Melanin‐Containing Films: Growth from Dopamine Solutions versus Layer‐by‐Layer Deposition

Films formed by oxidation of dopamine are of interest for functionalisation of solid–liquid interfaces owing to their versatility. However, the ability to modulate the properties of such films, for example, permeability to ionic species and the absorption coefficient, is urgently needed. Indeed, melanin films produced by oxidation of dopamine absorb strongly over the whole UV/Vis part of the electromagnetic spectrum and are impermeable to anions even for a film thickness as low as a few nanometers. Herein we combine oxidation of dopamine to produce a solution containing dopamine–melanin particles and their alternating deposition with poly(diallyldimethylammonium chloride) to produce films which have nearly the same morphology as pure dopamine–melanin films but are less compact, more transparent and more permeable to ferrocyanide anions.     

Crosslink effect and albumin adsorption onto chitosan/alginate multilayered systems: an in situ QCM-D study

The adsorption of HSA onto CHI/ALG multilayer assemblies was assessed in situ using QCM-D. It was found that the behavior of HSA on biomaterials surface can be tuned by adjusting parameters of the polyelectrolyte system such as pH, layer number, crosslinker and polymer terminal layer. Our results confirmed the key role of electrostatic interactions during HSA adsorption, since oppositely charged surfaces were more effective in promoting protein adhesion. QCM-D data revealed that crosslinking (CHI/ALG)(5) CHI films allows HSA to become adsorbed in physiological conditions. Our results suggested that the biological potential of biopolymers and the mild conditions of the LbL technique turn these natural nanoassemblies into a suitable choice to be used as pH-sensitive coatings.     

Fabrication of well‐aligned electrospun nanofibrous membrane based on fluorinated polyimide

We have fabricated novel nanofibrous fluorinated polyimide membranes on a specially designed collector, which is composed of conductive aluminum plates and glass insulator materials and can be removed from the apparatus, using an electrospinning method. We describe the structure and water flux properties of the nanofibrous fluorinated polyimide membranes. The electrospun nanofibers were deposited across the plates and uniaxially aligned to the collector. In addition, the multi‐layer stacked nanofibrous membranes, consisting of three‐dimensionally ordered nanopores, were produced. The pure water fluxes for the stacked membranes were measured, using a stirred dead‐end filtration cell, and were linearly decreased with an increasing deposition time, indicating that the nanopores formed in the nanofibrous membrane were further narrowed due to the regularly accumulated nanofibers. Copyright © 2009 John Wiley & Sons, Ltd.     

Control of organoclay structure in hydrocarbon polymers

Two different kinds of organoclays were prepared by mixing a pristine montmorillonite and a double‐chain ammonium salt in many different thermoplastic or elastomeric polymers. Independently of the chemical nature of the considered polymers, the obtained organoclays presented a basal spacing of 4 or 6 nm, when the mixing occurred in the absence or in the presence of a small amount of stearic acid (SA), respectively. X‐ray diffraction and Fourier transform infrared measurements support the hypothesis that these two kinds of organoclays correspond to paraffin‐type tilted and perpendicular bi‐layer intercalates, respectively. The co‐intercalation of SA molecules with the double‐chain amphiphile is suggested, to explain the observed expansion of the clay interlayer distance. The obtained results suggest an easy way to control the organoclay structure in polymer composites. Moreover, the authors on the basis of these results propose a criticism to the extensive literature that systematically explains most d basal spacing increase observed for clays in polymer with the penetration of apolar polymer chains in the clay interlayer space. Copyright © 2010 John Wiley & Sons, Ltd.     

PS-PBA粒子分散系的介电弛豫谱解析——同、反离子对弛豫的影响及表界面电参数的计算

制备了近纳米级的聚苯乙烯-丙烯酸丁酯(PS-PBA)复合微球粒子,并在40Hz～110×106Hz的宽频范围测量了该粒子分散在9种电解质中时的介电弛豫谱,发现了与PS微球粒子分散系不同的特异介电弛豫:低频弛豫对反离子种类具有敏感性而高频弛豫则与电解质种类几乎无关;根据Shilov-Dukhin模型和M-W-O模型分别分析了高、低频率的弛豫机制,并通过对介电谱的Cole-Cole拟合获得了各体系的介电参数.进一步利用Hanai方法由介电参数计算获得了所有体系的相参数;详细分析了体系的内部参数受PS-PBA微球自身结构以及电解质种类影响的原因;讨论了离子扩散系数对介电参数的影响,从而得出了低、高频的弛豫特征时间分别由同离子的扩散系数和反离子的扩散系数所决定之结论.最后,结合Grosse宽频介电理论计算了粒子表面的以及双电层的主要电参数,并分析了电解质种类差异对这些电参数的影响.     

