Recent progress on fluorous synthesis of biologically interesting compounds

This article highlights research papers published in 2011 and 2012 on fluorous linker-assisted synthesis of biologically interesting small molecules and biomolecules.     

Design considerations for SERS detection in colloidal solution: reduce spectral intensity fluctuation

The intensity fluctuation of surface‐enhanced Raman scattering (SERS) has seriously hampered its practical applications. The previous studies that involved SERS intensity fluctuation mostly focus on the assembled substrates or single molecule and single nanoparticle but have few attention on colloidal solutions containing numerous molecules and/or nanoparticles. Here, we studied the time‐elapsed SERS spectra of three different analytes in colloidal solution. Their peak intensities fluctuated simultaneously and uniformly throughout the acquisition process and had no correlation with their wavenumber wandering. Gravity‐induced inhomogeneous distributions of Ag nanocubes in solution led to the spatial and temporal variations of peak intensities, which could be reduced by altering the integration time, particle concentration, and solvent viscosity and density. Furthermore, the dissimilar interactions between analytes and Ag nanocubes showed non‐detectable influence over their intensity fluctuations. This investigation gives out the significant guidance for SERS detection in colloidal solution. Copyright © 2015 John Wiley & Sons, Ltd.     

High-resolution surface-plasmon imaging in air and in water: V(z) curve and operating conditions

We present what are believed to be the first images obtained with a far-field high-resolution scanning surface-plasmon microscope in an aqueous medium. Measurements of V(z), the output response of the microscope, versus defocus z give a signature of the surface-plasmon propagation. V(z) is strongly conditioned by the laser beam diameter and the objective's numerical aperture, and we show how the operating mode (in air and in water) must be chosen to maximize the surface-plasmon field and to minimize diffraction (edge) effects.     

利用聚(N-异丙基丙烯酰胺-co-丙烯酸)银纳米团簇构建宽pH响应范围的激发比率型荧光探针EI北大核心CSCD

以N-异丙基丙烯酰胺(NIPAM)和丙烯酸(AA)为pH敏感单体,合成聚(N-异丙基丙烯酰胺-co-丙烯酸),并以此作为模板制备了pH敏感的聚(N-异丙基丙烯酰胺-co-丙烯酸)银纳米团簇。结合了时间分辨荧光、透射电镜(TEM)、红外光谱(FT-IR)方法,对团簇的光学性能进行了研究。团簇的荧光对不同的pH具有灵敏的响应。团簇的荧光强度与pH在4.95~11.02的范围内呈线性关系,高pH(11.02)与低pH(4.95)相比,荧光强度降低约62.4%。同时,305 nm与453 nm处荧光激发强度的比值(I;/I;)与pH在5.94~11.02的宽范围内成线性关系,利用该荧光比率可以对pH进行定量检测。     

A Surface Enhanced Raman Scattering (SERS) microdroplet detector for trace levels of crystal violet

We report on a microfluidic platform that integrates a winding microdroplet chip and a surface-enhanced Raman scattering (SERS) detection system for trace determination of crystal violet (CV). Colloidal silver was applied to generate SERS. Compared to the continuous flow microfluidic system, the microdroplet based detection described here effectively eliminates any memory effects. Effects of flow pattern, droplet size, surfactant, and position of detection were optimized. Under optimal conditions, there is a linear correlation between signal and the concentration of CV in the 10 nM to 800 nM range, with a correlation coefficient (R²) of 0.9967. The limit of detection in water is 3.6 nM.

Palladium-catalyzed aziridination of alkenes using N,N-dichloro-p-toluenesulfonamide as nitrogen source

N,N-Dichloro-p-toluenesulfonamide (TsNCl₂) was found to be an efficient nitrogen source for the aziridination of unfunctionalized alkenes using palladium catalysts. Among the palladium salts, palladium acetate was the most effective catalyst for this reaction. A variety of alkenes were reacted at room temperature with TsNCl₂ to form the desired aziridines in moderate to good yields. This method can complement our previous protocol which is limited to the use of electron-deficient α,β-unsaturated alkenes.     

Electrochemiluminescence Quenching by Halide Ions at Bipolar Electrodes

Quenching of Ru(bpy)₃²⁺ electrochemiluminescence (ECL) by Cl^?, Br^?, and I^? ions was studied as a function of halide concentration in a bipolar electrochemical cell. All of the halides investigated showed similar qualitative behavior: above a critical concentration, ECL intensity was found to decrease linearly as the halide ion concentration was increased, due to dynamic quenching of Ru(bpy)₃²⁺ ECL. Stern‐Volmer slopes (K_SV) of 0.111±0.003, 4.2±0.3, and 6.2±0.3 mM^?1 were measured for Cl^?, Br^? and I^?, respectively. The magnitude of K_SV correlates with halide ion oxidation potential, consistent with an electron transfer quenching mechanism. Using the bipolar platform described herein, aqueous, halide‐containing solutions could be quantified rapidly using the sequential standard addition method. The lower detection limit is determined by a complex mechanism involving the competitive electrooxidation of halide ions and the ECL co‐reactants, as well as the passivation of the surface of the bipolar electrode, and was found to be 0.20±0.01, 0.08±0.01 and 10±1 mM, respectively, for I^?, Br^?, and Cl^?. The performance of the bipolar ECL quenching assay is comparable to previously published fluorescence quenching methods for the determination of halide ions, while being much simpler and less expensive to implement.     

