光纤SPR传感器的结构、膜材与应用进展

光纤表面等离子共振(Fiber optic surface plasmon resonance,FO-SPR)传感器由于体积小、易携带、抗电磁干扰等优点在生物、化学、医学及食品领域均具有广阔的应用前景。该文综述了光纤SPR传感器的结构、膜材料及其应用进展。其中终端反射式和在线传输式是光纤SPR传感器最重要的两种结构;最常用的膜材料包括金膜、银膜、复合膜和金属纳米颗粒。基于光纤SPR的实时检测、抗干扰能力强、可多通道检测等特点展望了其未来发展与应用前景。     

Ag@AgI/Ni薄膜的制备及其模拟太阳光催化性能

采用电化学方法制备Ag@AgI/Ni表面等离子体薄膜催化剂,使用扫描电镜(SEM),X射线衍射(XRD)和紫外-可见漫反射光谱(UV-Vis DRS)对薄膜的表面形貌、晶体结构、光谱特性以及能带结构进行分析表征,在模拟太阳光照射下,把罗丹明B作为模拟污染物对薄膜的光催化活性与稳定性进行评价,采用向反应体系中加入活性物种捕获剂的方法对薄膜光催化机理进行探究。结果表明:最佳工艺下制备的Ag@AgI/Ni薄膜表面是由附着少量Ag粒子的AgI纳米晶构成。薄膜具有显著的表面等离子共振作用、优异的光催化活性和突出的光催化稳定性。光催化反应60 min,薄膜对罗丹明B的降解率(81.1%)是AgI/Ni薄膜的1.35倍,是TiO_2(P25)/ITO薄膜的1.61倍。在薄膜光催化活性基本保持不变的前提下可循环使用5次。薄膜表面纳米Ag的等离子共振对光阴极反应的活化是光催化性能提高的重要原因。提出了薄膜光催化降解罗丹明B的反应机理。     

过渡元素掺杂Fe_3O_4(001)表面磁电性能的理论研究

采用基于密度泛函理论的第一性原理方法,计算Fe_3O_4,Fe_3O_4(001)表面以及过渡元素掺杂表面的电子结构和磁性。结果表明Fe_3O_4的半金属性主要来源于B位Fe离子,并且Fe的3d轨道发生强烈自旋极化;比较(001)表面不同终端A和B终端的表面能和电子结构,得出两种终端稳定性存在差异且A终端较稳定同时表现半金属性;由过渡元素V、Cr、Mn、Co、Cu和Zn取代Fe_3O_4(001)表面A终端A位Fe进行掺杂,形成的6种新表面结构都保持了半金属性。对比它们的表面能和磁矩,Mn掺杂的表面结构最稳定并且磁矩明显增大。     

基于MP-AES的在线检测技术在地表水中重金属监测中的应用

通过集成在线富集和在线热消解技术,建立了基于微波等离子体原子发射光谱法(MP-AES)的地表水中重金属的在线检测技术,对珠江干流之一的西江水样中重金属元素(Cd,Cu,Cr,Ni,Pb,Fe,Mn和Zn)进行现场同时在线监测。结果表明,该在线检测技术对这些重金属元素的定量检测能力满足地表水环境质量标准(GB 3838-2002)的限量要求;据环境标准样品中重金属元素分析结果,测定值与配制标准值一致;自来水加标样品的回收率为81.5%~102%。该检测技术对重金属的检出限为1.14~5.34μg/L,检测结果的相对标准偏差(RSD)为0.79%~9.4%,方法可满足地表水中重金属的现场、快速、连续、准确监测需求。     

Different supramolecular architectures mediated by different weak interactions in the crystals of three N‐aryl‐2,5‐dimethoxybenzenesulfonamides

