Unravel the regulatory mechanism of Yrr1p phosphorylation in response to vanillin stress in Saccharomyces cerevisiae.

Improving the resistance of Saccharomyces cerevisiae to vanillin, derived from lignin, will benefit the design of robust cell factories for lignocellulosic biorefining. The transcription factor Yrr1p mediates S. cerevisiae resistance to various compounds. In this study, eleven predicted phosphorylation sites were mutated, among which 4 mutants of Yrr1p, Y134A/E and T185A/E could improve vanillin resistance. Both dephosphorylated and phosphorylated mutations at Yrr1p 134 and 185 gathered in the nucleus regardless of the presence or absence of vanillin. However, the phosphorylated mutant Yrr1p inhibited target gene expression, while dephosphorylated mutants promoted expression. Transcriptomic analysis showed that the dephosphorylated Yrr1p T185 mutant, under vanillin stress, upregulated ribosome biogenesis and rRNA processing. These results demonstrate the mechanism by which Yrr1p phosphorylation regulates the expression of target genes. The identification of key phosphorylation sites in Yrr1p offers novel targets for the rational construction of Yrr1p mutants to improve resistance to other compounds.

Exploring the Dehydrogenation Reaction Pathway of Perhydro-Polycyclic Aromatic Hydrocarbons over the Pt/Al2O3 Catalyst as Liquid Organic Hydrogen Carriers by In Situ DRIFT.

Polycyclic aromatic hydrocarbons (PAHs) have been paid more attention as liquid organic hydrogen carriers (LOHCs) because of their high hydrogen storage, easy transportation, low price, and other advantages. Dehydrogenation is the key point of the PAH hydrogen storage. However, the dehydrogenation reaction rate of perhydro-PAHs is slow, and their pathway is still not clear. To clarify the PAH dehydrogenation pathway, three kinds of perhydro-PAHs containing six-membered rings (methylcyclohexane, perhydro-diphenylmethane, and perhydro-dibenzyltoluene) are selected, and their dehydrogenation processes over the Pt/Al2O3 catalyst are carried out by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFT). It was found that the dehydrogenation in the six-membered ring started in the para position of the -CH3 group, and then, the six-membered ring was transformed into a benzene ring gradually. Between the six-membered rings, dehydrogenation started from the side ring, which has fewer groups.

Proteomic analysis revealed the roles of YRR1 deletion in enhancing the vanillin resistance of Saccharomyces cerevisiae.

BACKGROUND: Vanillin is one of the important phenolic inhibitors in Saccharomyces cerevisiae for bioconversion of lignocellulosic materials and has been reported to inhibit the translation process in cells. In our previous studies, it was confirmed that the deletion of the transcription factor gene YRR1 enhanced vanillin resistance by promoting some translation-related processes at the transcription level. In this work, we investigated the effects of proteomic changes upon induction of vanillin stress and deletion of YRR1 to provide unique perspectives from a transcriptome analysis for comprehending the mechanisms of YRR1 deletion in the protective response of yeast to vanillin. RESULTS: In wild-type cells, vanillin reduced two dozens of ribosomal proteins contents while upregulated proteins involved in glycolysis, oxidative phosphorylation, and the pentose phosphate pathway in cells. The ratios of NADPH/NADP+ and NADH/NAD+ were increased when cells responded to vanillin stress. The differentially expressed proteins perturbed by YRR1 deletion were much more abundant than and showed no overlaps with transcriptome changes, indicating that Yrr1 affects the synthesis of certain proteins. Forty-eight of 112 upregulated proteins were involved in the stress response, translational and transcriptional regulation. YRR1 deletion increased the expression of HAA1-encoding transcriptional activator, TMA17-encoding proteasome assembly chaperone and MBF1-encoding coactivator at the protein level, as confirmed by ELISA. Cultivation data showed that the overexpression of HAA1 and TMA17 enhanced resistance to vanillin in S. cerevisiae. CONCLUSIONS: Cells conserve energy by decreasing the content of ribosomal proteins, producing more energy and NAD(P)H for survival in response to vanillin stress. Yrr1 improved vanillin resistance by increasing the protein quantities of Haa1, Tma17 and Mbf1. These results showed the response of S. cerevisiae to vanillin and how YRR1 deletion increases vanillin resistance at the protein level. These findings may advance our knowledge of how YRR1 deletion protects yeast from vanillin stress and offer novel targets for genetic engineering of designing inhibitor-resistant ethanologenic yeast strains.

