Chemical Reactions in Imperfect Cavities: Enhancement, Suppression, and Resonance
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Engineering topics
Publications and source records attributed to Wang, Yu.
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Nitrogen (N) is an important contributor in regulating plant growth and development as well as secondary metabolites synthesis, so as to promote the formation of tea quality and flavor. Theanine, polyphenols, and caffeine are important secondary metabolites in tea plant. In this study, the responses of Camellia sinensis roots to N deprivation and resupply were investigated by metabolome and RNA-seq analysis. N deficiency induced content increase for most amino acids (AAs) and reduction for the remaining AAs, polyphenols, and caffeine. After N recovery, the decreased AAs and polyphenols showed a varying degree of recovery in content, but caffeine did not. Meanwhile, theanine increased in content, but its related synthetic genes were down-regulated, probably due to coordination of the whole N starvation regulatory network. Flavonoids-related pathways were relatively active following N stress according to KEGG enrichment analysis. Gene co-expression analysis revealed TCS2 , AMT1;1 , TAT2 , TS , and GOGAT as key genes, and TFs like MYB, bHLH, and NAC were also actively involved in N stress responses in C. sinensis roots. These findings facilitate the understanding of the molecular mechanism of N regulation in tea roots and provide genetic reference for improving N use efficiency in tea plant.
Heterogeneously catalyzed hydroformylation reactions avert the problems of separation in homogeneous reactions, reduce the discharge of phosphorus-containing wastes, and prevent the loss of precious metals. This review summarizes the developments of catalysts for heterogeneous hydroformylation in the last decade and proposes potential modification methods for future improvements. The hydroformylation properties of different reactants are compared in order to emphasize the fact that various olefins face unique challenges. The hydroformylation of ethylene requires the enhancement of catalytic activity and chemoselectivity, whereas that of propylene needs improvements in both chemoselectivity and regioselectivity. The hydroformylation of longer-chain olefins and styrene seeks further improvement in regioselectivity. The catalytic properties of activity, selectivity, and stability can be tuned through electronic effects (bimetallic effects, phosphine ligands, and single-atom catalysts), steric hindrance (encapsulation structures, diphosphine ligands, and local functional groups), and reaction condition optimization (temperature, pressure, and solvents). Furthermore, the understanding of these effects is critical in future catalyst design for heterogeneous hydroformylation reactions.
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This project developed screening tools that enable evaluation of alternative cementitious binders that create concretes to significantly reduce energy and emissions while remaining cost competitive on both initial and long-term costs. The team began with the viewpoint that acceptance of new cementitious binder products has a substantially greater chance of successful implementation when capital investment is not excessive and the end product has customers that have experience and resources to use this. As such, a binder system that is based on portland cement with blended using industrial by-products (alternative cementitious materials) has the potential for dramatic and meaningful impact. The team has focused on developing implementable solutions in specifications and current practice. This however requires three main factors: 1) ability to screen byproducts and alternative materials for success, 2) ability to ‘treat’ materials chemically to enhance kinetics, and 3) ability to provide predictions of performance of both binders and concrete from first principles. The project developed/refined a state of the art and scientifically based screening test for SCM called the pozzolanic reactivity test. The team developed kinetic models to simulate these materials as well as experimental approaches to alter selected reactions. Simulation tools were developed that enable the performance of concrete to be predicted based on the chemistry and reactivity of the cement and alternative SCM. Specifically, this project: • enhanced the kinetic reactivity models for use in multi-scale computational programs that use thermodynamics to predict reaction products. 2 • developed scaling models to extend thermodynamic modeling to link these models with pore structure. This enables strength, transport property, and coupled transport prediction. • developed tools to predict performance of cementitious materials using the pozzolanic reactivity test and chemical composition. The predicted properties are consistent with AASHTO R101 and the CEB-FIP model code and can be measured using associated test procedures. • demonstrated mechanical and fracture based modeling tools that thermodynamic predictions and inputs to predict concrete service life. These results have been used to demonstrate the value of enabling specifications to include ASTM C 595 cement as well ASTM C150 cement. In addition, these products are being used to expedite the evaluation of alternative SCM to aide in determining which materials have potential value and what ‘compositions’ of blended cements merit further investment.
