Polyaniline encapsulated Ti-MOF/CoS for efficient photocatalytic hydrogen evolution

We report the study of conductive polyaniline (PANI) chain embedded Ti-MOF functionalized with CoS as a cocatalyst for hydrogen evolution reaction (HER) application. The post synthetically modified hybrid photocatalyst PANI/Ti-MOF/CoS greatly influences the redox and e^? ? h⁺ separation process and exhibits an impressive rate of HER (～1322 μmol h^?1g^?1), suppressing the pristine Ti-MOF (～62 μmol h^?1g^?1) with apparent quantum yield (AQY) of ～3.2 and transient current response of ～46.4 μA cm^?2. In this system, Ti-MOF provides the circulation of Ti³⁺ and Ti⁴⁺ to the reaction of photocatalytic H₂ generation, where the additional PANI and CoS amended the performance of H₂ production through electron enrichment and thereby improving the stability and integrity of Ti-MOF. The Electrochemical studies demonstrated increased photocurrent by interweaving Ti-MOF crystal with PANI through cation-π interaction thereby enhancing interface connection and then promoting electron transfers. The charge dynamics revealed the initial charge transfer from photoexcited PANI to encapsulated MOF framework to boost the photocatalytic performance of the system. Further, the electron movement at the Ti-MOF/CoS interface is investigated through work function and electrochemical potential of electrons (Fermi level). DFT results demonstrate the importance of CoS in improving the photocatalytic performance of hybrid Ti-MOF catalyst, which leads to superior catalytic behaviour. These results establish that the encapsulation of catalytic active sites inside MOFs with desirable energy band gaps would be an ideal choice for the production of solar fuels.     

IRS辅助的SWIPT系统中基于能效优先的波束成形设计与优化

以智能反射面(intelligent reflecting surface,IRS)辅助的无线携能通信(simultaneous wireless information and power transfer,SWIPT)系统为背景,研究了该系统中基于能效优先的多天线发送端有源波束成形与IRS无源波束成形联合设计与优化方法。以最大化接收端的最小能效为优化目标,构造在发送端功率、接收端能量阈值、IRS相移等多约束下的非线性优化问题,用交替方向乘子法(alternating direction method of multipliers,ADMM)求解。采用Dinkelbach算法转化目标函数,通过奇异值分解(singular value decomposition,SVD)和半定松弛(semi-definite relaxation,SDR)得到发送端有源波束成形向量。采用SDR得到IRS相移矩阵与反射波束成形向量。结果表明,该系统显著降低了系统能量收集(energy harvesting,EH)接收端的能量阈值。当系统总电路功耗为?15 dBm时,所提方案的用户能效为300 KB/J。当IRS反射阵源数与发送天线数均为最大值时,系统可达最大能效。     

Nanoraspberry-like palladium/spongy nickel oxide for electrooxidation of five light fuels

The spongy nickel oxide (SNO) was synthesized the solution combustion method. The SNO was selected as a promoter to boost the catalytic activity of nanoraspberry-like palladium (NRPd) toward electrooxidation of five light fuels (LFs): methanol, ethanol, formaldehyde, formic acid, and ethylene glycol. The X-ray powder diffraction, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy, and field emission scanning electron microscope techniques were used for the materials characterization. In comparison with nonpromoted Pd, the NRPd-SNO electrocatalyst shown an excellent efficiency in parameters like the electrochemical active surface area and anti-CO poisoning behavior. The turnover data and the parameters, including reaction order, activation energy, and the coefficients of electron transfer and diffusion, were evaluated for the each process of LFs electrooxidation. The outcome for NRPd-SNO activity toward LFs electrooxidation was compared to some reported electrodes. The SNO increases the removal of intermediates created in the oxidation of LFs that can poison the surface of palladium catalyst. This is due to the presence of the lattice oxygens in SNO structure and Ni switching between its high and low valances. The compatibility of the adsorption process of LFs on the surface of the NRPd-SNO catalyst with different isotherms was determined by studying the Tafel polarization and calculating the surface coverage.     

