A novel method for the synthesis of sulfur substituted-cyclopyrophosphate of cADPR analogs

A facile and efficient protocol for the synthesis of sulfur substituted-cyclopyrophosphate of cIDPRE(P_S~1-cIDPRE) was developed.The key step was the cyclization process which was completed by the sulfur substituted cyclization precursor 1b via the one-pot phosphoramidite strategy.     

Frequencies and absorption intensities of the fundamental and the first overtone of NH stretching vibrations of pyrroleacetylene and pyrroleethylene complexes studied by density-functional-theory calculation

The structures of pyrroleacetylene and pyrroleethylene complexes which form an NH–π hydrogen bonding were calculated by density-functional-theory calculation. The wavenumbers and absorption intensities of the fundamental and the first overtone of NH stretching of the complexes were investigated to compare effects of the hydrogen bonding on the fundamental and the first overtone of the NH stretching mode. One-dimensional Schrödinger equation in consideration of molecular vibrational anharmonicity was used for the estimation of the wavenumbers and absorption intensities of NH stretching modes of the complexes; it was found that the NH–π hydrogen-bond formation induced lower wavenumber shift for both the fundamentals and first-overtones of NH stretching mode and it increases absorption intensities of the fundamentals and decreases those of first overtones of NH stretching mode.     

Anisotropic charge carrier transport of optoelectronic functional selenium-containing organic semiconductor materials

Organic semiconductors (OSCs) materials are currently under intense investigation because of their potential applications such as organic field-effect transistors, organic photovoltaic devices, and organic light-emitting diodes. Inspired by the selenization strategy can promote anisotropic charge carrier migration, and selenium-containing compounds have been proved to be promising materials as OSCs both for hole and electron transfer. Herein, we now explore the anisotropic transport properties of the series of selenium-containing compounds. For the compound containing Se Se bond, the Se Se bond will break when attaching an electron, thus those compounds cannot act as n-type OSCs. About the different isomer compounds with conjugated structure, the charge transfer will be affected by the stacking of the conjugated structures. The analysis of chemical structure and charge transfer property indicates that Se-containing materials are promising high-performance OSCs and might be used as p-type, n-type, or ambipolar OSCs. Furthermore, the symmetry of the selenium-containing OSCs will affect the type of OSCs. In addition, there is no direct relationship between the R groups with their performance, whether it or not as p-type OSCs or n-types. This work demonstrates the relationship between the optoelectronic function and structure of selenium-containing OSCs materials and hence paves the way to design and improve optoelectronic function of OSCs materials.     

Transition-metal-free mono- or dinitration of protected anilines

Abstract

An amide-assisted arene nitration is presented, and both mono- and dinitration of protected anilines could be effected by using NaNO₂ and NaNO₃ as the mono- and bisnitrating agents, respectively. This divergent synthesis is transition-metal- and acid-free, and features a broad substrate scope, low cost, and ortho–para selectivity.     

A novel model for quantification of the moisture absorption of polymeric laminated composites

In the present study, a new model was developed that considers the amount of the environmental fluid absorption by different constituents of polymeric laminated composites including fibers, resin, fiber-matrix interphase region, ply interface region, and voids. By knowing the fluid absorption behavior of the composite constituents, the present model can predict the amount of fluid absorption of different constituents of polymeric laminated composites with an arbitrary resin volume fraction and stacking sequence. Test specimens were fabricated by glass fibers and vinyl ester resin. The environmental fluids, examined in this study, were distilled and saline water under different temperatures and salt concentrations. To investigate the absorption behavior of different constituents of polymeric composite, various tests were conducted on fibers, pure cured resin, unidirectional composite specimens, and laminated composites. Based on the results of the tests, a new theoretical model was developed to quantify and predict the amount of fluid absorption of different constituents of laminated polymeric composites. The thickness of the interphase region between the fiber and matrix was also measured using the scanning electron microscope (SEM) images and nano-indentation tests. The consistency of experimental results with the outcomes of the theoretical model indicates the accuracy of the model.     

Co9S8/MoS2异质结构的构筑及电催化析氢性能研究

利用前驱物形貌导向法,成功制备了Co₉S₈/MoS₂异质结构催化剂,该催化剂在碱性析氢反应（HER）中表现出优异的催化活性及稳定性,其在10 mA·cm^-2处的过电势仅为84 mV.通过X射线粉末衍射（XRD）、透射电子显微镜（TEM）、电子自旋共振（ESR）、拉曼光谱（Raman）、X射线光电子能谱（XPS）和同步辐射（XAFS）等表征,证明了CoS₂/MoS₂在H₂氛围下煅烧形成Co₉S₈/MoS₂的过程中,CoS₂中Co的配位模式从部分八面体向Co₉S₈中的四面体转变,这种转变可活化MoS₂的惰性平面,从而使其更有利于吸附H^*.除此之外,接触角数据表明：该催化剂具有良好的亲水性,有利于电解液渗透及气体分子的迅速扩散,从而促进HER反应速率.由于异质结构间具有强烈的相互作用,该催化剂可表现出良好的结构稳定性.本工作基于Co₉S₈/MoS₂异质结构的成功构筑及对其HER催化机理的充分探讨,为后续硫化物异质结及其在电催化中的应用提供了良好的思路和研究基础.     

