Decrypting the critical point of internal rotation of formaldehyde: A rotational study of the acrolein-formaldehyde complex.

The rotational spectrum of an acrolein-formaldehyde complex has been characterized using pulsed jet Fourier transform microwave spectroscopy complemented with quantum chemical calculations. One isomer has been observed in pulsed jets, which is stabilized by a dominant O=C⋯O tetrel bond (n → π* interaction) and a secondary C-H⋯O hydrogen bond. Splittings arising from the internal rotation of formaldehyde around its C2v axis were also observed, from which its V2 barrier was evaluated. It seems that when V2 equals or exceeds 4.61 kJ mol-1, no splitting of the spectral lines of the rotational spectrum was observed. The nature of the non-covalent interactions of the target complex is elucidated through natural bond orbital analysis. These findings contribute to a deeper understanding on the non-covalent interactions within the dimeric complex formed by two aldehydes.

C···S Tetrel Bond Favored in the Phenyl Isothiocyanate-CO2 Complex: A Rotational Study.

The rotational spectrum of the phenyl isothiocyanate-CO2 complex was investigated by pulsed-jet Fourier transform microwave spectroscopy complemented by quantum chemical calculations. Only one isomer, with CO2 almost in the plane of phenyl isothiocyanate, has been detected in the pulsed jet, of which the spectrum displays a quadrupole coupling hyperfine structure due to the presence of a 14N nucleus (I = 1). This structure is nearly equal to the lowest energy geometry obtained by B3LYP-D3(BJ)/6-311++G(d,p), which has been dominated by a C···S tetrel bond (n → π* interaction) and one secondary C-H···O hydrogen bond (n → σ* interaction). Molecular electrostatic potential and natural bond orbital analysis were used to characterize the noncovalent interactions of the complex. The results from this study would lay the groundwork for the design and advancement of materials that exhibit high efficiency in capturing CO2.

Conformational equilibria and interaction preference in the complex of isoprene-maleic anhydride.

The rotational spectrum of the isoprene-maleic anhydride complex has been investigated by pulsed jet Fourier transform microwave spectroscopy and interpreted with complementary quantum chemical calculations. Theoretical predictions have yielded four plausible isomers, all residing within an energy window of 12 kJ mol-1. However, two distinct isomers characterized by a π-π stacked configuration have been experimentally observed in pulsed jets, which have differed in the orientation of isoprene over maleic anhydride. The relative population ratio of the two detected isomers has been estimated to be NI/NII ≈ 3/1 from rigorous measurements of the relative intensity on a set of µc-type transitions. Remarkably, this study underscores the pivotal role played by the interaction between the CC bonding orbital (π) of isoprene and the CC antibonding orbital (π*) of maleic anhydride in stabilizing the target complex.

The Dunning-Kruger effect: subjective health perceptions on smoking behavior among older Chinese adults.

BACKGROUND: The intrinsic damage and external hazards of smoking are major risk factors for poorer health and are recognized as a global health issue of concern in geriatric health. This study aims to assess the Dunning-Kruger effect through the influence of subjective health perceptions on smoking behavior in older adults. METHODS: This study used data from the 2018 Chinese Longitudinal Healthy Longevity Survey (N = 9,683) provided by the Center for Healthy Aging and Development Studies at Peking University. A binary logistic model was used to examine whether the Dunning-Kruger effect affects smoking behavior in older adults, and a linear probability model was used as a commentary baseline model for logistic regression to prevent measurement bias. In addition, a mediating analysis was used to examine the mechanisms through which the Dunning-Kruger effect occurs. RESULTS: Older adults often overestimated their current health status and underestimated the health risks of smoking, causing the Dunning-Kruger effect to arise from their inadequate self-perceived health (i.e., older adults are more likely to smoke when they have better self-rated health or when hypertension, cardiopathy, stroke, and diabetes have little or no impact on their daily lives). These observations can be explained by the older adults' subjective health perceptions arising from their ingenuous understanding of their health, which indirectly influences their smoking behavior to some extent. CONCLUSION: Older adults' self-perceived health was associated with smoking behavior. Public health institutions should improve older adults' health perceptions so that they objectively understand their own health status.

A novel iron molybdate photocatalyst with heterojunction-like band gap structure for organic pollutant degradation by activation of persulfate under simulated sunlight irradiation.