Noncentrosymmetric Tetrel Pnictides RuSi4P4 and IrSi3P3: Nonlinear Optical Materials with Outstanding Laser Damage Threshold

Noncentrosymmetric (NCS) tetrel pnictides have recently generated interest as nonlinear optical (NLO) materials due to their second harmonic generation (SHG) activity and large laser damage threshold (LDT). Herein nonmetal-rich silicon phosphides RuSi₄P₄ and IrSi₃P₃ are synthesized and characterized. Their crystal structures are reinvestigated using single crystal X-ray diffraction and ²⁹Si and ³¹P magic angle spinning NMR. In agreement with previous report RuSi₄P₄ crystallizes in NCS space group P1, while IrSi₃P₃ is found to crystallize in NCS space group Cm, in contrast with the previously reported space group C2. A combination of DFT calculations and diffuse reflectance measurements reveals RuSi₄P₄ and IrSi₃P₃ to be wide bandgap (E_g) semiconductors, E_g = 1.9 and 1.8 eV, respectively. RuSi₄P₄ and IrSi₃P₃ outperform the current state-of-the-art infrared SHG material, AgGaS₂, both in SHG activity and laser inducer damage threshold. Due to the combination of high thermal stabilities (up to 1373 K), wide bandgaps (≈2 eV), NCS crystal structures, strong SHG responses, and large LDT values, RuSi₄P₄ and IrSi₃P₃ are promising candidates for longer wavelength NLO materials.     

Systemic Inflammation and the Breakdown of Intestinal Homeostasis Are Key Events in Chronic Spinal Cord Injury Patients

Our aim was to investigate the subset distribution and function of circulating monocytes, proinflammatory cytokine levels, gut barrier damage, and bacterial translocation in chronic spinal cord injury (SCI) patients. Thus, 56 SCI patients and 28 healthy donors were studied. The levels of circulating CD14^+highCD16⁻, CD14^+highCD16⁺, and CD14^+lowCD16⁺ monocytes, membrane TLR2, TLR4, and TLR9, phagocytic activity, ROS generation, and intracytoplasmic TNF-α, IL-1, IL-6, and IL-10 after lipopolysaccharide (LPS) stimulation were analyzed by polychromatic flow cytometry. Serum TNF-α, IL-1, IL-6 and IL-10 levels were measured by Luminex and LPS-binding protein (LBP), intestinal fatty acid-binding protein (I-FABP) and zonulin by ELISA. SCI patients had normal monocyte counts and subset distribution. CD14^+highCD16⁻ and CD14^+highCD16⁺ monocytes exhibited decreased TLR4, normal TLR2 and increased TLR9 expression. CD14^+highCD16⁻ monocytes had increased LPS-induced TNF-α but normal IL-1, IL-6, and IL-10 production. Monocytes exhibited defective phagocytosis but normal ROS production. Patients had enhanced serum TNF-α and IL-6 levels, normal IL-1 and IL-10 levels, and increased circulating LBP, I-FABP, and zonulin levels. Chronic SCI patients displayed impaired circulating monocyte function. These patients exhibited a systemic proinflammatory state characterized by enhanced serum TNF-α and IL-6 levels. These patients also had increased bacterial translocation and gut barrier damage.     

Surface Reconstruction Engineering with Synergistic Effect of Mixed-Salt Passivation Treatment toward Efficient and Stable Perovskite Solar Cells

Surface passivation treatment is a widely used strategy to resolve trap-mediated nonradiative recombination toward high-efficiency metal-halide perovskite photovoltaics. However, a lack of passivation with mixture treatment has been investigated, as well as an in-depth understanding of its passivation mechanism. Here, a systematic study on a mixed-salt passivation strategy of formamidinium bromide (FABr) coupled with different F-substituted alkyl lengths of ammonium iodide is demonstrated. It is obtained better device performance with decreasing chain length of the F-substituted alkyl ammonium iodide in the presence of FABr. Moreover, they unraveled a synergistic passivation mechanism of the mixed-salt treatment through surface reconstruction engineering, where FABr dominates the reformation of the perovskite surface via reacting with the excess PbI₂. Meanwhile, ammonium iodide passivates the perovskite grain boundaries both on the surface and top perovskite bulk through penetration. This synergistic passivation engineer results in a high-quality perovskite surface with fewer defects and suppressed ion migration, leading to a champion efficiency of 23.5% with mixed-salt treatment. In addition, the introduction of the moisture resisted F-substituted groups presents a more hydrophobic perovskite surface, thus enabling the decorated devices with excellent long-term stability under a high humid atmosphere as well as operational conditions.     

Effect of cooking temperature on texture and flavour binding of braised sauce porcine skin

To investigate the effect of cooking temperature (55, 65, 75, 85 and 95 °C) on texture and flavour binding of braised sauce porcine skin (BSPS), sensory acceptance, microstructure and flavour-binding capacity were investigated during the processing of BSPS. Samples cooked at 85 and 95 °C showed better texture and aroma scores. Hardness and chewiness of BSPS were obviously improved at 85 and 95 °C than control group. Collagen structure was significantly destroyed over 85 °C. The porcine skin collagen heated at 85 and 95 °C showed relatively higher flavour-binding capacity than other samples. The improvement of texture of BSPS was mainly attributed to the degradation of collagen. Higher aroma scores of BSPS were related to intense binding abilities with aroma compounds at 85 and 95 °C. Cooking at 85 or 95 °C could be an optimal cooking temperature for BSPS.     

