Furthermore, in contrast to the slow-cycling components whose turnover is strongly modulated by mineral association and exhibits low Q10, lignin turnover is mainly regulated by temperature and has a high Q10. Such contrasts resemble those between fast-cycling (i.e., light) and mineral-associated slow-cycling fractions from globally distributed soils. Collectively, our results suggest that warming may greatly accelerate the decomposition of lignin, especially in soils with relatively weak mineral associations.
Electrochemical disinfection (ED) is effective in removal of antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs) during wastewater treatment. However, the inner relationship of antibiotic-resistant phenotypes with their genotypes of ARB is still unclear in the ED process. This study explored the disinfection mechanism at the microcosmic level using four Escherichia coli (E. coli) strains with different antibiotic-resistant phenotypes. Results showed that bacteria with multiple antibiotic resistance tended to have stronger viability in disinfection compared with those resistant to fewer antibiotics. Interestingly, antibiotic-resistant phenotypes changed little in the disinfection process, while genotypes closely responded to bacterial resistance of different E. coli. In detail, beta-lactamase resistance genes played a leading role in the cross-resistance between antibiotics and electrochemical oxidation. They were proved to reduce oxidative destruction by increasing the strength of the cell wall and membrane. In addition, diaminopyrimidine and macrolide-lincosamide-streptogramin B resistance genes are also closely related to the bacterial resistance to ED. Combined with the quantitative determination of ARGs, the abundance of IntI1 and aminoglycoside resistance genes can be regarded as indicators for the risk of cross-resistance to antibiotics and electrochemical oxidation. This study provided important references for in depth understanding and accurate control of antibiotic resistance with advanced oxidation processes.
How speaking two languages affects executive functions has been a long-standing debate and the mechanisms underlying the observed cognitive advantages of bilingualism remain unspecified. Here, using multivariate pattern classification methods, we decoded spatial patterns of neural signals associated with Flanker task performance in mono-dialectal and bi-dialectal speakers of Chinese. While univariate approach to even-related potentials (ERPs) showed no between-group difference, decoding accuracy of ERPs was reduced in bi-dialectal as compared to mono-dialectal speakers in both congruent-neutral and incongruent-neutral classifications. There was no effect of bidialectalism, however, on decoding accuracy of alpha-band oscillations, an electrophysiological index implicated in inhibition. Behavioural data analysed using the Drift Diffusion Model (DDM) showed facilitating effects of bidialectalism on non-decision times but no effect on drift rates. These findings demonstrate that using two dialects on a daily basis enhances general attentional deployment rather than affecting specific component of executive functions such as inhibitory control. Given that the two dialects of Chinese differed almost exclusively in phonology, the bidialectalism effect was most likely motivated by resolving phonological competition at lexical processing level.
Perspective-taking, which is important for communication and social activities, can be cultivated through joint actions, including musical activities in children. We examined how rhythmic activities requiring coordination affect perspective-taking in a referential communication task with 100 Chinese 4- to 6-year-old children. In Study 1, 5- to 6-year-old children played an instrument with a virtual partner in one of three coordination conditions: synchrony, asynchrony, and antiphase synchrony. Eye movements were then monitored with the partner giving instructions to identify a shape referent which included a pre-nominal scalar adjective (e.g., big cubic block). When the target contrast (a small cubic block) was in the shared ground and a competitor contrast was occluded for the partner, participants who used perspective differences could, in principle, identify the intended referent before the shape was named. We hypothesized that asynchronous and antiphase synchronous musical activities, which require self-other distinction, might have stronger effects on perspective-taking than synchronous activity. Children in the asynchrony and antiphase synchrony conditions, but not the synchrony condition, showed anticipatory looks at the target, demonstrating real-time use of the partner's perspective. Study 2 was conducted to determine if asynchrony and antiphase asynchrony resulted in perspective-taking that otherwise would not have been observed, or if synchronous coordination inhibited perspective-taking that would otherwise have occurred. We found no evidence for online perspective-taking in 4- to 6-year-old children without music manipulation. Therefore, playing instruments asynchronously or in alternation, but not synchronously, increases perspective-taking in children of this age, likely by training self-other distinction and control.
Road transportation accounts for 56% of India's transportation sector's CO2 emissions. Reaching carbon neutrality before 2070 requires the deep decarbonization of this sector. This study assesses the potential of battery electric vehicles (BEV) and fuel-cell vehicles (FCV) as the least-cost pathway toward carbon neutrality. We estimate the future demand for passenger and freight services and evaluate the impact of EV policies using the Integrated Model of Energy, Environment, and Economy for Sustainable Development/Technology (IMED/TEC). The study covers road transport emissions, energy, and air pollution transitions under four scenarios, including reference, low, medium, and high penetration of BEV and FCV, which align with the decarbonization target agreed upon under India's national policy. Results show that the carbon neutrality target would be challenging with BEV alone in road passenger and freight transportation because it is less efficient. Combined penetration of BEV and FCV can reduce air pollutant emissions significantly. Operative implementation of FCV could diminish more than 96% of the total road transport CO2 emissions. The analytical framework also proposes local climate change policies towards a carbon neutrality strategy to escalate the share of BEV and FCV in the Indian road transport sector.
