Aggregation Behaviors of Novel Amphiphilic Dendrimers at Solid-Liquid Interface

Generation 1 poly(amidoamine) dendrimer is modified with different alkyl tails. A series of novel quaternary ammonium with dendrimeric framework has been obtained, which is abbreviated as QPAMC_m (m represents the carbon number of the alkyl tail). The modified dendrimers were deposited onto the mica substrate from the solution and the aggregation properties including the morphology and the dynamic process of the adsorption were studied by atomic force microscope (AFM), x-ray photoelectron spectroscopy (XPS), and contact angle measurement. Results show that the bulk concentration and the length of hydrophobic tails significantly affect the aggregate morphology at mica-aqueous interface. With the increasing of the bulk concentration and the adsorption time the sphere aggregates transform to semi-continuous film, which is very different from conventional surfactants and linear polymers. The interaction between the hydrophobic tails might be stronger and the alkyl chains may tilt or wind when the end tail is long enough. The contact angle measurement indicates that the hydrophobicity of the solid surface adsorbed with the dendrimers vary regularly. The contact angles rise with the increasing periphery alkyl chains length of the dendrimers.     

In Situ Vesicle Formation by Native Chemical Ligation

Phospholipid vesicles are of intense fundamental and practical interest, yet methods for their de novo generation from reactive precursors are limited. A non‐enzymatic and chemoselective method to spontaneously generate phospholipid membranes from water‐soluble starting materials would be a powerful tool for generating vesicles and studying lipid membranes. Here we describe the use of native chemical ligation (NCL) to rapidly prepare phospholipids spontaneously from thioesters. While NCL is one of the most popular tools for synthesizing proteins and nucleic acids, to our knowledge this is the first example of using NCL to generate phospholipids de novo. The lipids are capable of in situ synthesis and self‐assembly into vesicles that can grow to several microns in diameter. The selectivity of the NCL reaction makes in situ membrane formation compatible with biological materials such as proteins. This work expands the application of NCL to the formation of phospholipid membranes.     

Measuring Level Alignment at the Metal–Molecule Interface by In Situ Electrochemical 13C NMR

A new technique to measure energy‐level alignment at a metal–molecule interface between the Fermi level of the metal and the frontier orbitals of the molecule is proposed and experimentally demonstrated. The method, which combines the electrochemistry of organo‐ligand‐stabilized Au nanoparticles with ¹³C NMR spectroscopy (i.e. in situ electrochemical NMR), enables measuring both occupied and unoccupied states.     

In Situ Ellipsometry Measurements on the Halide Phase Segregation of Mixed Halide Lead Perovskites**

Methylammonium lead iodide bromides MAPb(Br_xI_1-x)₃ are a class of mixed halide lead perovskites, materials that offer high-power conversion efficiencies and bandgap tunability. For these reasons, they are a promising absorber material for future solar cells, although their use is still limited due to several factors. The reversible phase segregation under even low light intensities is one of them, lowering the effective bandgap due to local segregation into iodide-rich and bromide-rich phases. While several studies have been done to illuminate the mechanism and suppression of phase segregation, challenges remain to understand its kinetics. We obtained dynamic ellipsometric measurements from x=0.5 mixed halide lead perovskite thin films protected by a polystyrene layer under green laser light with a power density of ∼11 W/cm². Time constants between 1.7(±0.7)×10⁻³ s⁻¹ for the segregation and 1.5(±0.6)×10⁻⁴ s⁻¹ for recovery were calculated. The phase segregation rate constants are surprisingly two orders of magnitude slower than and the recovery rate is consistent with those measured using photoluminescence methods under similar conditions. These results confirm a concern in the literature about the complexity in the phase separation kinetics measured from photoluminescence. We expect ellipsometry to serve as a complementary technique to other spectroscopies in studying mixed-halide lead perovskites phase segregation in the future.     

In Situ Spectroscopic Analysis of Nanocluster Formation

The importance of small metal clusters in catalysis and the problems in understanding the clustering process in solution are outlined. A new analysis method for UV/Vis spectra is presented and applied to monitor the kinetics of ion reduction and cluster formation in situ. This method, which is based on a combination of two chemometric techniques, takes into account the entire UV/Vis spectrum and offers better interpretation possibilities than the traditional “band‐assignment” approach. This is particularly true for nanoclusters because these have significant spectral contributions also outside the broad plasmon band that is usually associated with them. The reduction of palladium, gold, and silver ions and the formation of the corresponding clusters is monitored in the presence of two different reducing agents, sodium borohydride and tetraoctylammonium acetate. While Pd²⁺ is found to reduce and cluster directly, the spectral decomposition of the Au³⁺ reduction profiles shows two species corresponding to the Au⁺ intermediate and the Au⁰ clusters. The rates of reduction and clustering for Pd, Au, and Ag are compared and the possibilities of synthesising multimetallic clusters of these metals by coreduction are discussed.     

