Enhanced photoreactivity of MOFs by intercalating interlayer bands via simultaneous ?NCO and ?SCu modification

Herein, we propose a novel method to enhance the photoreactivity of an MOF catalyst by grafting isocyanate bonds ( NCO) and sulfhydryl-complexed copper ( SCu) onto ZIF-8 (NIF-SCu). The grafting process intercalated interlayer bands between the conduction and valence bands of ZIF-8, thereby providing a “ladder” for facile electron transition. The extreme improvement in the photoreactivity of NIF-SCu could be attributed to the enhancement in light responses in the range of 350–450 nm by  NCO groups and the widening of the visible light range of the MOF by  SCu groups. The formation of staggered energy levels in NIF-SCu could also narrow the band gap, lower the resistance, and facilitate the transfer of photogenerated carriers, thereby generating electrons with strong reduction potential in the  SCu conduction band. This study provides a new strategy for improving or even endowing the photoactivity of environmental functional materials with wide bandgaps.     

Indirect charge transfer of holes via surface states in ZnO nanowires for photoelectrocatalytic applications

In this work, ZnO nanowires with high aspect ratio were obtained by fast and simple electrochemical anodization. Morphological, structural and photoelectrochemical characteristics of the synthesized ZnO nanowires were evaluated by using different techniques: field emission scanning electron microscopy, atomic force microscopy, high resolution transmission electron microscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV–VIS spectroscopy, Mott-Schottky analysis and photoelectrochemical impedance spectroscopy. The synthesized ZnO nanowires presented high roughness and high crystallinity. Besides, surface defects were identified in the sample. The value of the donor density (N_D) was in the order of 10¹⁹ cm^?3 in the dark and 10²⁰ cm^?3 under illumination. In addition, the ZnO nanowires presented good photosensibility, with a photocurrent density response 85 times higher than a ZnO compact layer, and lower resistance to charge transfer. The charge transfer processes taking place at the ZnO/electrolyte interface were studied, since these processes strongly influence the photoelectrocatalytic efficiency of the material. According to the results, the charge transfer of holes in the synthesized ZnO nanowires occurs indirectly via surface states. In this regard, surface states may be an important feature for photoelectrocatalytic applications since they could provide lower onset voltages and higher anodic current densities.     

氮杂环卡宾-钯功能化的配位聚合物（NHC-Pd@Zn-L）：合成、表征及催化Suzuki-Miyaura交叉偶联反应

以\mathrm{1,3}-二(1-羧乙基)咪唑盐(HL)和Zn(NO₃)₂·6H₂O反应合成二维配位聚合物[Zn(L)₂] _n (Zn-L)，产物再与K₂PdCl₄在四氢呋喃溶液中反应引入氮杂环卡宾-钯（NHC-Pd）催化位点，制得催化剂NHC-Pd@Zn-L，并通过PXRD、TGA、ICP、SEM、EDS和XPS进行表征。结果表明，NHC-Pd@Zn-L具有良好的热稳定性且修饰后晶体的框架结构没有发生变化，Pd以NHC-Pd的形式结合在Zn-L中，并均匀分散在配位聚合物中。将NHC-Pd@Zn-L用于催化Suzuki-Miyaura交叉偶联反应，当以苯硼酸和溴苯为底物，催化剂用量为15 mg，乙醇为溶剂，碳酸钾为碱的条件下60℃反应6 h，产率达到>99%，而且催化剂易于回收并可循环使用3次。     

Dual functions of three-dimensional hierarchical architecture on improving the rate capability and cycle performance of LiNi0.8Co0.1Mn0.1O2 cathode material for lithium-ion battery

The main obstacles in lithium-ion battery are limited by rate performance and the rapid capacity fading of LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811). Herein, a novel three-dimensional (3D) hierarchical coating material has been fabricated by in situ growing carbon nanotubes (CNTs) on the surfaces of Ni–Al double oxide (Ni–Al-LDO) sheets (named as LDO&CNT) with Ni–Al double hydroxide (Ni–Al-LDH) as both the substrate and catalyst precursor. The resultant LDO&CNT nanocomposites are uniformly coated on the surfaces of NCM811 by the physical mixing method. The rate capability of the resultant cathode material retains to 78.80% at a current rate of 3C. Its capacity retention increases by 6.7–14.42% compared with pristine NCM811 after 100 cycles within a potential range of 2.75–4.3 V at 0.5C. The improved rate capability and cycle performance of NCM811 are assigned to the synergistic effects between Ni–Al-LDO and CNTs. The hierarchical LDO&CNT nanocomposites coating on the surface of NCM811 avoids the aggregation of conductive CNTs and the stacking of Ni–Al-LDO nanosheets. Furthermore, it accelerates Li⁺ and electrons shuttle and reduces the reaction of Li₂O with H₂O and CO₂ in air, which results in Li₂CO₃ and LiOH alkali formation on the NCM811 surface.     

