Microstructure transition of hydrophilic modified ibuprofen and Pluronic copolymer F127 complexes

The effect of the aggregation state of Pluronic copolymer (PEO₁₀₀–PPO₆₅–PEO₁₀₀, F127) and the concentration of hydrophilic modified ibuprofen (Ibuprofen–PEG800, IP800) on the interaction between F127 and IP800 was systematically investigated by nuclear magnetic resonance, dynamic light scatter (DLS), surface tension, and freeze-fractured transmission electron microscopy. In the solution of F127 unimers (5 °C), F127 unimers tended to wrap around IP800 micelles, and the binding model of F127 unimers to IP800 micelles transferred from wrapping around to partly threading through with increasing IP800 concentration. The latter binding model was straightly confirmed by nuclear Overhauser enhancement spectroscopy. As the aggregation state of F127 is in the beginning of the micellization (20 °C), the addition of IP800 significantly promoted the micellization of F127 to form the F127/IP800 complex with F127 micelles as the skeleton called the F127–micelle complex. The sudden decrease of the size obtained from DLS stemmed from the disruption of the F127–micelle complex and accompanying rehydration of PPO which is weaker compared with refs. The amount of IP800 to disintegrate the F127–micelle complex increased in the F127–micelle-dominated solution (40 °C) compared to that at 20 °C.     

Some experiments on complex spontaneous emulsification in the system water–benzene–ethanol

The system water–benzene–ethanol was used to illustrate the complexity of spontaneous emulsification, when water-poor emulsions are brought in contact with water. In the first case, an O/W emulsion located close to the plait point in the system was used. The aqueous phase in the emulsion was incompatible with water, and a strong spontaneous emulsification to an O/W between the two liquids took place in the water layer close to the interface between layers. In the second case, a W/O emulsion, also close to the plait point, was brought in contact with water. Now, the spontaneous emulsification between the water and the oil phase of the original emulsion to an O/W emulsion also took place in the water layer forming a distinct emulsion layer beneath the interface.     

A Supersymmetric AKNS Problem and Its Darboux‐Bäcklund Transformations and Discrete Systems

In this paper, we consider a supersymmetric AKNS spectral problem. Two elementary and a binary Darboux transformations are constructed. By means of reductions, Darboux and Bäcklund transformations are given for the supersymmetric modified Korteweg‐de Vries, sinh‐Gordon, and nonlinear Schrödinger equations. These Darboux and Bäcklund transformations are adopted for the constructions of integrable discrete super systems, and both semidiscrete and fully discrete systems are presented. Also, the continuum limits of the relevant discrete systems are worked out.     

Detection of bleomycin based on N and S co-doped graphene quantum dots as a fluorescence probeEI北大核心CSCD

N and S co-doped graphene quantum dotsNS-GQDswith excellent fluorescence properties were synthesized by hydrothermal method using citrate and thiourea as ingredientsand were characterized. The fluorescence signal was notably reduced in the presence of single stranded DNAssDNAsince ssDNA can adsorb on the surface of NS-GQDs through p-p stacking interaction. Whereas a significantly restored fluorescence signal was observed in the presence of bleomycinowing to the irreversible cleavage of ssDNA by bleomycin with Fe2+ as cofactor. Thusa fluorescence sensor for bleomycin detection was developed. The linear range was from 1.8 to 1200 nmol/L and the detection limit was 0.25 nmol/L. The method was used to detect bleomycin content in human serum samples with satisfactory results. © 2022, Youke Publishing Co.,Ltd. All rights reserved.     