The synthesis and evaluation of the pharmacological activities of molecules containing the sulfonamide moiety have attracted interest as these compounds are important pharmacophores. The crystal structures of three closely related N‐aryl‐2,5‐dimethoxybenzenesulfonamides, namely N‐(2,3‐dichlorophenyl)‐2,5‐dimethoxybenzenesulfonamide, C₁₄H₁₃Cl₂NO₄S, (I), N‐(2,4‐dichlorophenyl)‐2,5‐dimethoxybenzenesulfonamide, C₁₄H₁₃Cl₂NO₄S, (II), and N‐(2,4‐dimethylphenyl)‐2,5‐dimethoxybenzenesulfonamide, C₁₆H₁₉NO₄S, (III), are described. The asymmetric unit of (I) consists of two symmetry‐independent molecules, while those of (II) and (III) contain one molecule each. The molecular conformations are stabilized by different intramolecular interactions, viz. C—H…O interactions in (I), N—H…Cl and C—H…O interactions in (II), and C—H…O interactions in (III). The crystals of the three compounds display different supramolecular architectures built by various weak intermolecular interactions of the types C—H…O, C—H…Cl, C—H…π(aryl), π(aryl)–π(aryl) and Cl…Cl. A detailed Hirshfeld surface analysis of these compounds has also been conducted in order to understand the relationship between the crystal structures. The d _norm and shape‐index surfaces of (I)–(III) support the presence of various intermolecular interactions in the three structures. Analysis of the fingerprint plots reveals that the greatest contribution to the Hirshfeld surfaces is from H…H contacts, followed by H…O/O…H contacts. In addition, comparisons are made with the structures of some related compounds. Putative N—H…O hydrogen bonds are observed in 29 of the 30 reported structures, wherein the N—H…O hydrogen bonds form either C (4) chain motifs or R ₂²(8) rings. Further comparison reveals that the characteristics of the N—H…O hydrogen‐bond motifs, the presence of other interactions and the resultant supramolecular architecture is largely decided by the position of the substituents on the benzenesulfonyl ring, with the nature and position of the substituents on the aniline ring exerting little effect. On the other hand, the crystal structures of (I)–(III) display several weak interactions other than the common N—H…O hydrogen bonds, resulting in supramolecular architectures varying from one‐ to three‐dimensional depending on the nature and position of the substituents on the aniline ring.     

Evidence of Structure Sensitivity in the Fischer–Tropsch Reaction on Model Cobalt Nanoparticles by Time-Resolved Chemical Transient Kinetics

The Fischer–Tropsch process, or the catalytic hydrogenation of carbon monoxide (CO), produces long chain hydrocarbons and offers an alternative to the use of crude oil for chemical feedstocks. The observed size dependence of cobalt (Co) catalysts for the Fischer–Tropsch reaction was studied with colloidally prepared Co nanoparticles and a chemical transient kinetics reactor capable of measurements under non-steady-state conditions. Co nanoparticles of 4.3 nm and 9.5 nm diameters were synthesized and tested under atmospheric pressure conditions and H₂/CO=2. Large differences in carbon coverage (Θ_C) were observed for the two catalysts: the 4.3 nm Co catalyst has a Θ_C less than one while the 9.5 nm Co catalyst supports a Θ_C greater than two. The monomer units present on the surface during reaction are identified as single carbon species for both sizes of Co nanoparticles, and the major CO dissociation site is identified as the B₅-B geometry. The difference in activity of Co nanoparticles was found to be a result of the structure sensitivity caused by the loss of these specific types of sites at smaller nanoparticle sizes.     

Effect of Polyethylene glycol methyl ether blend Humic acid on poly (vinylidene fluoride-co-hexafluropropylene) PVDF-HFP membranes: pH responsiveness and antifouling behavior with optimization approach