Centimeter-scale low-damage micromachining on single-crystal 4H–SiC substrates using a femtosecond laser with square-shaped Flat-Top focus spots

Femtosecond (fs) lasers have been proved to be reliable tools for high-precision and high-quality micromachining of ceramic materials. Nevertheless, fs laser processing using a single-mode beam with a Gaussian intensity distribution is difficult to obtain large-area flat and uniform processed surfaces. In this study, we utilize a customized diffractive optical element (DOE) to redistribute the laser pulse energy from Gaussian to square-shaped Flat-Top profile to realize centimeter-scale low-damage micromachining on single-crystal 4H–SiC substrates. We systematically investigated the effects of processing parameters on the changes in surface morphology and composition, and an optimal processing strategy was provided. Mechanisms of the formation of surface nanoparticles and the removal of surface micro-burrs were discussed. We also examined the distribution of subsurface defects caused by fs laser processing by removing a thin surface layer with a certain depth through chemical mechanical polishing (CMP). Our results show that laser-induced periodic surface structures (LIPSSs) covered by fine SiO₂ nanoparticles form on the fs laser-processed areas. Under optimal parameters, the redeposition of SiO₂ nanoparticles can be minimized, and the surface roughness Sa of processed areas reaches 120 ± 8 nm after the removal of a 10 μm thick surface layer. After the laser processing, micro-burrs on original surfaces are effectively removed, and thus the average profile roughness Rz of 2 mm long surface profiles decreases from 920 ± 120 nm to 286 ± 90 nm. No visible micro-pits can be found after removing ~1 μm thick surface layer from the laser-processed substrates.     

Prediction of Chameleonic Efficiency

Chameleonic properties, i. e., the capacity of a molecule to hide polarity in non-polar environments and expose it in water, help achieving sufficient permeability and solubility for drug molecules with high MW. We present models of experimental measures of polarity for a set of 24 FDA approved drugs (MW 405-1113) and one PROTAC (MW 1034). Conformational ensembles in aqueous and non-polar environments were generated using molecular dynamics. A linear regression model that predicts chromatographic apparent polarity (EPSA) with a mean unsigned error of 10 Ų was derived based on separate terms for donor, acceptor, and total molecular SASA. A good correlation (R²=0.92) with an experimental measure of hydrogen bond donor potential, Δlog P_oct-tol, was found for the mean hydrogen bond donor SASA of the conformational ensemble scaled with Abraham's A hydrogen bond acidity. Two quantitative measures of chameleonic behaviour, the chameleonic efficiency indices, are introduced. We envision that the methods presented herein will be useful to triage designed molecules and prioritize those with the best chance of achieving acceptable permeability and solubility.     

The Age-Sensitive Efficacy of Calorie Restriction on Mitochondrial Biogenesis and mtDNA Damage in Rat Liver

Calorie restriction (CR) is the most efficacious treatment to delay the onset of age-related changes such as mitochondrial dysfunction. However, the sensitivity of mitochondrial markers to CR and the age-related boundaries of CR efficacy are not fully elucidated. We used liver samples from ad libitum-fed (AL) rats divided in: 18-month-old (AL-18), 28-month-old (AL-28), and 32-month-old (AL-32) groups, and from CR-treated (CR) 28-month-old (CR-28) and 32-month-old (CR-32) counterparts to assay the effect of CR on several mitochondrial markers. The age-related decreases in citrate synthase activity, in TFAM, MFN2, and DRP1 protein amounts and in the mtDNA content in the AL-28 group were prevented in CR-28 counterparts. Accordingly, CR reduced oxidative mtDNA damage assessed through the incidence of oxidized purines at specific mtDNA regions in CR-28 animals. These findings support the anti-aging effect of CR up to 28 months. Conversely, the protein amounts of LonP1, Cyt c, OGG1, and APE1 and the 4.8 Kb mtDNA deletion content were not affected in CR-28 rats. The absence of significant differences between the AL-32 values and the CR-32 counterparts suggests an age-related boundary of CR efficacy at this age. However, this only partially curtails the CR benefits in counteracting the generalized aging decline and the related mitochondrial involvement.