纳米自组装聚电解质超薄多层膜

相反电荷的聚电解质在溶液中通过静电相互作用自组装形成超薄多层膜，这种膜的结构可实现分子水平上的控制。就其复合、结构及其影响因素、以及应用进行了概述。     

Excessive Iodine Enabled Ultrathin Inorganic Perovskite Growth at the Liquid-Air Interface

The liquid-air interface offers a platform for the in-plane growth of free-standing materials. However, it is rarely used for inorganic perovskites and ultrathin non-layered perovskites. Herein the liquid-air interfacial synthesis of inorganic perovskite nanosheets (Cs₃Bi₂I₉, Cs₃Sb₂I₉) is achieved simply by drop-casting the precursor solution with only the addition of iodine. The products are inaccessible without iodine addition. The thickness and lateral size of these nanosheets can be adjusted through the iodine concentration. The high volatility of the iodine spontaneously drives precursors that normally stay in the liquid to the liquid-air interface. The iodine also repairs in situ iodine vacancies during perovskite growth, giving enhanced optical and optoelectronic properties. The liquid-air interfacial growth of ultrathin perovskites provides multi-degree-of-freedom for constructing perovskite-based heterostructures and devices at atomic scale.     

“电极/溶液”界面的椭圆偏振测量技术研究进展

椭圆偏振测量技术是通过解析偏振光束在界面上或薄膜中反射或透射时偏振状态的变化,获取界面或薄膜的厚度、复折射率等性质的一种光学方法,是一种高灵敏度、非破坏性的原位实时表征技术,被广泛应用于“电极/溶液”界面的研究. 本文简要介绍了椭圆偏振测量技术的基本原理及其最新发展,并着重评述了能源电化学、材料电化学、电分析与生物电化学等领域中,应用椭圆偏振测量技术研究“电极/溶液”界面的现状.     

Structural Conformation of Bovine Serum Albumin Layers at the Air-Water Interface Studied by Neutron Reflection

The adsorption of bovine serum albumin (BSA) at the air-water interface has been studied by specular neutron reflection. The variation of the adsorbed amount and the total thickness of the BSA layer with respect to bulk BSA concentration was determined at pH 5, close to its isoelectric point (IP). While the surface excess showed a steady increase with bulk concentration the thickness of the protein layer was found to be close to the short axial length of 40 ? of the globular solution structure of BSA at concentrations below 0.1 g dm-3, suggesting that BSA molecules adsorb with their long axes parallel to the surface of water. At 1 g dm-3 the adsorbed layer can be modeled as an upper layer of 40 ? with a volume fraction of 0.4 and a sublayer of 30 ? underneath the top main layer with a volume fraction of 0.12. The results suggest that, although there is some structural deformation accompanying adsorption, there is no denaturation. The extent of immersion of the BSA in water was determined by performing the measurements in D2O and in a mixture of H2O and D2O whose contrast matches that of BSA. The signal is then only from the part of the layer out of water. At pH 5 this layer was about 10 +/- 5 ? at a bulk concentration of 5 x 10(-4) g dm-3 and decreased to 5 +/- 3 ? at 1 g dm-3. The fraction of the BSA layer immersed in water therefore varies from about 70 to over 90%. The effect of pH on the adsorption was examined at two BSA concentrations. While pH had little effect on the adsorption at a low BSA concentration of 5 x 10(-3) g dm-3, both surface excess and layer thickness showed pronounced peaks at pH 5 at the higher concentration of 1 g dm-3. The increased adsorption at pH 5 is attributed to the reduced lateral electrostatic repulsion around the IP. This adsorption pattern became less pronounced when the total ionic strength was increased from 0.02 to 1 M, indicating that the electrolyte screens the electrostatic repulsions within the adsorbed layer. Copyright 1999 Academic Press.     