Few-Layer Boron Nitride with Engineered Nitrogen Vacancies for Promoting Conversion of Polysulfide as a Cathode Matrix for Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have become one of the most promising candidates as next-generation batteries, owing to their high specific capacity, low cost, and environmental benignity. Although many strategies have been proposed to restrain the shuttle of lithium polysulfides (LiPSs) through physical trapping and chemical binding, the sluggish kinetics of PS conversion still degrade the capacity, rate, and cycling performance of Li-S batteries. Herein, a novel kind of few-layer BN with engineered nitrogen vacancies (v-BN) has been developed as a cathode matrix for Li-S batteries. The positive vacancies in the BN nanosheets not only promote the immobilization and conversion of LiPSs, but also accelerate the lithium ion diffusion in cathode electrodes. Compared with pristine BN, the v-BN cathodes exhibit higher initial capacities from 775 mA h g-1 to 1262 mA h g-1 at 0.1 C and a high average coulombic efficiency of over 98 % during 150 cycles. Upon increasing the current density to 1 C, the cell still preserves a capacity of 406 mA h g-1 after 500 cycles, exhibiting a capacity decay of only 0.084 % per cycle. The new vacancy-engineered material provides a promising method for achieving excellent performance in Li-S batteries.

Bimetallic Rh-Fe catalysts for N2O decomposition: effects of surface structures on catalytic activity.

Well-homogenized RhFe alloy nanoparticles and core-shell structured Fe@Rh nanoparticles were highly dispersed on SBA-15 and then applied to N2O catalytic conversion. Compared to RhFe/SBA-15, Fe@Rh/SBA-15 showed a higher catalytic activity for N2O decomposition. This is because the Rh layers covering the Fe core were able to protect against oxidization and so Fe@Rh/SBA-15 was prevented from deactivating. DFT calculations were performed to study the reaction mechanism of N2O decomposition. The rate-determining step, which was found to be the formation of O2 from adsorbed oxygen atoms on the surfaces of RhFe and Fe@Rh, revealed that O atoms prefer to be adsorbed on exposed Fe atoms on the surface of RhFe rather than that of Fe@Rh. The calculation results indicate that the exposed Fe atoms tend to be oxidized on the surface of RhFe, resulting in the deactivation of RhFe/SBA-15 during the experiment.

Graphene-Analogues Boron Nitride Nanosheets Confining Ionic Liquids: A High-Performance Quasi-Liquid Solid Electrolyte.

Solid electrolytes are one of the most promising electrolyte systems for safe lithium batteries, but the low ionic conductivity of these electrolytes seriously hinders the development of efficient lithium batteries. Here, a novel class of graphene-analogues boron nitride (g-BN) nanosheets confining an ultrahigh concentration of ionic liquids (ILs) in an interlayer and out-of-layer chamber to give rise to a quasi-liquid solid electrolyte (QLSE) is reported. The electron-insulated g-BN nanosheet host with a large specific surface area can confine ILs as much as 10 times of the host's weight to afford high ionic conductivity (3.85 × 10(-3) S cm(-1) at 25 °C, even 2.32 × 10(-4) S cm(-1) at -20 °C), which is close to that of the corresponding bulk IL electrolytes. The high ionic conductivity of QLSE is attributed to the enormous absorption for ILs and the confining effect of g-BN to form the ordered lithium ion transport channels in an interlayer and out-of-layer of g-BN. Furthermore, the electrolyte displays outstanding electrochemical properties and battery performance. In principle, this work enables a wider tunability, further opening up a new field for the fabrication of the next-generation QLSE based on layered nanomaterials in energy conversion devices.

A novel Ni-WC/AC catalyst with enhanced electroactivity for glucose oxidation.

