Monitoring the Thiol/Thiophenol Molecule-Modulated Plasmon-Mediated Silver Oxidation with Dark-Field Optical Microscopy

Surface plasmon can trigger or accelerate many photochemical reactions, especially useful in energy and environmental industries. Recently, molecular adsorption has proven effective in modulating plasmon-mediated photochemistry, however the realized chemical reactions are limited and the underlying mechanism is still unclear. Herein, by using in situ dark-field optical microscopy, the plasmon-mediated oxidative etching of silver nanoparticles (Ag NPs), a typical hot-hole-driven reaction, is monitored continuously and quantitatively. The presence of thiol or thiophenol molecules is found essential in the silver oxidation. In addition, the rate of silver oxidation is modulated by the choice of different thiol or thiophenol molecules. Compared with the molecules having electron donating groups, the ones having electron accepting groups accelerate the silver oxidation dramatically. The thiol/thiophenol modulation is attributed to the modulation of the charge separation between the Ag NPs and the adsorbed thiol or thiophenol molecules. This work demonstrates the great potential of molecular adsorption in modulating the plasmon-mediated photochemistry, which will pave a new way for developing highly efficient plasmonic photocatalysts.     

基于2,5-二溴对苯二甲酸配体的锌/钴配合物合成、晶体结构及性质

将有机物2,5-二溴对苯二甲酸(H₂L₁)和2,2′-联吡啶(L₂)作为双配体,使用溶剂热法和七水合硫酸锌(ZnSO₄·7H₂O)、六水合硝酸钴(Co(NO₃)₂·6H₂O)分别反应,得到配合物[Zn(L₁)(L₂)(H₂O)]_n(1)和配合物[Co(L₁)(L₂)(H₂O)]_n(2)。采用单晶X射线衍射、元素分析、红外光谱、紫外光谱、荧光光谱、热重分析等测试方法对这两种物质进行分析研究。单晶测试结果表明配合物1是单斜晶系,以Zn²⁺配位连接L^2-₁与L₂形成一维链状结构,各条链在分子间氢键和π…π共轭作用下有规律地堆叠形成三维网络结构。配合物2是三斜晶系,Co1离子和Co1ⁱ离子由H₂L₁上的羧酸氧原子O4和O4ⁱ连接,形成双齿螯合的配位结构单元,以Co²⁺配位连接 L^2-₁和L₂形成二维网格结构,各层在O—H…O分子间氢键和范德瓦耳斯力作用下有规律的堆叠形成三维网络结构。配合物1和2均含有芳香杂环、羧基杂环和氮杂环,具有良好的荧光性质和热稳定性,最大发射波长分别为345 nm和333 nm。     

MWCNTs/hydroxypropyl cellulose/polyethylene glycol-based shape-stabilized phase change materials

Journal of Thermal Analysis and Calorimetry - Polyethylene glycol (PEG) is widely used as phase change materials (PCMs). However, the leakage and low thermal conductivity issues restrict its...     

Systematic Modulation of Thiol Functionalities in Inexpensive Porous Polymers for Effective Mercury Removal

Through accumulation, mercury contamination in aquatic systems still poses serious health risks despite the strict regulations on drinking water and industrial discharge. One effective strategy against this is adsorptive removal, in which a suitably functionalized porous material is added to water treatment protocols. Thiol (SH) group-grafted structures perform commendably; however, insufficient attention is paid to the cost, scalability, and reusability or how the arrangement of sulfur atoms could affect the Hg^II binding strength. We used an inexpensive and scalable porous covalent organic polymer (COP-130) to systematically introduce thiol functional groups with precise chain lengths and sulfur content. Thiol-functionalized COP-130 demonstrates enhanced wettability and excellent Hg^II uptake of up to 936 mg g⁻¹, with fast kinetics and exceptionally high selectivity. These Hg adsorbents are easily regenerated with HCl and can be used at least six times without loss of capacity even after treatment with strong acid, a rare performance in the domain of Hg-removal research.     

Effects of different modifiers on thermal stability,constituents and microstructures of asphalt-based sealant

Journal of Thermal Analysis and Calorimetry - Nowadays, the stability and heat transfer properties of nanofluids have been extensively studied. However, for the practical application, the dynamic...     

以含碘氨基酸类激素为例刍议微量非金属元素在生物体内的作用机制

选取第五周期元素碘,结合多学科的研究方法论对含碘氨基酸类激素在生物体内的合成和分解代谢进行系统性分析。通过解析碘元素本身性质及其各个氧化态之间的转化,探讨碘元素在生物体内的作用机制,揭示自然界对物质代谢的精细调控。这一教学模式探索性地融入无机化学、元素有机化学、分子生物学、生物化学、生物物理学、化学生物学等一系列学科内容,旨在让学生在领悟生命科学内在规律,从而激发其科研及学习热情,并训练学生的类比思维和思辨能力。期对培养21世纪跨学科综合型人才的培养有所助益。     

On the New Shear Constraint for Plane-Stress Orthotropic Plasticity Modeling of Sheet Metals

Experimental Mechanics - A shear constraint was very recently proposed by Abedini et al. (Int. J. Solids and Structures 151: 118–134 2018) to evaluate and calibrate advanced non-quadratic...     

Solidifying framework nucleic acids

正Living organisms have developed their unique strategies during the natural evolution for building hard tissues with minerals, including silica, calcium carbonate, calcium phosphate, and ferric oxide [1]. Such biomineralized materials generally have complex hierarchical structures with excellent mechanical properties. Although bioinspired approaches have led to the creation of well-defined synthetic structural materials ranging from micro to macro scales, the rational design of discrete biomimetic structures at the nanoscale remains a grand challenge.     

Effects of multiple delays on dynamics of a five-neuron network model

A five-neuron network model with multiple delays is proposed. This paper presents the combined effect of different delays on the dynamics of the proposed network. Pitchfork bifurcation is discussed in detail with the variation of the value of coupled weight or attenuation rate of internal neurons. By analyzing the corresponding characteristic equation, some stable criteria on delay-dependence and delay-independence are derived including multiple delays and coupled weights and the periodic oscillation arises bifurcated from the trivial equilibrium after the network loses its stability. Stable regions on delay-dependence are displayed in the two delayed parameter plane. It is shown that multiple delays can produce stability switching between resting state and periodic activity. Finally, theoretical results are justified by providing two illustrative examples.     

Infinitely many reducts of homogeneous structures

It is shown that the countably infinite dimensional pointed vector space (the vector space equipped with a constant) over a finite field has infinitely many first order definable reducts. This implies that the countable homogeneous Boolean-algebra has infinitely many reducts.