镧系元素钨硅杂多配合物异构体的合成与表征

关于[Ln(XM_(11)O_(39))_2]~(n-)类配合物合成有一些报道,但它们均未指出其中配体及所得配合物的构型,本文以α-和β_2-SiW_(11)O_(39)~(8-)为配体,首次合成了双-(11-钨硅酸根)合镧系元素钾盐的异构体并进行了结构表征。 1 实验部分 1.1 仪器和试剂 pHS-2型酸度计;883型笔录式极谱仪,384B型极谱分析仪,阿尔法     

空间非傍轴激光束在非线性克尔介质中的相互作用

对于非线性克尔介质中的非傍轴双脉冲激光束的传输,通过数值求解修正的非线性Schroödinger方程发现:当入射光强度在一定的能量阈值以上,入射光束的间隔达到一定值时,空间双脉冲激光束在传输过程中会发生相互作用.这种相互作用不同于一般傍轴激光束之间的相互作用,它的作用效果以一束很小的分束光的形式表现出来.文中对这种相互作用的效果进行了报道,并对此做出了理论的解释.     

Tailoring Transition‐Metal Hydroxides and Oxides by Photon‐Induced Reactions

Controlled synthesis of transition‐metal hydroxides and oxides with earth‐abundant elements have attracted significant interest because of their wide applications, for example as battery electrode materials or electrocatalysts for fuel generation. Here, we report the tuning of the structure of transition‐metal hydroxides and oxides by controlling chemical reactions using an unfocused laser to irradiate the precursor solution. A Nd:YAG laser with wavelengths of 532 nm or 1064 nm was used. The Ni²⁺, Mn²⁺, and Co²⁺ ion‐containing aqueous solution undergoes photo‐induced reactions and produces hollow metal‐oxide nanospheres (Ni_0.18Mn_0.45Co_0.37O_x) or core–shell metal hydroxide nanoflowers ([Ni_0.15Mn_0.15Co_0.7(OH)₂](NO₃)_0.2?H₂O), depending on the laser wavelengths. We propose two reaction pathways, either by photo‐induced redox reaction or hydrolysis reaction, which are responsible for the formation of distinct nanostructures. The study of photon‐induced materials growth shines light on the rational design of complex nanostructures with advanced functionalities.     

Core-shell nanoparticles coated with molecularly imprinted polymers: a review

Core-shell surface molecular imprinting technology represents a rather new trend in analytical sciences. In this kind of material, the imprinting sites are located on the surface of the cores or shells of nanoparticles (NPs). This material can improve the capability of recognizing target molecules (analytes), reduce nonspecific adsorption, increase the relative adsorption capacity and selectivity, and accelerate the rate of mass transfer. This review (with 158 references) focuses on recent trends in core-shell MIPs. Following an introduction into the field, a first main section covers common core-materials including silica, magnetic NPs, quantum dots (including semiconductor quantum dots and carbon dots), gold and silver nanoclusters, and up-conversion materials. A further section covers the materials and reagents required for preparing MIPs (with subsections on templates, functional monomers, cross-linkers, initiators, and effects of solvent). A next main section covers synthetic approaches such as precipitation polymerization, emulsion polymerization, and grafting approach. A final section gives examples for applications of core-shell MIPs in analytical assays and in sensing.

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Graphical abstract This review (with 158 references) focuses on recent trends in core-shell nanoparticles coated with molecularly imprinted polymers (core-shell MIPs). Three significant synthesis methods are introduced: precipitation, emulsion and grafting approach. Applications of core-shell MIPs concentrate on solid phase extraction, fluorescent probe, surface-enhanced Raman scattering-based sensors and electrochemical sensors.