Advanced oxidation processes (AOPs) applied to wastewater treatment have become increasingly well developed and the ability of a single technology to remove difficult organic pollutants is limited. One of the main limiting factors is the insufficient variety and quantity of active species generated during the reaction process and catalyst failure. The coupling of the two methods is a practical and effective approach. In this study, different types of semiconductor persulfate (PS) activators, iron molybdate nanoparticles (I-FeMoO4, II-FeMoO4, and III-FeMoO4), were synthesized by simple solvothermal and calcination methods and applied to photo-assisted activation of PS systems. In addition, the relationship between the intrinsic physicochemical and optoelectronic properties of FeMoO4 and the catalytic degradation performance was revealed by a series of characterization tools, and the dominant catalysts were screened. At an unadjusted pH of 4.86, 0.6 g L-1 of PS and 0.4 g L-1 of I-FeMoO4 could achieve efficient degradation of several difficult organic dye contaminants (rhodamine b (Rh B), methylene blue (MB), malachite green (MG), methyl orange (MO), and tartrazine (TTZ)) and other antibiotic contaminants (sulfamethoxazole (SMX), tetracycline (TC), norfloxacin (NOR), and carbamazepine (CBZ)) within 5-60 min. Possible degradation mechanisms in the I-FeMoO4/PS/Light reaction system were suggested by radical trapping experiments and electron paramagnetic resonance (EPR) tests. Recovery tests demonstrated that I-FeMoO4 has good recoverable stability and did not cause secondary pollution. Finally, our study provided a new perspective on the application of coupled wastewater treatment technologies in the practical treatment of organic wastewater.

Insights into the Diels-Alder Reaction of Furan with Maleic Anhydride from Its Prereactive Intermediate.

The prereactive intermediate in the furan-maleic anhydride cycloaddition, a classical Diels-Alder reaction, has been captured and characterized in pulsed jets by Fourier transform microwave spectroscopy for the first time. The observed species is stabilized by the π-π* interaction between the two moieties, which connects to the endo channel of the cycloaddition. The secondary interactions between the C=C and C=O in the observed isomer are accountable for its lower energy with respect to the one with the exo channel. The present study tries to fill the significant void of the experimental information on prereactive intermediates as the first stage of Diels-Alder cycloadditions, by outlining the stability of the prereactive intermediate and its accurate molecular structure and by emphasizing the role of the π-π* interaction in governing the stereochemical outcome of the reaction.

Surface-modified, dye-sensitized niobate nanosheets enabling an efficient solar-driven Z-scheme for overall water splitting.

While dye-sensitized metal oxides are good candidates as H2 evolution photocatalysts for solar-driven Z-scheme water splitting, their solar-to-hydrogen (STH) energy conversion efficiencies remain low because of uncontrolled charge recombination reactions. Here, we show that modification of Ru dye-sensitized, Pt-intercalated HCa2Nb3O10 nanosheets (Ru/Pt/HCa2Nb3O10) with both amorphous Al2O3 and poly(styrenesulfonate) (PSS) improves the STH efficiency of Z-scheme overall water splitting by a factor of ~100, when the nanosheets are used in combination with a WO3-based O2 evolution photocatalyst and an I3-/I- redox mediator, relative to an analogous system that uses unmodified Ru/Pt/HCa2Nb3O10. By using the optimized photocatalyst, PSS/Ru/Al2O3/Pt/HCa2Nb3O10, a maximum STH of 0.12% and an apparent quantum yield of 4.1% at 420 nm were obtained, by far the highest among dye-sensitized water splitting systems and comparable to conventional semiconductor-based suspended particulate photocatalyst systems.

Geometric and Scaling Effects in the Speed of Catalytic Enzyme Micropumps.

Self-powered, biocompatible pumps in the nanometer to micron length scale have the potential to enable technology in several fields, including chemical analysis and medical diagnostics. Chemically powered, catalytic micropumps have been developed but are not able to function well in biocompatible environments due to their intolerance of salt solutions and the use of toxic fuels. In contrast, enzymatically powered catalytic pumps offer good biocompatibility, selectivity, and scalability, but their performance at length scales below a few millimeters, which is important to many of their possible applications, has not been well tested. Here, urease-based enzyme pumps of millimeter and micrometer dimensions were fabricated and studied. The scaling of the pumping velocity was measured experimentally and simulated by numerical modeling. Pumping speeds were analyzed accurately by eliminating Brownian noise from the data using enzyme patches between 5 mm and 350 µm in size. Pumping speeds of microns per second could be achieved with urease pumps and were fastest when the channel height exceeded the width of the catalytic pump patch. In all cases, pumping was weak when the dimensions of the patch were 100 µm or less. Experimental and simulation results were consistent with a density-driven pumping mechanism at all sizes studied and served as a framework for the in silico study of more complex two-dimensional (2D) and three-dimensional (3D) geometries. Attempts to create directional flow by juxtaposing inward and outward pumps were unsuccessful because of the symmetry of convection rolls produced by millimeter-size pump patches and the slow speeds of smaller pumps. However, simulations of a corrugated ratchet structure showed that directional pumping could be achieved with pump patches in the millimeter size range.

For Sustainable Career Development: Framework and Assessment of the Employability of Business English Graduates.

