Boronic Acid‐Based Carbohydrate Sensing

The covalent boron–diol interaction enables elaborate design of boronic acid‐based saccharide sensors. Over the last decade, this research topic has been well developed thanks to the integration of boronic acid chemistry with a range of techniques, including supramolecular chemistry, materials chemistry, surface modification, and nanotechnology. New sensing strategies and platforms have been introduced and remarkable progress has been achieved to fully utilize the unique property of boron–diol interaction and to improve the binding affinity towards different targets, especially under physiological conditions. In this review, the latest progress over the past 30 months (from late 2012 to early 2015) is highlighted and discussed to shed light on this versatile and promising platform for saccharide sensing.     

两种功能化纳米金粒子固酶电极的催化性能

以合成的4-巯基苯甲酸功能化纳米金粒子和聚乙烯基吡啶包覆纳米金粒子分别作为固酶载体,制备了2种新型固酶电极,在此基础上组装了2种酶燃料电池。采用电化学方法结合紫外可见分光光度法、透射电镜技术等手段研究了固酶载体的形貌,酶-载体间相互作用对电极表面固定酶分子的光谱学性质,酶-电极间直接电子迁移能力和催化底物反应性能的影响,进一步评估和比较了两种酶燃料电池的能量输出性能。实验结果表明：4-巯基苯甲酸功能化纳米金粒子固酶基电极可以实现酶-电极间的直接电子迁移而且对葡萄糖和氧气具有良好的催化性能(催化反应起始电位分别为-0.03和0.96 V,底物转化频率分别是1.3和0.5 s^-1),其催化性能的重现性、长期使用性能、酸碱耐受性和热稳定性良好,随着自组装固酶层数的增加,催化性能随之增强直至达到极限催化电流;电池性能测试结果表明4-巯基苯甲酸功能化纳米金粒子固酶基燃料电池的开路电压为0.88 V,最大输出能量密度：864.0 μW·cm^-2,长期使用性能优异(储存3 周后仍可达到最佳能量输出的80%以上)。     

Gold‐Catalyzed Suzuki Coupling of ortho‐Substituted Hindered Aryl Substrates

A method that allows hindered ortho ‐substituted aryl iodides to be efficiently coupled to phenylboronic acid using a gold‐catalyzed C−C bond formation is presented. The use of a molecularly‐defined dinuclear gold chloride catalytic precursor that is stabilized by a new tetradentate (N ,N′ )‐diamino‐(P,P′ )‐diphosphino ferrocene hybrid ligand in a Suzuki‐type reaction is described for the first time. Electron‐rich isopropyl groups on phosphorus were found essential for a superior activity, while the performances of a set of analogous gold dinuclear complexes that were fully characterized by multinuclear NMR spectroscopy and XRD analysis, were investigated. Therefore, arylation of para and ortho ‐substituted iodoarenes bearing electron‐rich, electron‐poor functional groups, and even hindered polycyclic aromatic compounds is described.     

Functionalized carbon dots as sensors for gold nanoparticles in spiked samples: Formation of nanohybrids

This paper reports the synthesis, passivation and functionalization of luminescent carbon dots (CDs) possessing surface thiol ending groups. A simple procedure involving amidation of passivated carbon dots (p-CDs) with cysteamine boosts their photoluminescent properties and enables their use as easily controlled fluorescent nanosensors for determining citrate–gold nanoparticles (AuNPs). The mechanism behind the quenching phenomenon was established from fluorescence measurements at high temperatures and lifetime tests, and found to involve static quenching leading to the formation of CD–AuNP nanohybrids. A method for determining AuNPs in complex matrices was developed and validated by application to spiked drinking water and mussel tissues. The limits of detection and quantitation for AuNPs thus obtained were 0.20 and 0.66 nmol L^–1, respectively.     

Prussian blue–gold nanoparticles-ionic liquid functionalized reduced graphene oxide nanocomposite as label for ultrasensitive electrochemical immunoassay of alpha-fetoprotein

In this work, poly(diallyldimethylammonium chloride) (PDDA) protected Prussian blue/gold nanoparticles/ionic liquid functionalized reduced graphene oxide (IL-rGO-Au-PDDA-PB) nanocomposite was fabricated. The resulting nanocomposite exhibited high biocompatibility, conductivity and catalytic activity. To assess the performance of the nanocomposite, a sensitive sandwich-type immunosensor was constructed for detecting alpha-fetoprotein (AFP). Greatly enhanced sensitivity for this immunosensor was based on triple signal amplification strategies. Firstly, IL-rGO modified electrode was used as biosensor platform to capture a large amount of antibody due to its increased surface area, thus amplifying the detection response. Secondly, a large number of Au-PDDA-PB was conjugated on the surface of IL-rGO, which meant the enrichment of the signal and the more immobilization of label antibody. Finally, the catalytic reaction between H₂O₂ and the IL-rGO-Au-PDDA-PB nanocomposite further enhanced the signal response. The signals increased linearly with AFP concentrations in the range of 0.01–100 ng mL⁻¹. The detection limit for AFP was 4.6 pg mL⁻¹. The immunosensor showed high sensitivity, excellent selectivity and good stability. Moreover, the immunosensor was applied to the analysis of AFP in serum sample with satisfactory result.     