新型可见光响应的 InVO4-Cu2O-TiO2三元纳米异质结：制备及其光催化性能

由于日益严重的环境和能源危机,可见光催化剂的开发已成为当今最具挑战和紧迫的任务之一.将 TiO2和其它窄禁带半导体复合,已被证明是一种有效的可提高其可见光光催化性能的策略. Cu2O是一种禁带宽度为2.0 eV的 p型窄禁带半导体, InVO4则是一种禁带宽度为2.0 eV的 n型半导体,因它们可用于可见光光解水产氢和有机污染物的可见光降解而在过去的数年中引起了人们广泛的关注.但是纯的 Cu2O和 InVO4由于光生电子空穴对在其内部快速地复合,光催化活性通常都比较低.基于能带工程的策略本文设计了一种新型的可见光响应的 InVO4-Cu2O-TiO2三元纳米异质结,并通过普通的湿化学法进行制备：先通过水热法制备 InVO4,再通过溶胶-凝胶法制备 InVO4-TiO2二元复合物,最后通过沉淀和还原过程制备得到 InVO4-Cu2O-TiO2三元纳米异质结.
　　在10%InVO4-40%Cu2O-50%TiO2三元纳米异质结的 X-射线衍射谱中没有观察到明显的杂质峰;通过透射电子显微技术和高分辨透射电子显微技术观察到了它们之间异质结的形成,纳米颗粒的尺寸范围在5?20 nm;经紫外可见漫反射光谱估算得到10%InVO4-40%Cu2O-50%TiO2的禁带宽度为2.78 eV,在可见光区域具有较强的吸收.以普通的9 W节能灯作为可见光光源光照甲基橙5 h后,纯的 InVO4, TiO2和 Cu2O几乎没有光催化活性;10%InVO4-90%TiO2的光催化活性也很低,甲基橙降解率为8%;70%Cu2O-30%TiO2对甲基橙降解率达84%,但初始活性较低;10%InVO4-40%Cu2O-50%TiO2对甲基橙降解率接近90%,并且循环使用6次后,其光催化活性的保持率还维持在90%以上,而50%Cu2O-50%TiO2光催化活性的保持率只有74%.
　　经对使用过的10%InVO4-40%Cu2O-50%TiO2进行 X射线光电子能谱表征发现,存在一弱小的 Cu(II)震动卫星峰,表明在 InVO4-Cu2O-TiO2的光催化过程中 Cu2O的光蚀并不严重.从能带工程的角度分析, InVO4-Cu2O-TiO2三元纳米异质结具有优异的可见光催化性能的主要原因为： InVO4的导带电极电位约为?0.5 eV(vs. SHE,下同),价带电位约为+1.5 eV, Cu2O的分别约为?1.6和+0.4 eV,与 TiO2(导带和价带电极电位分别约为?0.23和+2.97 eV)相比,它们的导带位置更负,将它们组装成三元复合结构,可见光激发的导带电子就可能从 InVO4和 Cu2O的导带迁移到 TiO2的导带上去.同时, n型的 TiO2和 InVO4都与 p型的 Cu2O形成 p-n异质结, n型的 TiO2和 InVO4之间形成 n-n异质结,由于 p-n异质结中内电场的存在以及不同能级相互耦合,可进一步促进可见光激发的导带电子从 InVO4和 Cu2O的导带迁移到 TiO2的导带上去,以及可见光激发的价带空穴从 InVO4的价带迁移到 Cu2O的价带上去,从而实现光生载流子空间上的有效分离.本文有望为新型可见光响应的半导体复合催化剂的设计和制备提供新的思路.     

Observing the Reversible Single Molecule Electrochemistry of Alexa Fluor 647 Dyes by Total Internal Reflection Fluorescence Microscopy

Alexa Fluor 647 is a widely used fluorescent probe for cell bioimaging and super‐resolution microscopy. Herein, the reversible fluorescence switching of Alexa Fluor 647 conjugated to bovine serum albumin (BSA) and adsorbed onto indium tin oxide (ITO) electrodes under electrochemical potential control at the level of single protein molecules is reported. The modulation of the fluorescence as a function of potential was observed using total internal reflectance fluorescence (TIRF) microscopy. The fluorescence intensity of the Alexa Fluor 647 decreased, or reached background levels, at reducing potentials but returned to normal levels at oxidizing potentials. These electrochemically induced changes in fluorescence were sensitive to pH despite that BSA‐Alexa Fluor 647 fluorescence without applied potential is insensitive to pH between values of 4–10. The observed pH dependence indicated the involvement of electron and proton transfer in the fluorescence switching mechanism.     

Surface plasmon resonance characterization of thermally evaporated thin gold films

The heterogeneous character of thin gold films prepared by thermal evaporation and the dependence of this heterogeneity on the rate of their deposition must be considered when exploiting their optical properties for biosensor purposes. For instance, the performance of thin gold films for surface plasmon resonance (SPR) biosensors may drastically be degraded if care is not taken to prepare a film with a high fraction of gold (>95%). We use three different models to interpret the SPR response of gold films prepared by thermal evaporation. We show that the interpretation of the SPR curves requires considering both a global heterogeneity of the gold films and a surface roughness. Our conclusions are further corroborated by scanning surface plasmon microscope (SSPM) images of these thin gold films.