Machine learning (ML) algorithms have been increasingly successful in their applications to solve energy and environmental engineering problems. ML algorithms have the advantage of being able to solve highly nonlinear issues effectively. Furthermore, considering the limited sample size of data collected in energy and environmental engineering, obtaining a ML model with reasonable accuracy is simple. Unfortunately, the vast majority of the current applications of ML algorithms lack effective screening of dominant factors and comprehensive model validation, which weakens the predictive ability of the models. The present study takes the minimum miscible pressure (MMP) of CO 2 - oil systems as an example. It establishes a systematic and robust predictive model to address this issue. Based on 147 sets of slim tube tests, the predictive models of the MMPs are investigated by application of eight ML algorithms. The paper concludes that most of the published ML models in the field of energy and environmental engineering prediction are not reliable. Furthermore, it addresses the main reasons for the poor performance of some predictive models built by ML and provides guidelines on how to make such models robust. Further, to the best of our knowledge, this is the first study to point out the defects of current ML modeling methods and propose countermeasures for their application in energy and environmental engineering problems.
High temperature stress seriously affects the growth of cucumber seedlings, and even leads to a decline in yield and quality. miRNAs have been shown to be involved in regulating the response to stress in plants, but little is known about its effects on cucumber high temperature stress tolerance. Here, we found that high temperature stress induced the expression of miR9748 in cucumber. Overexpression of cucumber miR9748 in Arabidopsis improved high temperature tolerance. Transcriptome analysis revealed that miR9748 might mediate high temperature tolerance through plant hormone signal pathway. 5′ RNA ligase-mediated rapid amplification of cDNA ends (5′ RLM-RACE) and transient transformation technology demonstrated that CsNPF4.4 was the target gene of miR9748. CsNPF4.4 overexpression plants decreased high temperature tolerance accompanied by reducing the content of jasmonic acid (JA), but alleviated by foliar application of methyl jasmonate, indicating that CsNPF4.4 negatively regulated high temperature stress tolerance through inhibition JA signal pathway. Furthermore, high temperature stress also increased the expression level of CsbZIP2 . Yeast one-hybrid and dual-luciferase assays showed that CsbZIP2 directly bound to the promoter of MIR9748 to induce its expression. Taken together, our results indicated that CsbZIP2 directly regulated miR9748 expression to cleave CsNPF4.4 to mediate high temperature tolerance through JA pathway.
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Aim Currently, there is little evidence on the relationship between laughter and the risk of dementia, and since laughter is mainly a social behavior, we aimed to examine the association between various occasions for laughter and the risk of dementia in Japanese older adults. Methods We draw upon 6‐year follow‐up data from the Japan Gerontological Evaluation Study, including 12 165 independent older adults aged 65 years or over. Occasions for laughter were assessed using a questionnaire, while dementia was diagnosed using the standardized dementia scale of the long‐term care insurance system in Japan. Cox proportional hazards models were estimated, yielding hazard ratios and 95% confidence intervals (CIs). Results The multivariable hazard ratio of dementia incidence for all participants in the groups for high versus low variety of occasions for laughter was 0.84 (95% CI: 0.72–0.98, P for trend <0.001). A greater variety of occasions for laughter was associated with a lower risk of dementia 0.78 (95% CI: 0.63–0.96, P for trend <0.001) among women, but was less pronounced for men, with significant associations only for the medium group. Laughing during conversations with friends, communicating with children or grandchildren, and listening to the radio were primarily associated with decreased risk. Conclusion A greater variety of laughter occasions in individual and social settings was associated with a reduced risk of dementia. Geriatr Gerontol Int 2022; 22: 392–398 .
