Analogy in adsorption behavior of homopolyelectrolyte mixtures as compared to analogous diblock polyampholytes

The adsorption behavior of aqueous mixtures of the homopolyelectrolytes poly(methacrylic acid) (PMAA) and poly[(dimethylamino)ethyl methacrylate] (PDMAEMA) was investigated in comparison with the adsorption of the ampholytic diblock copolymer PMAA‐b‐PDMAEMA on silicon substrates. Ellipsometry was used to determine the amount of adsorbed homopolyelectrolyte and diblock polyampholyte. Furthermore, the topography of the adsorbed polymers was investigated with atomic force microscopy (AFM) and compared with the structures observed in aqueous solutions by dynamic light scattering (DLS). For all types of investigated polyelectrolytic mixtures or the single polyampholyte, the adsorption was strongly influenced by the pH of the polymer solution. Although single homopolyelectrolytes showed only one maximum in adsorption according to their charge, the mixtures made from these homopolyelectrolytes showed two or three maxima. The third maximum near the isoelectric point of the mixture was assigned to a new species formed by aggregation of the two homopolyelectrolytes. Altogether, the adsorption behavior of the polyelectrolytic mixtures was in between the behavior of the pure homopolyelectrolytes and the analogous polyampholytes and therefore understandable from both of these polymer species. © 2002 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 338–345, 2002; DOI 10.1002/polb.10091     

TiO2纳米膜表面结构形态特征

采用反胶束法制备TiO2纳米溶胶,用浸渍提拉法在不同的条件下制备了三种TiO2多孔纳米薄膜,并利用AFM、SEM、XRD等方法对膜表面结构物理化学特性进行表征.结果表明三种膜基本上由粒径约为59 nm的纳米粒子以不同的方式堆积而成,溶胶刚生成时浸提一次,干燥、焙烧得到膜上纳米粒子分布均匀,所生成的二次粒子粒径最小,二次粒子形成的二次表面粗糙度最小,浸提10次得到膜上纳米粒子间存在较丰富缝隙结构,二次粒子粒径及其形成的表面粗糙度较大,而溶胶制备好陈化6 h后浸提得到的膜上二次粒子粒径最大,表面粗糙度最高.由分形理论估算得到三种膜的分形维数分别是2.22、2.20和2.27. XRD测试表明,膜上TiO2为锐钛矿晶相.这些结果表明,采用不同制备步骤得到的膜,其表面结构形态存在较大的差异.     

牛血清白蛋白与十二烷基硫酸钠作用的机理

利用电动势法得到了牛血清白蛋白(BSA)与十二烷基硫酸钠(SDS)相互作用的结合等温线. 通过四阶导数紫外光谱法和荧光光谱法研究了相互作用过程中芳香族氨基酸残基微环境极性的变化. 通过研究发现, 随着SDS浓度的逐渐增大, SDS在BSA上的平均结合数(v)逐渐增大, 色氨酸(Trp)残基所处微环境的极性在减弱后保持基本不变, 酪氨酸残基所处微环境的极性在明显增强后稍有减弱, 苯丙氨酸残基所处微环境的极性略有增强. 结果表明, 当v由0增大到14时, SDS主要结合在BSA的Trp-213附近并逐渐形成聚集体, 从而诱导BSA由结构域ⅡA 开始逐渐展开. 此后, SDS呈正协同作用的特点与BSA 结合, v急剧增大. 当v约为302 时, SDS在BSA上的结合基本达到饱和, BSA的构象趋于稳定.     

牛血清白蛋白与十二烷基硫酸钠作用的机理

利用电动势法得到了牛血清白蛋白(BSA)与十二烷基硫酸钠(SDS)相互作用的结合等温线. 通过四阶导数紫外光谱法和荧光光谱法研究了相互作用过程中芳香族氨基酸残基微环境极性的变化. 通过研究发现, 随着SDS浓度的逐渐增大, SDS在BSA上的平均结合数(v)逐渐增大, 色氨酸(Trp)残基所处微环境的极性在减弱后保持基本不变, 酪氨酸残基所处微环境的极性在明显增强后稍有减弱, 苯丙氨酸残基所处微环境的极性略有增强. 结果表明, 当v由0增大到14时, SDS主要结合在BSA的Trp-213附近并逐渐形成聚集体, 从而诱导BSA由结构域ⅡA 开始逐渐展开. 此后, SDS呈正协同作用的特点与BSA 结合, v急剧增大. 当v约为302 时, SDS在BSA上的结合基本达到饱和, BSA的构象趋于稳定.     