Metal-Organic Frameworks-derived Indium Clusters/Carbon Nanocomposites for Efficient CO2 Electroreduction

Electrochemical reduction of carbon dioxide into value-added products is a promising way to recycle the greenhouse gas, thus solving the crisis of global warming. Pressing challenges remain in regulating the catalytic selectivity. In this work, we demonstrated a metal-organic frameworks-assisted approach to synthesizing In species loaded on the surface of N doped carbon matrix. By controlling the particle sizes, the catalytic selectivity can be easily altered. The obtained In_c/NC possesses the outstanding capability for converting CO₂ into CO. And 80.09% Faraday efficiency (FE) of CO can be achieved at 0.8 V vs. RHE. While the In₂O₃/C exhibits different catalytic behaviors, the main product is formic acid and the FE is more than 50% at 0.8 V vs. RHE. The selectivity reversal can be attributed to the strong interactions between In clusters and N atoms of carbon supports, which efficiently inhibits the formation of the by-product, formic acid. Our research has paved a new way to modulate catalytic selectivity by manipulating the fine structures of the catalysts.     

Phase‐Junction Electrocatalysts towards Enhanced Hydrogen Evolution Reaction in Alkaline Media

To ensure sustainable hydrogen production by water electrolysis, robust, earth‐abundant, and high‐efficient electrocatalysts are required. Constructing a hybrid system could lead to further improvement in electrocatalytic activity. Interface engineering in composite catalysts is thus critical to determine the performance, and the phase‐junction interface should improve the catalytic activity. Here, we show that nickel diphosphide phase junction (c‐NiP₂/m‐NiP₂) is an effective electrocatalyst for hydrogen production in alkaline media. The overpotential (at 10 mA cm^?2) for NiP₂‐650 (c/m) in alkaline media could be significantly reduced by 26 % and 96 % compared with c‐NiP₂ and m‐NiP₂, respectively. The enhancement of catalytic activity should be attributed to the strong water dissociation ability and the rearrangement of electrons around the phase junction, which markedly improved the Volmer step and benefited the reduction process of adsorbed protons.     

O2 dissociative adsorption on the Cu‐, Ag‐, and W‐doped Al(111) surfaces from DFT computation

The O₂ adsorption and dissociation on M‐doped (M = Cu, Ag, W) Al(111) surface were studied by density functional theory. The adsorption energy of adsorbate, the average binding energy and surface energy of Al surface, and the doping energy of doping atom were calculated. All the doped atoms can be stably combined with Al atoms, while being slightly embedded in the surface to a certain depth. The TOP‐type surfaces are the most stable doped surfaces for O₂ adsorption, which is related to the orbital hybridization between the adsorbate and the surface atoms, the electronegativity, and the orbital energy level of the doping atoms. Moreover, the O atoms and doping atoms contribute significantly to the density of states (DOS), especially the O‐p orbital electrons and the d orbital electrons of doping atoms. The degree of O₂ dissociation is related to the doping atoms on Al surfaces, and the doping atoms actually resist the dissociation of O₂. W atoms have the best resistance effect on the O₂ dissociation as compared with Cu and Ag atoms, especially W‐1NN surface, which has both large barrier energy and reaction energy.     

How the Aggregates Determine Bound Rubber Models in Silicone Rubber? A Contrast Matching Neutron Scattering Study

The correlation between aggregates and bound rubber structures in silicone rubbers(S(phr)) with various silica fractions(ΦSi) has been investigated by contrast matching small-angle neutron scattering(SANS), swelling kinetics, and low-field nuclear magnetic resonance(NMR).Mixed solvents with deuterated cyclohexane fractions of 4.9% and 53.7% were chosen to match the scattering length densities of the matrix(SMP(phr)) and the filler(SMS(phr)), respectively. All the data consistently suggest that:(i) There is a critical threshold ΦSic between 10 and 30 phr;below ΦSic, the isolated aggregates are dominant, while beyond ΦSic, some rubber fraction is trapped among the agglomerate;(ii) ΦSiindependent thicknesses around 7.5 nm(NMR) and 8.6 nm(SANS) suggest that the bound rubber formation is determined by inherent properties of the components, and the power-law around 4.2 suggests an exponential changed gradient density of the bound rubber;(iii) SMS(80) presents a bicontinuous bound rubber with three characteristic lengths of 41, 100, and 234 nm. The expanded correlation length, a 20 nm smaller aggregate sizes suggest that such existent bicontinuous network in dry samples with less ΦSi is kind of impacted by swelling. With the obtained bound rubber models, the reinforcing mechanism of filled silicone rubber is elucidated.     