WC-doped Ni over an active carbon catalyst (Ni-WC/AC), prepared by incipient wetness impregnation, is proposed as an anode for the amplified electrochemical oxidation of glucose in 0.1 M KOH solution. Cyclic voltammetry and morphology characterizations were used to explore these electrocatalysts. It was found that Ni-WC/AC catalysts were nanoparticles with a diameter of 10 nm and the 20%wtNi-20%wtWC/AC catalyst showed superior electrocatalytic activity toward glucose oxidation. The extraordinary activity obtained at the 20%wtNi-20%wtWC/AC modified glass carbon electrode (GCE) is attributed to the synergistic effect between Ni and WC toward glucose electroxidation.

Manifold Learning-Based Common Spatial Pattern for EEG Signal Classification.

EEG signal classification using Riemannian manifolds has shown great potential. However, the huge computational cost associated with Riemannian metrics poses challenges for applying Riemannian methods, particularly in high-dimensional feature data. To address these, we propose an efficient ensemble method called MLCSP-TSE-MLP, which aims to reduce the computational cost while achieving superior performance. MLCSP of the ensemble utilizes a Riemannian graph embedding strategy to learn intrinsic low-dimensional sub-manifolds, enhancing discrimination. TSE uses the Euclidean mean as the reference point for tangent space mapping and reducing computational cost. Finally, the ensemble incorporates the MLP classifier to offer improved classification performance. Classification results conducted on three datasets demonstrate that MLCSP-TSE-MLP achieves significant superior performance compared to various competing methods. Notably, the MLCSP-TSE module achieves a remarkable increase in training speed and exhibits much lower test time compared to traditional Riemannian methods. Based on these results, we believe that the proposed MLCSP-TSE-MLP is a powerful tool for handling high-dimensional data and holds great potential for practical applications.

Catalytic Fast Pyrolysis of Tar-Rich Coal with a Bauxite Residue for Upgrading High-Value Products: Product Distribution and Kinetic Analysis.

Fast pyrolysis technology can reduce the secondary reactions, improve the volatile product yield, and reduce the semicoke yield. Still, the high proportion of heavy tar components affects the development of fast pyrolysis industrialization. Therefore, this paper put forward a catalytic upgrading method of coal based on the solid waste bauxite residue (BR) as a catalyst. This study investigated the impact of varying particle sizes of pulverized coal and the addition of the BR catalyst on the product distribution and kinetics of coal fast pyrolysis. The results found that the tar yield was the highest at 600 °C when the particle size of pulverized coal was 75-150 µm, which was 19.44%. In the range of 550-650 °C, the relative content of benzene and toluene xylene (BTX) in liquid products increased with the temperature. With the increase of the proportion of the BR catalyst, the yield of semicoke in coal pyrolysis products increased, the yield of the gas phase also increased, and the yield of the liquid phase decreased.

Autophagy and Inflammation: Regulatory Roles in Viral Infections.

Autophagy is a highly conserved intracellular degradation pathway in eukaryotic organisms, playing an adaptive role in various pathophysiological processes throughout evolution. Inflammation is the immune system's response to external stimuli and tissue damage. However, persistent inflammatory reactions can lead to a range of inflammatory diseases and cancers. The interaction between autophagy and inflammation is particularly evident during viral infections. As a crucial regulator of inflammation, autophagy can either promote or inhibit the occurrence of inflammatory responses. In turn, inflammation can establish negative feedback loops by modulating autophagy to suppress excessive inflammatory reactions. This interaction is pivotal in the pathogenesis of viral diseases. Therefore, elucidating the regulatory roles of autophagy and inflammation in viral infections will significantly enhance our understanding of the mechanisms underlying related diseases. Furthermore, it will provide new insights and theoretical foundations for disease prevention, treatment, and drug development.

Thermodynamic Analysis on In Situ Underground Pyrolysis of Tar-Rich Coal: Secondary Reactions.