羊抗人IgG在金纳米通道中的迁移

以聚碳酸酯超滤膜为基板,用化学镀的方法在超滤膜上沉积金,制得直径在45nm左右的金纳米通道阵列,利用制得的金纳米通道阵列搭建离子电流测量平台,可实现对羊抗人IgG分子的浓度检测.当羊抗人IgG分子通过直径45nm的金纳米通道时,由于物理占位及表面电荷的影响,会引起离子电流发生变化;在KCl浓度为0.15mol/L(pH7.48)溶液中,IgG分子的物理占位对离子电流有阻塞作用,会导致电流减小,IgG浓度在1.8～18ng/mL范围内,减小量与浓度成线性关系;实现了对IgG的定量检测.KCl浓度降低到0.025mol/L时,由于IgG分子扩散层内反离子对通道内离子浓度的贡献占主导地位,从而造成离子电流随着IgG浓度增大而增大.     

Atomistic in situ investigation of the morphogenesis of grains during pressure-induced phase transitions: molecular dynamics simulations of the B1-B2 transformation of RbCl

The mechanistic details of the pressure-induced B1-B2 phase transition of rubidium chloride are investigated in a series of transition path sampling molecular dynamics simulations. The B2→B1 transformation proceeds by nucleation and growth involving several, initially separated, nucleation centers. We show how independent and partially correlated nucleation events can function within a global mechanism and explore the evolution of phase domains during the transition. From this, the mechanisms of grain boundary formation are elaborated. The atomic structure of the domain-domain interfaces fully support the concept of Bernal polyhedra. Indeed, the manifold of different grain morphologies obtained from our simulations may be rationalized on the basis of essentially only two different kinds of Bernal polyhedra. The latter also play a crucial role for the B1→B2 transformation and specific grain boundary motifs are identified as preferred nucleation centers for this transition.     

堆焊熔敷层表面纳米晶层摩擦磨损性能研究

用预压力滚压技术在堆焊修复层表面制备纳米晶层.利用TEM、SEM分析技术研究表面纳米晶层微观结构,利用CETR-3型多功能摩擦磨损试验机考察在干摩擦条件下堆焊层表面纳米晶层的摩擦磨损性能.结果表明堆焊修复层表面经表面纳米化处理后,表面形成厚度约为10μm(晶粒尺寸小于100 nm)的纳米晶层,最表面层平均晶粒尺寸约为10 nm.纳米压痕试验表明纳米晶层的硬度提高,最表面纳米晶层的硬度约为原始堆焊层硬度的3倍.与原始堆焊试样相比,表面纳米化试样的摩擦系数降低了10%,磨损体积降低了25%~30%左右.表面纳米化样品的磨损机制由原始堆焊层的磨粒磨损和黏着磨损转变为磨粒磨损,分析表明晶粒细化导致的高硬度、低塑性是摩擦磨损性能改善和磨损机制改变的主要原因.     

Cubic smoothing splines background correction in on-line liquid chromatography–Fourier transform infrared spectrometry

A background correction method for the on-line coupling of gradient liquid chromatography and Fourier transform infrared spectrometry (LC–FTIR) is proposed. The developed approach applies univariate background correction to each variable (i.e. each wave number) individually. Spectra measured in the region before and after each peak cluster are used as knots to model the variation of the eluent absorption intensity with time using cubic smoothing splines (CSS) functions. The new approach has been successfully tested on simulated as well as on real data sets obtained from injections of standard mixtures of polyethylene glycols with four different molecular weights in methanol:water, 2-propanol:water and ethanol:water gradients ranging from 30 to 90, 10 to 25 and from 10 to 40% (v/v) of organic modifier, respectively. Calibration lines showed high linearity with coefficients of determination higher than 0.98 and limits of detection between 0.4 and 1.4, 0.9 and 1.8, and 1.1 and 2.7 mg mL⁻¹ in methanol:water, 2-propanol:water and ethanol:water, respectively. Furthermore the method performance has been compared with a univariate background correction approach based on the use of a reference spectra matrix (UBC-RSM) to discuss the potential as well as pitfalls and drawbacks of the proposed approach. This method works without previous variable selection and provides minimal user-interaction, thus increasing drastically the feasibility of on-line coupling of gradient LC–FTIR.     

CdS量子点敏化ZnO纳米棒阵列电极的制备和光电化学性能

采用连续式离子层吸附与反应法制备了CdS量子点敏化的ZnO纳米棒电极.应用扫描电子显微镜(SEM)、X射线衍射(XRD)和透射电子显微镜(TEM)对CdS量子点/ZnO纳米棒电极的形貌、晶型和颗粒尺寸进行了分析和表征;采用光电流-电位曲线和光电流谱研究了不同CdS循环沉积次数及不同沉积浓度对复合电极的光电性能影响.结果表明,前驱体浓度都为0.1mol·L-1且沉积15次敏化后的ZnO纳米棒阵列电极光电性能最好.与单纯的ZnO纳米棒阵列电极和单纯的CdS量子点电极相比,其光电转换效率显著提高,单色光光子-电流转换效率(IPCE)在380nm处达到76%.这是因为CdS量子点可以拓宽光的吸收到可见光区,并且在所形成的界面上光生载流子更容易分离.荧光光谱实验进一步说明了光电增强的原因是,两者间形成的界面中表面态大大减少,有利于减少光生电子和空穴的复合.