新型磺酸功能化离子液体理化性质的研究

合成了三类磺酸功能化离子液体,通过STA、DSC-TG、UV-Vis、运动粘度/密度计等手段考察了离子液体的热力学性质、酸度、粘度和密度等理化性质,发现离子液体阴阳离子的结构对这些理化性质有不同程度的影响,并对离子液体的结构与理化性质变化关系进行初步探讨.     

Banana fiber/chemically functionalized polypropylene composites with in-situ fiber/matrix interfacial adhesion by Palsule process

Chemically functionalized maleic anhydride (MAH)-grafted polypropylene matrix has been used (in place of polypropylene as matrix with compatibilizer) to process banana fiber/chemically functionalized polypropylene (BF/CFPP) composites, without using any compatibilizer and without any fiber modification by Palsule process. Fiber/matrix interfacial adhesion generated, in-situ, due to interactions between BF and the MAH of the CFPP matrix has been established by Fourier transform infrared spectroscopy and scanning electron microscopy. Mechanical properties of the BF/CFPP composites developed by Palsule process with in-situ fiber/matrix interfacial adhesion in this study have been found to be higher than those of the matrix and it increases with increasing amounts of fibers in composites, and are better than properties of literature reported BF/polypropylene composites processed with compatibilizers. Measured modulus of BF/CFPP composites compares well with values predicted by rule of mixtures, Hrisch model, Halpin-Tsai equations and its modified Nielsen version, and with Palsule equation. The feasibility of developing natural fiber/MAH grafted polyolefin composites by Palsule process without using any compatibilizer and without any fiber treatment is demonstrated.     

Synthesis of well‐defined polymers end‐functionalized with crosslinkable aziridine groups by living anionic polymerization

Well‐defined end‐functionalized polystyrene, poly(α‐methylstyrene), and polyisoprene with polymerizable aziridine groups were synthesized by the termination reactions of the anionic living polymers of styrene, α‐methylstyrene, and isoprene with 1‐[2‐(4‐chlorobutoxy)ethyl]aziridine in tetrahydrofuran at ?78 °C. The resulting polymers possessed the predicted molecular weights and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.1) as well as aziridine terminal moieties. The cationic ring‐opening polymerization of the ω‐monofunctionalized polystyrene having an aziridinyl group with Et₃OBF₄ gave the polymacromonomer, whereas the α,ω‐difunctional polystyrene underwent crosslinking reactions to afford an insoluble gel. Crosslinking products were similarly obtained by the reaction of the α,ω‐diaziridinyl polystyrene with poly(acrylic acid)‐co‐poly(butyl acrylate). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4126–4135, 2005     

Electrospray ionization mass spectrometry of organic-inorganic materials: identification and gas-phase reactivity of functionalized octahedral rhenium(III) clusters

Electrospray ionization mass spectrometry was used for the analysis of functionalized rhenium clusters such as [Re6Se8(o-Me2TTFPPh2)6]2+ (1), {Re6Se8[(o-Me2TTF)2PPh]6}2+ (2) and [Re6Se8(MePPh2)6]2+ (3). The high-resolution mass spectra of the intact clusters, performed in dichloromethane, confirm the identification of the compounds by comparison with the theoretical isotopic distributions. Low-resolution full-scan mass spectra recorded at increasing desolvation cone voltage values allow the study of the intrinsic reactivity of ionic species. The survival yield curves illustrating the bimolecular reactivity of 1 and 2 suggest that a bisdimethyltetrathiafulvalene(phenyl)phosphine ligand increases the stability of the functionalized ML6(2+) cluster 2. In the case of the 3, instead of loss of a neutral ligand, ligand exchange is observed either with traces of water present in dichloromethane or with acetonitrile used as solvent.     

工科基础物理实验课程教学改革与实践

提出了模块化教学体系的新思路及具体实施方案。在教学上将传统内容与现代高新技术相互结合;教学方法上将程序式与多元式相结合,注重了基本技能、实验总结能力和创新精神的培养。总结了试点以来取得的教学经验和体会,并对不足之处进行了分析。