To develop the in situ underground pyrolysis process of tar-rich coal more scientifically, the effect of temperature and pressure on the distribution of pyrolysis products should be clarified. This paper selected the typical components in five distillates of light tar, phenol tar, naphthalene tar, washing tar, and anthracene tar as the main reaction products. 32 typical secondary reactions were constructed. Based on the thermodynamic analysis strategy, the variation of the Gibbs free energy and equilibrium constant of secondary reactions was investigated. The results showed that pressure mainly affected the reaction characteristics of molecule-increasing reactions. The Gibbs free energy value of the molecule-increasing reactions increased with increasing pressure. The trend that the reaction could proceed spontaneously gradually weakened. The initial temperature of some reactions that could proceed spontaneously would need to increase by dozens or even hundreds of degrees. Due to the influence of formation pressure, the generation of related components of light tar, naphthalene tar, washing tar, and anthracene tar would be inhibited to varying degrees in the in situ underground pyrolysis process. The secondary reactions related to phenol tar were equimolecular reactions, which were almost unaffected by stratal pressure. Axial pressure and confining pressure of different coal seam depths should be considered in the process of in situ underground pyrolysis.

Thermodynamic Analysis of In Situ Underground Pyrolysis of Tar-Rich Coal: Primary Reactions.

In situ underground pyrolysis of tar-rich coal is significant for alleviating the scarcity of oil and gas resources and realizing the green and efficient development and utilization of coal in China. Tar-rich coal is often subjected to high axial pressure, surrounding pressure, and pore pressure in the in situ underground pyrolysis environment. Consequently, laboratory simulation conditions are difficult to meet the actual needs. This paper conducts a thermodynamic study of the pyrolysis characteristics of tar-rich coal under an in situ environment. Typical thermodynamic functions of tar-rich coal, including the standard enthalpy of formation, standard formation Gibbs free energy, and standard entropy, were determined. Ten representative primary reactions were constructed with typical tar-rich coal pyrolysis oil components as a guide. The Gibbs free energy and equilibrium constant change laws of the above reactions were analyzed for pyrolysis temperatures from 200 to 800 °C and pyrolysis pressures from atmospheric pressure to 10 MPa. The results showed that the standard enthalpy of formation of tar-rich coal was -72.27 kJ·mol-1, the standard entropy was -37.79 J·mol-1·K-1, and the standard formation Gibbs free energy was -60.01 kJ·mol-1. When the reaction pressure increased from atmospheric pressure to 10 MPa, the thermodynamically feasible initial temperature fractions of the primary reaction of tar-rich coal pyrolysis all showed different degrees of increase. In the underground environment, the initial temperature of the primary reaction of in situ underground pyrolysis of tar-rich coal moves to a higher-temperature gradient to some extent, so the adjustment of the reaction temperature and pressure could guide the directional regulation of the in situ underground pyrolysis products of tar-rich coal.

Kinetics for the hydrogen-abstraction of CH4 with NO2.

The detailed mechanism of the NO(2)+CH(4) reaction has been computationally investigated at the M06-2X/MG3S, B3LYP/6-311G(2d,d,p), and MP2/6-311+G(2df,p) levels. The direct dynamics calculations were preformed using canonical transition state theory with tunneling correction and scaled generalized normal-mode frequencies including anharmonic torsion. The calculated results indicate that the NO(2)+CH(4) reaction proceeds by three distinct channels simultaneously, leading to the formation of trans-HONO (1a), cis-HONO (1b), and HNO(2) (1c), and each channel involves the formation of intermediate having lower energy than the final product. The anti-Hammond behavior observed in channel 1a is well analyzed. Proper treatment of anharmonic torsions about the C···H···O (or N) axis in the transition structures greatly improves the accuracy of kinetics predictions. The activation energy for each channel increases substantially with temperature, but is not strictly a linear function of temperature. Therefore, the thermal rate constants are fitted to the four-parameter expression recommended for this case over the wide temperature range 400-4000 K.

Capture Hi-C reveals the influence on dynamic three-dimensional chromosome organization perturbed by genetic variation or vanillin stress in Saccharomyces cerevisiae.