Flat sheet asymmetric membranes were fabricated with homogeneous solution of poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) using N-methyl-2-pyrrolidone (NMP) as solvent via phase inversion method. PEGME (Poly ethylene glycol methyl ether) (M_n 5000) blend Humic Acid (HA), of different mole ratio was used as additive. Characterization of the membranes was done by Field emission scanning electron microscope (FESEM), Fourier Transform Infrared (FTIR) spectroscopy, Atomic force microscopy (AFM) and Differential scanning calorimetry (DSC) studies. Liquid-liquid displacement porosimetry (LLDP) study evaluated the morphological parameters, average pore size and pore size distribution. Bovine serum albumin (BSA) (M_W - 68,000 Da) was used to study the antifouling effect and pore blocking mechanism of the membranes. The pure water flux (PWF), solute rejection and flux recovery ratio drastically increases for the PEGME blended HA membranes whereas the water contact angle decreases significantly. The pH responsiveness character of the prepared membranes altered the hydraulic permeability and rejection % at different pH. Finally, optimization of the variables contributing towards the PWF and BSA rejection of the desired membrane was performed using Design expert software 9.0 TRIAL through ANOVA (analysis of variance) using the combination of response surface methodology (RSM) and central composite design (CCD).     

Cucurbituril‐mediated immobilization of fluorescent proteins on supramolecular biomaterials

The reversible introduction of functionality at material surfaces is of interest for the development of functional biomaterials. In particular, the use of supramolecular immobilization strategies facilitates mild reaction and processing conditions, as compared to other covalent analogues. Here, the engineering of multicomponent supramolecular materials, beyond the use of a single supramolecular entity is proposed. Cucurbit[8]uril (Q8) mediated host–guest chemistry is combined with hydrogen bonding supramolecular 2‐ureido‐4‐pyrimidinone (UPy)‐based materials. The modular incorporation of a UPy‐additive that presents one guest to incorporate into the Q8 host allows for selective supramolecular functionalization at the water–polymer material interface. Supramolecular ternary complex formation at the material surface was studied by X‐ray photoelectron spectroscopy, which as a result of large overlap in atomic composition of the different components showed minor changes is surface composition upon complex formation. Surface MALDI‐ToF MS measurements revealed useful insights in the formation of complexes. Protein immobilization was monitored using both fluorescence spectroscopy and quartz crystal microbalance with dissipation monitoring, which successfully demonstrated ternary complex formation. Although proteins could selectively be immobilized onto the surfaces, control of the system's stability remains a challenge as a result of the dynamicity of the host–guest assembly. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3607–3616     

Global X2A′ potential energy surface of Li2H and quantum dynamics of H + Li2 (X1Σg+) → Li + LiH (X1Σ+) reaction

A global potential energy surface (PES) for the electronic ground state of Li₂H system is constructed over a large configuration space. About 30 000 ab initio energy points have been calculated by MRCI‐F12 method with aug‐cc‐pVTZ basis set. The neural network method is applied to fit the PES and the root mean square error of the current PES is only 1.296 meV. The reaction dynamics of the title reaction has been carried out by employing time‐dependent wave packet approach with second order split operator on the new PES. The reaction probability, integral cross section and thermal rate constant are obtained from the dynamics calculation. In most of the collision energy regions, the integral cross sections are in well agreement with the results reported by Gao et al. The rate constant calculated from the new PES increases in the temperature range of present investigation.     

Surface analysis of ripple pattern on PS and PEN induced with ring‐shaped mask due to KrF laser treatment

The approach for ripple nanopattern construction on surface of two polymer substrates [polyethylene naphthalate (PEN) and polystyrene (PS)] exposed by a KrF pulse excimer UV laser through a contact lithographic mask with circular slit was proposed in this paper. Thin layer of gold was deposited on samples after the laser treatment. Changes in the morphology of the surface of both the shielded and exposed areas of the substrates, as well as the dimensions of the laser‐induced periodic surface structures, were determined (by atomic force microscopy, laser confocal microscopy and scanning electron microscopy), compared with observations and measurements made on samples treated directly (without a contact mask) under the same conditions. The morphology of the interface between the treated and untreated regions was also closely studied. Surface chemistry of treated samples was studied in detail by X‐ray Photoelectron Spectroscopy. The detailed study of surface chemistry of modified PEN and PS revealed a significant increase of oxygen concentration for laser treated PS and increase of carboxyl groups in case of PEN. The potential application of this research can be found in biotechnology, micro technology and several other fields. Copyright © 2016 John Wiley & Sons, Ltd.