A three-dimensional surface measurement system implemented with Gaussian process based adaptive sampling

Self-adaptive surface measurements that can reduce data redundancy and improve time efficiency are in high demand in many fields of science and technology. For this purpose, a system implemented with Gaussian process (GP) adaptive sampling is developed. The non-parametric GP model is applied to reconstruct the topography and guide the subsequent sampling position, which is determined from the inference uncertainty estimation. A criterion is proposed to terminate the GP adaptive measurement automatically without any prior model or data of the topography. Experiments on typical surfaces validate the intelligence, adaptability, and high accuracy of the GP method along with the stabilization of the automatic iteration termination. Compared with traditional raster sampling, data redundancy is reduced and the time efficiency is improved without sacrificing the surface reconstruction accuracy. The proposed method can be implemented in other systems with similar measurement principles, thus benefitting surface characterizations.     

Electron transfer mediator PCN secreted by aerobic marine Pseudomonas aeruginosa accelerates microbiologically influenced corrosion of TC4 titanium alloy

Titanium alloys possess excellent corrosion resistance in marine environments,thus the possibility of their corrosion caused by marine microorganisms is neglected.In this work,microbiologically influenced corrosion (MIC) of TC4 titanium alloy caused by marine Pseudomonas aeruginosa was investigated through electrochemical and surface characterizations during a 14-day immersion test.Results revealed that the unstable surface caused by P.aeruginosa resulted in exposure of Ti2O3 and severe pitting corrosion with maximum pit depth of 5.7 μm after 14 days of incubation.Phenazine-1-carboxy[ate (PCN),secreted by P.aeruginosa,promoted extracellular electron transfer (EET) and accelerated corrosion.Deletion of the phzH gene,which codes for the enzyme that catalyzes PCN production,from the P.aeruginosa genome,resulted in significantly decreased rates of corrosion.These results demonstrate that TC4 titanium alloy is not immune to marine MIC,and EET contributes to the corrosion of TC4 titanium alloy caused by P.aeruginosa.     

Structural Cues for Understanding eEF1A2 Moonlighting

Spontaneous mutations in the EEF1A2 gene cause epilepsy and severe neurological disabilities in children. The crystal structure of eEF1A2 protein purified from rabbit skeletal muscle reveals a post-translationally modified dimer that provides information about the sites of interaction with numerous binding partners, including itself, and maps these mutations onto the dimer and tetramer interfaces. The spatial locations of the side chain carboxylates of Glu301 and Glu374, to which phosphatidylethanolamine is uniquely attached via an amide bond, define the anchoring points of eEF1A2 to cellular membranes and interorganellar membrane contact sites. Additional bioinformatic and molecular modeling results provide novel structural insight into the demonstrated binding of eEF1A2 to SH3 domains, the common MAPK docking groove, filamentous actin, and phosphatidylinositol-4 kinase IIIβ. In this new light, the role of eEF1A2 as an ancient, multifaceted, and articulated G protein at the crossroads of autophagy, oncogenesis and viral replication appears very distant from the “canonical” one of delivering aminoacyl-tRNAs to the ribosome that has dominated the scene and much of the thinking for many decades.     

Unleashing the Power of Biocatalysts

Biocatalysis is a continuously expanding subfield in chemical biology. Herein, I describe two categories of biocatalysts, the LEGO-brick-like and game-console-like type, both of which can streamline the synthetic routes to therapeutics. A multi-disciplinary approach to expand the biocatalytic toolkit will open up opportunities to develop new therapeutics.     

Synthesis of Diamond@SiO2@Ag composite materials for high SERS effect

Among various carbon materials, diamond stands out due to excellent physical and chemical properties. In this work, we designed Dia@SiO₂@Ag composites combining diamond micropowder and Ag nanoparticles by a simple chemical method and obtained stable substrate for surface enhanced Raman scattering (SERS) owing to its high surface-to-volume ratio, low density, as well as close bond between diamond and Ag. As-prepared Dia@SiO₂@Ag presented high activity to detect crystal violet and rhodamine 6G molecules, which was demonstrated by significantly enhanced SERS spectra and high enhancement factor values (10⁸-10⁹). Moreover, Dia@SiO₂@Ag also showed desired sensitivity, which was investigated by detection limit. Therefore, our study provided more theoretical support and broadened the functional applications of diamond, particularly in Raman detection.     

Chemical Bonding by the Chemical Orthogonal Space of Reactivity

The fashionable Parr–Pearson (PP) atoms-in-molecule/bonding (AIM/AIB) approach for determining the exchanged charge necessary for acquiring an equalized electronegativity within a chemical bond is refined and generalized here by introducing the concepts of chemical power within the chemical orthogonal space (COS) in terms of electronegativity and chemical hardness. Electronegativity and chemical hardness are conceptually orthogonal, since there are opposite tendencies in bonding, i.e., reactivity vs. stability or the HOMO-LUMO middy level vs. the HOMO-LUMO interval (gap). Thus, atoms-in-molecule/bond electronegativity and chemical hardness are provided for in orthogonal space (COS), along with a generalized analytical expression of the exchanged electrons in bonding. Moreover, the present formalism surpasses the earlier Parr–Pearson limitation to the context of hetero-bonding molecules so as to also include the important case of covalent homo-bonding. The connections of the present COS analysis with PP formalism is analytically revealed, while a numerical illustration regarding the patterning and fragmentation of chemical benchmarking bondings is also presented and fundamental open questions are critically discussed.