Studying the mechanisms of resistance to vanillin in microorganisms, which is derived from lignin and blocks a major pathway of DNA double-strand break repair in yeast, will benefit the design of robust cell factories that produce biofuels and chemicals using lignocellulosic materials. A high vanillin-tolerant Saccharomyces cerevisiae strain EMV-8 carrying site mutations compared to its parent strain NAN-27 was selected for the analyses. The dynamics of the chromatin structure of eukaryotic cells play a critical role in transcription and the regulation of gene expression and thus the phenotype. Consequently, Hi-C and transcriptome analyses were conducted in EMV-8 and NAN-27 in the log phase with or without vanillin stress to determine the effects of mutations and vanillin disturbance on the dynamics of three-dimensional chromosome organization and the influence of the organization on the transcriptome. The outcomes indicated that the chromosome interaction pattern disturbed by vanillin stress or genetic mutations in the log phase was similar to that in mouse cells. The short chromosomes contact the short chromosomes, and the long chromosomes contact the long chromosomes. In response to vanillin stress, the boundaries of the topologically associating domain (TAD) in the vanillin-tolerant strain EMV-8 were more stable than those in its parent strain NAN-27. The motifs of SFL1, STB3, and NHP6A/B were enriched at TAD boundaries in both EMV-8 and NAN-27 with or without vanillin, indicating that these four genes were probably related to TAD formation. The Indel mutation of YRR1, whose absence was confirmed to benefit vanillin tolerance in EMV-8, caused two new interaction sites that contained three genes, WTM2, PUP1, and ALE1, whose overexpression did not affect vanillin resistance in yeast. Overall, our results revealed that in the log phase, genetic mutations and vanillin disturbance have a negligible effect on three-dimensional chromosome organization, and the reformation or disappearance of TAD boundaries did not show an association with gene expression, which provides an example for studying yeast chromatin structure during stress tolerance using Hi-C technology.

Zwitterionic Covalent Organic Frameworks: Attractive Porous Host for Gas Separation and Anhydrous Proton Conduction.

Ionic covalent organic frameworks (COFs) consisting of an anionic or cationic skeleton and corresponding counterions have demonstrated great potential in many application fields such as ion conduction, molecular separation, and catalysis. However, arranging anionic and cationic groups into the same COF to form zwitterionic materials is still unexplored. Herein we design the synthesis of three zwitterionic COFs as attractive porous hosts for SO2/CO2 separation and anhydrous proton conduction. The separated cationic and anionic groups in zwitterionic COFs' channels can act as two different polar sites for SO2 adsorption, allowing zwitterionic COFs to achieve a high SO2 adsorption capacity (216 mL/g, 298 K) and impressive SO2/CO2 selectivity (118, 298 K). Furthermore, after loading with triazole/imidazole, the zwitterionic groups in COFs' channels can induce complete proton carrier deprotonation, producing more freely migrating protons. The free protons migrate along a continuous hydrogen-bonding network in zwitterionic COFs' channels, leading to outstanding anhydrous proton conductivity up to 4.38 × 10-2 S/cm, which is much higher than other N-heterocyclic-doped porous materials under anhydrous conditions. Proton dissociation energy calculations combined with frequency-dependent dielectric analysis give insight into the role of zwitterionic COFs for proton conductivity. Our work provides the possibility to design well-defined zwitterionic frameworks for gas separation and ion conduction.

Kinetics of liquid phase catalytic hydrogenation of dicyclopentadiene over Pd/C catalyst.

To investigate the kinetics behaviors of dicyclopentadiene hydrogenation, a series of experiments were performed at different temperatures (323-353 K) under varying hydrogen pressure (0.5-1.5 MPa) with a range of Pd/C catalyst loading (0.25-1.00 wt %) using ethanol as solvent in a batch reactor. The time dependent concentration variations for each component were traced under the conditions of removing both the internal and external diffusion effects. The Langmuir-Hinshelwood mechanism was proposed with the consideration of the noncompetitive adsorption between the organic species with hydrogen, and the surface reaction was the rate-determining step. The kinetic equations for the sequence reaction were derived on the basis of the analysis of mechanisms, and the model parameters were determined by fitting the experimental data in differential temperature using the method of Runge-Kutta. The reaction activation energies for the first and second steps are 3.19 and 31.69 kJ x mol(-1), respectively, and the reliability of the model was verified by these experimental results to change hydrogen pressure, reactant concentration and catalyst loading. The simulation results agreed well with the experimental data.