Employability is an important indicator of the competency of the employees. Employability model is a useful analytical framework for studying the ever-changing relationship between higher education and the job market. At present, the demand for business English graduates is increasing, however, there is a skill gap between their educational readiness and the recruitment requirements. In order to solve this problem, this study adopted mixed methods research and carried out the research design according to the exploratory sequence design to construct an employability model for business English graduates. A 46-item scale was developed to measure the employability of business English graduates' employability. After assessment, it was found that the employability of business English graduates was multi-dimensional, with three dimensions-professional knowledge, generic competencies, and career management and 10 sub-dimensions-English language skills, foreign trade competencies, computer and internet application skills, social skills, learning and development, personal traits, thinking ability, work ethics, career identity and planning, and service awareness. This study verified that the employability of business English graduates reached the standard of talent training and met the requirements of employers. There were employability differences in gender, places of origin and educational institutions. From this study, it could be inferred that cultivation of business English majors should be multi-dimensional.

COVID-19 Pandemic: The Influence of Culture and Lessons for Collaborative Activities.

The rapid epidemiological shift from an epidemic/outbreak in Wuhan, China, to a global pandemic of COVID-19 in less than 3 months came with lessons the world's health system should learn to prepare for the future outbreaks. Since February 20, 2020, the total number of confirmed cases of COVID-19 has been increased very slowly in the countries of East Asia, including Japan, South Korea, and China, when compared with those in the Western countries. This chapter begins with an overview of the impact of COVID-19 on healthcare workers and public health facilities, followed by immediate global actions and research in response to the newly emerged pandemic. It includes an evaluation of the potential influence of culture on the implementation of different protective measures to combat the COVID-19 pandemic while at the same time offering suggestions that will make it easier for all populations to adapt protective steps against COVID-19 and other respiratory infectious diseases. Finally, the chapter provides a detailed discussion of lessons we have learned from the pandemic, leading to the conclusion that the transition from individualism to collaborative efforts is the treatment of universal pandemics.

Lessons learned from the 2019-nCoV epidemic on prevention of future infectious diseases.

Only a month after the outbreak of pneumonia caused by 2019-nCoV, more than forty-thousand people were infected. This put enormous pressure on the Chinese government, medical healthcare provider, and the general public, but also made the international community deeply nervous. On the 25th day after the outbreak, the Chinese government implemented strict traffic restrictions on the area where the 2019-nCoV had originated-Hubei province, whose capital city is Wuhan. Ten days later, the rate of increase of cases in Hubei showed a significant difference (p = 0.0001) compared with the total rate of increase in other provinces of China. These preliminary data suggest the effectiveness of a traffic restriction policy for this pandemic thus far. At the same time, solid financial support and improved research ability, along with network communication technology, also greatly facilitated the application of epidemic prevention measures. These measures were motivated by the need to provide effective treatment of patients, and involved consultation with three major groups in policy formulation-public health experts, the government, and the general public. It was also aided by media and information technology, as well as international cooperation. This experience will provide China and other countries with valuable lessons for quickly coordinating and coping with future public health emergencies.

Understanding photoelectrochemical kinetics in a model CO2 fixation reaction.

Kinetic studies of photo- and photoelectro-catalysis fixation of CO2 are rare. Herein, a typical CO2 reduction addition to trans-stilbene is studied. Through Tafel analyses, the reaction rate-determining step (RDS) is identified as the first step of an anion free radical generation from the substrate, and the reaction order is 0.5.

Selective CO Production by Photoelectrochemical Methane Oxidation on TiO2.

The inertness of the C-H bond in CH4 poses significant challenges to selective CH4 oxidation, which often proceeds all the way to CO2 once activated. Selective oxidation of CH4 to high-value industrial chemicals such as CO or CH3OH remains a challenge. Presently, the main methods to activate CH4 oxidation include thermochemical, electrochemical, and photocatalytic reactions. Of them, photocatalytic reactions hold great promise for practical applications but have been poorly studied. Existing demonstrations of photocatalytic CH4 oxidation exhibit limited control over the product selectivity, with CO2 as the most common product. The yield of CO or other hydrocarbons is too low to be of any practical value. In this work, we show that highly selective production of CO by CH4 oxidation can be achieved by a photoelectrochemical (PEC) approach. Under our experimental conditions, the highest yield for CO production was 81.9%. The substrate we used was TiO2 grown by atomic layer deposition (ALD), which features high concentrations of Ti3+ species. The selectivity toward CO was found to be highly sensitive to the substrate types, with significantly lower yield on P25 or commercial anatase TiO2 substrates. Moreover, our results revealed that the selectivity toward CO also depends on the applied potentials. Based on the experimental results, we proposed a reaction mechanism that involves synergistic effects by adjacent Ti sites on TiO2. Spectroscopic characterization and computational studies provide critical evidence to support the mechanism. Furthermore, the synergistic effect was found to parallel heterogeneous CO2 reduction mechanisms. Our results not only present a new route to selective CH4 oxidation, but also highlight the importance of mechanistic understandings in advancing heterogeneous catalysis.