失效原子力显微镜硅针尖再生

原子力显微镜的传统商品硅针尖在使用过程中极易因磨损而失效，本文研究了一种在实验室条件下简易可行的回收利用失效硅针尖的方法。在原子力显微镜的敲击模式下使用曲率半径大于100 nm的失效硅针尖对生长单壁碳纳米管的样品表面进行扫描，把样品表面的单壁碳纳米管管束粘接到硅针尖上，可制得直径在5～20 nm的碳纳米管针尖。实验对碳纳米管针尖和新的商品硅针尖进行了成像对比，所制备的碳纳米管针尖不仅在成像分辨率而且在成像稳定性上都优于新的商品硅针尖。     

N-苄叉基-1-氨基-萘及其类似物的构象与分子扭曲的共轭 驱动力

确定了N-[(4-二甲基氨基)-苄叉基]-2-氨基苯并咪唑(1)，N-[(4-二甲基氨基)-苄叉基]-2-氨基苯并噻唑(2)和N-苄叉基-1-氨基-萘(3)的晶体结构。利用AM1，RHF，DFT方法和STO-3G,4-31G,6-311G及6-311G基组，优化每个分子的23个扭曲构象(θ=0°～-89°)。尽管不同方法得到的最优构象的扭角不同，分子扭曲的驱动力总是起因于电子作用，在任一分子、任何电子态中，离域的π体系总是失稳定的，全平面构象不是π体系最稳定的构象。π电子的离域是分子扭曲的驱动力之一，与经典观点相反，非键原子间的核排斥作用是分子扭曲的阻力，而不是动力。     

The effect of electrochemically treated glassy carbon on the activity of supported Pt catalyst in methanol oxidation

Effect of electrochemical oxidation of glassy carbon on deposition of platinum particles and electrocatalytic activity of platinum supported on oxidized glassy carbon (Pt/GC_OX) were studied for methanol oxidation in H₂SO₄ solution. Platinum was potentiostatically deposited from H₂SO₄ + H₂PtCl₆ solution. Glassy carbon was anodically polarised in 0.5 M H₂SO₄ at 2.25 V vs. saturated calomel electrode (SCE) during 35 s. Electrochemical treatment of GC support, affecting not significantly the real Pt surface area, leads to a better distribution of platinum on the substrate and has remarkable effect on the activity. The activity of the Pt/GC_OX electrode for methanol oxidation is larger than polycrystalline Pt and for more than one order of magnitude larger than Pt/GC electrode. This increase in activity indicates the pronounced role of organic residues of GC support on the properties of Pt particles deposited on glassy carbon.     

Synthesis and properties of novel polyurethanes containing 3,4‐dioxybenzylidenecyanoacetate group as a nonlinear optical chromophore

Methyl 3,4‐di‐(2′‐hydroxyethoxy)benzylidenecyanoacetate ( 3 ) was prepared by hydrolysis of methyl 3,4‐di‐(2′‐vinyloxyethoxy)benzylidenecyanoacetate ( 2 ). Diol 3 was condensed with 2,4‐toluenediisocyanate, 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate, and 1,6‐hexamethylenediisocyanate to yield polyurethanes 4 – 6 containing the nonlinear optical chromophore 3,4‐dioxybenzylidenecyanoacetate. The resulting polyurethanes 4 – 6 were soluble in common organic solvents such as acetone and dimethylformamide. Polymers 4 – 6 indicated thermal stability up to 300 °C in thermogravimetric thermograms with glass‐transition temperature values obtained from differential scanning calorimetric thermograms in the range of 78–102 °C. The second‐harmonic generation coefficients (d₃₃) of the poled polymer films were around 6.9 × 10^?9 esu. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1742–1748, 2002     

Scanning force microscopy based rapid force curve acquisition on supported lipid bilayers: experiments and simulations using pulsed force mode.

In situ pulsed force mode scanning force microscopy (PFM-SFM) images of phase separated solid-supported lipid bilayers are discussed with the help of computer simulations. Simultaneous imaging of material properties and topography in a liquid environment by means of PFM-SFM is severely hampered by hydrodynamic damping of the cantilever. Stiffness and adhesion images of solid-supported membranes consisting of cholesterol, sphingomyelin, and 1,2-dioleyl-phosphatidylcholine obtained in aqueous solution exhibit contrast inversion of adhesion and stiff. ness images depending on parameters such as driving frequency, amplitude, and trigger setting. Simulations using a simple harmonic oscillator model explain experimental findings and give a deeper insight into the way PFM-SFM experiments have to be performed in order to obtain interpretable results and hence pave the way for reliable material contrast imaging at high speed.     

二氧化钛纤维表面担载Pt纳米结构的原子力显微镜研究

通过原子力显微镜研究了二氧化钛纤维表面担载Pt的表面形貌及其结构.结果表明,TiO2纤维表面担载的Pt具有微米尺度的近似六边形或者近似长方形的结构,与在单晶TiO2(110)表面的Pt纳米簇形貌相似,但尺度较大.TiO2纤维担载的Pt表面明显存在不同高度的台阶结构,台阶高度以2~4倍Pt(111)晶面面间距的高度为主.由Pt在TiO2纤维表面的形貌与纤维的纳米晶粒排布有序性推测可知,Pt与TiO2纤维存在强的相互作用,可能正是这种强相互作用和表面台阶结构才使TiO2表面担载的Pt虽是微米尺寸但仍具有高光催化活性.