Co-pyrolysis behavior of microalgae biomass and low-rank coal: Kinetic analysis of the main volatile products.

This work studied the kinetic characteristics of volatile products from co-pyrolysis of microalgae and low-rank coal. Iso-conversional method was applied to calculate the reaction order, activation energy and pre-exponential factor of gaseous products (H2, CO, CH4, and CO2) and benzene. The results indicated the activation energy of H2 generating from both individual and mixing samples was the highest, meaning H2 was the hardest to generate during the pyrolysis process. The values of activation energy from the formation of CO and benzene from low-rank coal and green algae were 31.11, 32.44, 18.21 and 24.31 kJ·mol-1, respectively. The formation of benzene and CO were easier than other volatile products due to the lower activation energy. Synergistic effects were observed from the formation of CO2, the addition of green algae decreased the activation energy. The order of the activation energy was in agreement with that of the releasing sequence of main volatile products.

Enhanced Cycling Performance for Lithium-Sulfur Batteries by a Laminated 2D g-C3 N4 /Graphene Cathode Interlayer.

Decay in electrochemical performance resulting from the "shuttle effect" of dissolved lithium polysulfides is one of the biggest obstacles for the realization of practical applications of lithium-sulfur (Li-S) batteries. To meet this challenge, a 2D g-C3 N4 /graphene sheet composite (g-C3 N4 /GS) was fabricated as an interlayer for a sulfur/carbon (S/KB) cathode. It forms a laminated structure of channels to trap polysulfides by physical and chemical interactions. The thin g-C3 N4 /GS interlayer significantly suppresses diffusion of the dissolved polysulfide species (Li2 Sx ; 2

High-Charge Density Polymerized Ionic Networks Boosting High Ionic Conductivity as Quasi-Solid Electrolytes for High-Voltage Batteries.

Solid-state electrolytes are actively sought for their potential application in energy storage devices, especially lithium metal rechargeable batteries. However, one of the key challenges in the development of solid-state electrolytes is their lower ionic conductivity compared with that of liquid electrolytes (10-2 S cm-1 at room temperature), where a large gap still exists. Therefore, the pursuit of high ionic conductivity equal to that of liquid electrolytes remains the main objective for the design of solid-state electrolytes. Here, we show a series of high-charge density polymerized ionic networks as solid-state electrolytes that take inspiration from poly(ionic liquid)s. The obtained quasi-solid electrolyte slice displays an astonishingly high ionic conductivity of 5.89 × 10-3 S cm-1 at 25 °C (the highest conductivity among those of the state-of-art polymer gel electrolytes and polymer solid electrolytes) and ultrahigh decomposition potential, >5.2 V versus Li/Li+, which are attributed to the continuous ion transport channel formed by an ultrahigh ion density and an enhanced chemical stability endowed by highly cross-linked networks. The Li/LiFePO4 and Li/LiCoO2 batteries (3.0-4.4 V) assembled with the solid electrolytes show high stable capacities of around 155 and 130 mAh g-1, respectively. In principle, our work breaks new ground for the design and fabrication of the solid-state electrolytes in various energy conversion devices.

Hexaaqua-(5,7-dihydr-oxy-4-oxo-2-phenyl-4H-chromene-8-sulfonato)calcium(II) 5,7-dihydr-oxy-4-oxo-2-phenyl-4H-chromene-8-sulfonate trihydrate.

In the title compound, [Ca(C(15)H(9)O(7)S)(H(2)O)(6)](C(15)H(9)O(7)S)·3H(2)O, the Ca centre has a distorted deca-hedral geometry, coordinated by six O atoms from water mol-ecules and one sulfonate O atom. The crystal structure is stabilized by aromatic π-π inter-actions, with centroid-centroid distances of 3.765 (5) and 3.896 (5) Šbetween the phenyl ring and the benzene ring of the chromene unit of neighbouring mol-ecules. In addition, the stacked mol-ecules exhibit inter- and intra-molecular O-H⋯O hydrogen bonds, including the uncoordinated water mol-ecules.