     

Design and synthesis of hybrid solids based on the tetravanadate core toward improved catalytic properties

Five inorganic–organic hybrid vanadates based on tetravanadate cores, transition metals and N-donor ligands have been designed and synthesized under hydrothermal conditions, namely, [Zn(eIM)_3]_2V_4O_(12)(1), [Zn(pIM)_3]_2V_4O_(12)H_2O(2), [Zn(ipIM)_3]_2V_4O_(12)(3), [Co(e IM)_3]_2V_4O_(12)H_2O(4), [Cu(eIM)_2(H+2O)]_2V_4O_(12)(_5)(eIM = 1-ethylimidazole, p IM = 1-propylimidazole, ip IM = isopropylimidazole). All compounds were fully characterized by single-crystal XRD, powder XRD, elemental analysis, TGA, and FT-IR spectroscopy.The hybrid zinc vanadates(1–3) and cobalt vanadate(4) exhibit interesting 2D folded structures and the hybrid copper vanadate(5) presents a 1D chain configuration. All compounds can catalyze olefin epoxidation reactions when using TBHP(TBHP = tert-butyl hydroperoxide) as an oxidant in acetonitrile.The introduction of transition metal ions into tetravanadate cores not only improved the catalytic activity but also fulfilled the heterogeneous catalytic behavior. 1–5 all exhibit extraordinary efficiency in converting olefins to the corresponding epoxides with high conversion and selectivity(particularly,conv. up to 97.1%, sele. up to 100% for 1). Leaching test was also carried out to prove the heterogeneous behavior.     

Giant Hollow Heterometallic Polyoxoniobates with Sodalite‐Type Lanthanide–Tungsten–Oxide Cages: Discrete Nanoclusters and Extended Frameworks

The first series of niobium–tungsten–lanthanide (Nb‐W‐Ln) heterometallic polyoxometalates {Ln₁₂W₁₂O₃₆(H₂O)₂₄(Nb₆O₁₉)₁₂} (Ln=Y, La, Sm, Eu, Yb) have been obtained, which are comprised of giant cluster‐in‐cluster‐like ({Ln₁₂W₁₂}‐in‐{Nb₇₂}) structures built from 12 hexaniobate {Nb₆O₁₉} clusters gathered together by a rare 24‐nuclearity sodalite‐type heterometal–oxide cage {Ln₁₂W₁₂O₃₆(H₂O)₂₄}. The Nb‐W‐Ln clusters present the largest multi‐metal polyoxoniobates and a series of rare high‐nuclearity 4d‐5d‐4f multicomponent clusters. Furthermore, the giant Nb‐W‐Ln clusters may be isolated as discrete inorganic alkali salts and can be used as building blocks to form high‐dimensional inorganic–organic hybrid frameworks.     

Exploring the Binding Proteins of Glycolipids with Bifunctional Chemical Probes

Glycolipids are important structural components of biological membranes and perform crucial functions in living systems, including signaling transduction and interaction with extracellular environment. However, the mechanistic exploration of glycolipids in vivo is challenging because they are not genetically encoded. Herein, we designed and synthesized a series of bifunctional monogalactosyldiacylglycerol (MGDG) probes as a model by introducing diazirine and terminal alkyne moieties on an aliphatic chain. In combination with proteome profiling and molecular modeling, we have demonstrated that MGDG alleviates inflammation by antagonizing TLR4.     

基于加权改进的AR模型的负载预测研究

负载预测在故障管理中有着十分重要的作用,通过对CPU负载以及内存使用率的预测可以对系统进行实时监控,预知未来时间段资源的可用性,发出异常告警;文中提出一种加权改进的自回归模型,通过对最小二乘法求出的参数进行加权处理,结合时间序列分析理论,建立一个负载预测模型,用于CPU负载和内存使用率的预测;实验证明,对AR模型的参数进行加权的方法优化了参数估计,预测误差减小了60%~80%。     

Enhanced surface free energy of polyimide fibers by alkali treatment and its interfacial adhesion behavior to epoxy resins

In this article, polyimide (PI) fibers were modified by alkali treatment, and PI fiber-reinforced epoxy composites were fabricated. The effects of different alkali treatment times on the surface properties of the PI fibers and the adhesion behaviors of PI fiber/epoxy composites were studied. The surface morphologies, chemical compositions, mechanical properties, and surface free energy of the PI fibers were characterized by atomic force microscopy, X-ray photoelectron spectroscopy, single-fiber tensile strength analysis, and dynamic contact angle analysis, respectively. The results show that alkali treatment plays an important role in the improvement of the surface free energy and the wettability of PI fibers. We also found that, after the 3 min, 30 °C, 20 wt% NaOH solution treatment, the fibers possessed good mechanical properties and surface activities, and the interlaminar shear strength of the composites increased to 64.52 MPa, indicating good interfacial adhesion properties.