哌啶并[2,3-b]哌嗪类衍生物的设计、合成及其抗血小板聚集活性研究

以2,3-二氨基吡啶和2,3-丁二酮为起始原料,经环化、催化氢化和亲核取代反应合成了10个新型哌啶并[2,3-b]哌嗪类衍生物(3a~3j),其结构经¹H NMR、¹³C NMR和HR-MS确证。体外抗血小板聚集活性研究表明,化合物3d、3e、3g、3h和3j具有一定的抗血小板聚集作用,其中化合物3h(IC₅₀=1.24mmol/L)的活性显著优于母体化合物川芎嗪(IC₅₀=3.96mmol/L)和阳性药物阿司匹林(IC₅₀=2.41mmol/L)。     

乙炔氢氯化反应中的负载金-离子液体催化剂:离子态金物种的稳定机制

聚氯乙烯(PVC)作为世界通用工程塑料之一,具有优异的物理、化学和机械性能,在工业、农业、建筑、包装、电力等行业中应用广泛.氯乙烯是生产聚氯乙烯的重要单体.氯乙烯的生产主要有电石法和乙烯法两种工艺路线,由于我国“贫油、富煤、少气”的资源现状,电石法产能占全部产能的83%以上.电石法生产氯乙烯的原理是在氯化汞催化剂存在下,将电石水解精制后的乙炔气与氯化氢加成直接合成氯乙烯.随着节能减排及环保要求的逐渐提高和国际涉汞公约的实施,开发新一代绿色无汞催化剂具有重要的战略意义.近年来,金基催化剂是无汞催化剂基础研究和技术开发中最重要的方向.在之前的工作中,我们课题组首先报道了负载离子液体-金催化剂体系(Au-SILP)在电石法生产氯乙烯工艺中的应用,并发现离子液体的存在可以显著提高金活性物种在载体表面的分散度和稳定其化学价态.在后续研究中,我们在负载离子液体-金催化体系中引入金属铜离子(Cu^2+),利用反应过程中Au-Cu之间的氧化还原循环,设计并制备了金属铜基配位离子液体,构建了负载离子液体-金-铜催化剂体系.铜离子的引入形成了一个催化剂自身维持氧化态的微环境,实现了被还原金物种的原位氧化再生.本文在上述研究基础上,利用配位离子液体[Bmim][N(CN)2]中[N(CN)2^–]阴离子和阳离子金之间的强配位作用,构建出比Au-Cl键更稳定的Au–N键,并通过X射线光电子能谱(XPS)、球差校正-扫描透射电镜(AC-STEM)和扩展X射线吸收精细结构(EXAFS)表征证明了Au以单原子状态存在于载体表面.制备的Au-N(CN)2/AC催化剂在乙炔氢氯化反应中表现出比Au-Cl/AC和Au/AC催化剂更高的稳定性和催化活性以及更短的诱导期.进一步表征分析发现,[N(CN)2^–]配体促进了阳离子金和配体之间的电子转移,提高了阳离子金的电子云密度,削弱了乙炔在阳离子金上的吸附强度,抑制了其还原,提高了催化剂的稳定性.更重要的是,与阳离子金配位的[N(CN)2^–]配体使得反应过程中的氯化氢在氮位点发生化学解离,促进了氯化氢活化,同时降低了反应能垒.对负载配位离子液体-金催化体系反应诱导期的分析结果表明,反应诱导期与反应物(乙炔、氯化氢)分子在离子液体层中的溶解度无关,而主要取决于催化剂中Au(Ⅲ)物种的含量和反应物分子在离子液体中的扩散速率.上述研究结果进一步深化了离子液体和活性金物种之间电子的作用机理,建立了负载离子液体-金催化剂体系对反应物的活化机制和反应机理,为进一步开发具有工业应用价值的乙炔氢氯化反应无汞催化剂提供了科学基础和参考.