In this study, the 2008 earthquake in Wenchuan, China serves as a natural experiment for examining the effect of natural disasters on high-stakes exam performance among students who were admitted to four-year colleges between 2005 and 2011. Results of a generalized difference-in-differences model show that, on average, the earthquake reduced a student's National College Entrance Examination (NCEE) standard score by 55% of a standard deviation. The findings have implications for higher education and China's economy, because earthquake exposure lowers a student's probability of being accepted to an elite college, pursuing a major in a high-salary field, and moving to a highly developed urban area for education or employment.
Phosphate addition is commonly applied to remediate lead contaminated sites via the formation of lead phosphate particles with low solubility. However, the effects of natural organic matter (NOM) with different properties, as well as the contributions of specific interactions (particle-particle, particle-NOM, and NOM-NOM) in enhanced stabilization or flocculation of the particles, are not currently well understood. This study investigates the influence of two aquatic NOM and two soil or coal humic acid (HA) extracts on the aggregation behavior of lead phosphate particles and explores the controlling mechanisms. All types of NOM induced disaggregation and steric stabilization of the particles in the presence of Na+ (100 mM) or low (1 mM) Ca2+ concentrations, as well as at low NOM concentrations (1 mgC/L). However, for the soil and coal HA, a threshold at NOM concentrations of 10 mgC/L and high (3 mM) Ca2+ concentrations was observed where bridging flocculation (rather than steric stabilization) occurred. In situ attenuated total reflectance – Fourier transform infrared characterization confirmed adsorption of the soil and coal humic acid extracts (10 mgC/L) onto the surface of the lead phosphate particles in 3 mM Ca2+, whereas dynamic and static light scattering demonstrated extensive HA flocculation that dominated the overall scattered light intensities. These results imply that the accelerated aggregation was induced by a combination of HA adsorption and bridging flocculation by Ca2+. Overall, this research demonstrates that the type of NOM is critical to predict the colloidal stability of lead phosphate particles. Aquatic NOM stabilized the particles under all conditions evaluated, but soil or coal HA with higher molecular weight and aromaticity showed highly variable stabilization or flocculation behavior depending on the HA and Ca2+ concentrations available to adsorb to the particles and participate in bridging. These results provide new mechanistic insights on particle stabilization or destabilization by NOM.
Abstract Spatiotemporal manipulation of biological processes in living animals using noninvasive, remote-controlled stimuli is a captivating but challenging endeavor. Herein, we present the development of a biocompatible photocatalytic technology termed CAT-NIR, which uses external near infrared light (NIR, 740?nm) to trigger decaging reactions in living mice. The Os(II) terpyridine complex was identified as an efficient NIR photocatalyst for promoting deboronative hydroxylation reactions via superoxide generation in the presence of NIR light, resulting in the deprotection of phenol groups and the release of bioactive molecules under living conditions. The validation of the CAT-NIR system was demonstrated through the NIR-triggered rescue of fluorophores, prodrugs as well as biomolecules ranging from amino acids, peptides to proteins. Furthermore, by combining genetic code expansion and computer-aided screening, CAT-NIR could regulate affibody binding to the cell surface receptor HER2, providing a selective cell tagging technology through external NIR light. In particular, the tissue-penetrating ability of NIR light allowed for facile prodrug activation in living mice, enabling noninvasive, remote-controlled rescue of drug molecules. Given its broad adaptability, this CAT-NIR system may open new opportunities for manipulating the functions of bioactive molecules in living animals using external NIR light with spatiotemporal resolution.
The porous defective MIL-88B(Fe) with abundant oxygen vacancies and Fe-N sites was fabricated to accomplish nearly zero peroxydisulfate (PDS) consumption for persistent bisphenol A (BPA) degradation via electron-transfer pathway (ETP). Interestingly, the generated sulfates during ETP were oxidized to yield the confined sulfate radicals and to accomplish the peroxydisulfate regeneration in the fine-tuned MIL-88B(Fe), which was verified by series experiments and DFT calculations. Further studies suggested that the optimal De-MIL-88B(Fe)-1.25 catalyst achieved the persistent nonradical reactions for BPA decomposition under visible light irradiation with both low input and low consumption of PDS. It was the first case to achieve nearly zero PDS consumption for emerging pollutants elimination, which provided new strategy to design and tune defective metal-organic frameworks for the purpose of reducing the stoichiometry between PDS and contaminants for nearly zero PDS consumption.
Given the deficiencies of traditional government capacity indicators and cultural factors (e.g., individualism) in explaining the discrepancies of different agents' responses to the coronavirus disease 2019 (COVID-19) pandemic, the present study proposed and examined the role of neoliberalism, a novel cultural tradition of knowledge emphasizing the principles of free markets and self-governance, as an additional explanation of the discrepancies in the governmental and individual responses to the pandemic. Analyzing policy responses of 106 nations and personal responses from 105,203 individuals in 104 nations during the first wave of the pandemic, we found that nation-level neoliberalism (delineated by the economic freedom index) negatively predicted the nonlinear trajectories of government policy responses to contain the pandemic. Specifically, in more neoliberal countries, stringent containment policy responses showed a sharper decline in the later stage of the first wave of the pandemic. Moreover, nation-level neoliberalism negatively predicted individuals' pandemic-protective attitudes and behaviors. All these effects are independent of and incremental to those of nation-level individualism. In conclusion, this study sheds light on how neoliberalism could lead to negative consequences during large-scale, long-lasting public threats, offering practical guidance for adjusting public crisis management in the future.