初中化学教科书表格呈现方式及其教学功能价值的研究

以现行4个版本的义务教育化学教科书为研究对象,根据教科书中表格功能的不同,将其分为实验记录型表格、归纳总结型表格、习题型表格、资料卡片型表格等4类,对4类不同表格的教学功能价值进行了分析说明。并以沪教版为例,对当前初中化学教师使用教科书表格进行教学的情况进行了抽样调查与分析,由此提出3点教学建议。     

General Strategy for Synthesis of Ordered Pt3M Intermetallics with Ultrasmall Particle Size

Controllable synthesis of atomically ordered intermetallic nanoparticles (NPs) is crucial to obtain superior electrocatalytic performance for fuel cell reactions, but still remains arduous. Herein, we demonstrate a novel and general hydrogel‐freeze drying strategy for the synthesis of reduced graphene oxide (rGO) supported Pt₃M (M=Mn, Cr, Fe, Co, etc.) intermetallic NPs (Pt₃M/rGO‐HF) with ultrasmall particle size (about 3 nm) and dramatic monodispersity. The formation of hydrogel prevents the aggregation of graphene oxide and significantly promotes their excellent dispersion, while a freeze‐drying can retain the hydrogel derived three‐dimensionally (3D) porous structure and immobilize the metal precursors with defined atomic ratio on GO support during solvent sublimation, which is not afforded by traditional oven drying. The subsequent annealing process produces rGO supported ultrasmall ordered Pt₃M intermetallic NPs (≈3 nm) due to confinement effect of 3D porous structure. Such Pt₃M intermetallic NPs exhibit the smallest particle size among the reported ordered Pt‐based intermetallic catalysts. A detailed study of the synthesis of ordered intermetallic Pt₃Mn/rGO catalyst is provided as an example of a generally applicable method. This study provides an economical and scalable route for the controlled synthesis of Pt‐based intermetallic catalysts, which can pave a way for the commercialization of fuel cell technologies.     

Effective removal of cation dyes from aqueous solution using robust cellulose sponge

Cellulose sponge was proposed to an attractive bio-absorbent owing to its highly efficient, low-cost, biodegradable, and renewable sourcing. In this work, the wasted cotton linter as raw materials, the highly porous and lightweight cellulose sponges were synthesized via a facile chemical crosslinking and freeze-drying process. The resultant cellulose sponge (CA) exhibited an interconnected three-dimensional porous structure through crosslinked with N,N′-methylene bisacrylamide (MBA), which was beneficial to remove organic dyestuffs. The effects of various factors including solution pH, contact time, initial dye concentration, and ionic strength on the adsorption behavior were investigated in detail. Herein, Langmuir isotherm models were selected to determine the adsorption capacity, and the maximum theoretical adsorption capacity for Methylene blue (MB) and Crystal violet (CV) was 123.46 and 76.63 mg/g, respectively. Particularly, the results of kinetic and thermodynamic tests showed that the adsorption performance was a spontaneous endothermic reaction and the adsorption process followed the pseudo-second-order kinetic. Furthermore, cellulose sponges could maintain maximum adsorption capacity even after twelve cycles. Therefore, the eco-friendly cellulose sponge would be a promising adsorbent for effective wastewater treatment.     

Solvent‐Free Self‐Assembly for Scalable Preparation of Highly Crystalline Mesoporous Metal Oxides

Mesoporous metal oxides (MMOs) have been demonstrated great potential in various applications. Up to now, the direct synthesis of MMOs is still limited to the solvent induced inorganic‐organic self‐assembly process. Here, we develop a facile, general, and high throughput solvent‐free self‐assembly strategy to synthesize a series of MMOs including single‐component MMOs and multi‐component MMOs (e.g., doped MMOs, composite MMOs, and polymetallic oxide) with high crystallinity and remarkable porous properties by grinding and heating raw materials. Compared with the traditional solution self‐assembly process, the avoidance of solvents in this method not only greatly increases the yield of target products and synthesis efficiency, but also reduces the environmental pollution and the consumption of cost and energy. We believe the presented approach will pave a new avenue for scalable production of advanced mesoporous materials for various applications.