Sr 4 (Ru 0.99 Fe 0.01 ) 3 O 10 shows a ferromagnetic (FM) transition at T C ~ 105 K with the magnetic easy axis in the ab plane, followed by a metamagnetic transition (MMT) at low temperatures when the magnetic field H is applied along the c axis, which is in sharp contrast to that of the pure Sr 4 Ru 3 O 10 , where the easy axis is along the c axis and the MMT is in the ab plane. Here, we studied the MMT in the Sr 4 (Ru 0.99 Fe 0.01 ) 3 O 10 nanosheet by the Hall effect. It was found that the ordinary Hall coefficient of Sr 4 (Ru 0.99 Fe 0.01 ) 3 O 10 is almost the same as that of the pure Sr 4 Ru 3 O 10 , while a sudden increase in the Hall resistance R xy is observed below ~50 K, above which the R xy presents the conventional anomalous Hall effect up to T C . Analysis of the results indicates that the MMT has no direct correlation to the electronic structure but closely relates to the magnetic moment locking, where the magnetic-field-induced breakdown of the locked moments is responsible for the MMT.
Understanding of recently reported putative close-to-room-temperature superconductivity in C-S-H compounds at 267 GPa demands a reproducible synthesis protocol as well as knowledge of the compounds' structure and composition. Here, we synthesized C-S-H compounds with various carbon compositions at high pressures from elemental carbon C and methane CH 4 , sulfur S, and molecular hydrogen H 2 . Here, we focus on compounds synthesized using methane as these allow a straightforward determination of their structure and composition by combining single-crystal x-ray diffraction and Raman spectroscopy. We applied a two-stage synthesis of [(CH 4 ) x (H 2 S) (1-x) ] 2 H 2 compounds with various compositions by first reacting sulfur and mixed methane-hydrogen fluids and forming CH 4 -doped H 2 S crystals at 0.5-3 GPa and then by growing single crystals of the desired hydrogen-rich compound. Raman spectroscopy applied to this material shows the presence of CH 4 molecules incorporated into the lattice and allows the determination of the CH 4 content, while single-crystal x-ray diffraction results suggest that the methane molecules substitute H 2 S molecules. The structural behavior of these compounds is very similar to the previously investigated methane-free crystals demonstrating a transition from Al 2 Cu type I4/mcm molecular crystal to a modulated molecular structure at 20-30 GPa and back to the same basic I4/mcm structure in an extended modification with greatly modified Raman spectra. This latter phase demonstrates a distortion into a Pnma structure at 132-159 GPa and then transforms into a common Im$\bar{3}$m H 3 S phase at higher pressures; however, no structural anomaly is detected near 220 GPa, where a sharp upturn in T c has been reported.
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The past decade has seen significant progress in the field of metabolic engineering and synthetic biology. The exponentially growing multi-omics data and technological advances in the development of efficient genetic manipulation tools and techniques have allowed scientists to explore and expand their understanding of microbial metabolisms and further develop sophisticated engineering strategies to realize the use of industrial "workhorses" and non-conventional microorganisms for sustainable bioconversion and biorefinery. There is of great interest for the research community in using C1 compounds (i.e., CO 2 , CO/syngas, methane, methanol) as the next generation feedstocks for microbial cell factories and biocatalysts to promote the sustainable development of a green economy (Figure 1). Considering lowering input costs is also a main consideration for successful business ventures, the use of inexpensive, abundant, and widely accessible C1 compounds is envisioned as a promising route for the sustainable production of fine chemicals, fuels, and other high-value products. Many C1 compounds are waste gases from industrial activities and may have detrimental effects on climate change upon emission into the atmosphere. Therefore, promoting the use of C1 compounds as renewable carbon feedstocks can greatly contribute to the reduction of anthropogenic emission of air pollutants.
Nanographenes have kindled considerable interest in the fields of materials science and supramolecular chemistry as a result of their unique self-assembling and optoelectronic properties. Encapsulating the contorted nanographenes inside artificial receptors, however, remains challenging. Herein, we report the design and synthesis of a trigonal prismatic hexacationic cage, which has a large cavity and adopts a relatively flexible conformation. It serves as a receptor, not only for planar coronene, but also for contorted nanographene derivatives with diameters of approximately 15 Å and thicknesses of 7 Å. A comprehensive investigation of the host-guest interactions in the solid, solution and gaseous states by experimentation and theoretical calculations reveals collectively an induced-fit binding mechanism with high binding affinities between the cage and the nanographenes. Notably, the photostability of the nanographenes is improved significantly by the ultrafast deactivation of their excited states within the cage. Encapsulating the contorted nanographenes inside the cage provides a noncovalent strategy for regulating their photoreactivity.
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