In Situ Monitoring of Selective Catalysts on Urethane Formation by FT-IR Spectroscopy

A number of tertiary amines and organotin catalysts for the phenyl isocyanate- 1,2-propylene glycol reaction were investigated by using in situ FT-IR. The reaction rate of each hydroxyl group, which is defined as the ratio between the rate constant of the secondary hydroxyl group and the rate constant of the primary hydroxyl group, is described with a second-order equation. The influence of different catalyst concentrations as well as the reaction temperature is discussed. It is observed that the selectivity depends on temperature but not on concentration, and stannous octoate is the most effective catalyst. The thermodynamic parameters were determined for the catalyzed reactions, primary and secondary hydroxyl groups being differentiated.     

用自组装法制备聚合物纳米复合膜

文章比较了自组装法（ｓｅｌｆ－ａｓｓｅｍｂｌｙ,ＳＡ）与Ｌａｎｇｍｕｉｒ－Ｂｌｏｄｇｅｔｔ技术（ＬＢ）及其它方法在制备聚合物纳米复合膜时的优劣。ＳＡ法由于操作简单、膜的结构稳定性较高,因此较ＬＢ技术等具有更大的实用价值。利用ＳＡ法,可以制备各种有机聚电解质与其带相反电荷的有机聚电解质、粘土化合物及无机纳米颗粒等组成的聚合纳米复合膜。     

用椭偏光谱法测量很薄固体膜的光性

本文讨论了利用棉偏光谱法测量很薄固体膜的光性的原理和方法,包括椭偏计算模型的建立、模型的合适性等问题,考察了环境介质-薄膜-衬底三根系统和环境介质-薄膜-界面过渡层-衬底四相系统,并引入了一种简化椭偏计算的方法。此外,本文也给出了两个研究实例,包括Si衬底上的Pt膜和PtSi膜。     

In Situ Formation of Particulate Silica in Natural Rubber Matrix by the Sol-Gel Reaction

The sol-gel reaction of tetraethoxysilane was conducted in natural rubber (NR) matrix to obtain NR/in situ silica mixtures. In other words, in situ filling of silica onto NR was conducted. The mixtures were compounded with curing regents, and their viscosities were evaluated. The in situ silica with a coupling agent afforded the lowest viscosity compared not only with a conventional silica (VN-3) but also with a carbon black (HAF). The curing behaviors were most favorable for in situ silica compound. Physical properties of the vulcanizates were also evaluated, and again in situ silica stock gave the best result.     

金属锌表面膜形成的椭圆偏振技术研究

介绍了近年作者课题组使用椭圆偏振技术研究金属锌表面氧化膜的形成,包括多晶锌表面自然氧化物薄膜的形成及其光学性能和电子结构、不同气氛自然氧化物膜的生长研究以及在碱性碳酸盐介质金属锌的电化学过程等方面的工作. 旨在通过原位和非原位椭圆偏振技术了解金属锌表面氧化物膜层的光、电性能以及膜层结构的改变和生长动力学,这对评估锌氧化层的总体性能有着重要意义.     

Ellipsometry and Infrared Reflection Absorption Spectroscopy of Adsorbed Layers of Soluble Surfactants at the Air-Water Interface

Optical techniques play an increasingly important role in the characterization of microstructure and surface densities of thin films at various interfaces. In this study, ellipsometry and infrared reflection absorption spectroscopy (IRRAS) were used for determining the surface densities of adsorbed layers of cationic surfactants in situ at the air-water interface. The surfactants were N(alpha)-lauroyl-arginine methyl ester (LAM) and N(alpha), N(omega)-bis(N(alpha)-lauroyl-arginine)-alpha,omega-alkylidenediamide (C(6)(LA)(2)). In ellipsometry, the ellipsometric phase angle Delta was obtained at various surfactant concentrations and was referenced to that of the solvent. Three algorithms were used for analyzing the data. The surface densities are 3.3+/-0.3x10(-6) mol/m(2) at 1 mM for LAM and 1.5+/-0.3x10(-6) mol/m(2) at 0.1 mM for C(6)(LA)(2) by using an algorithm for which the monolayer thickness was estimated from molecular modeling. The corresponding surface densities from literature surface tension data and the Gibbs adsorption isotherm procedure are 2.2+/-0.4x10(-6) mol/m(2) and 1.2+/-0.2x10(-6) mol/m(2), respectively. In addition, IRRAS spectra were obtained from monolayers of LAM and C(6)(LA)(2) at the air-water interface. The frequencies of the methylene stretching vibration bands indicate that the monolayers are liquid-like. The surface densities were determined from the reflectance-absorbance data by using the model of either an isotropic film or an anisotropic film on the aqueous subphase. The IRRAS-based surface densities from either model, by using DPPC monolayers for calibration, are 2.4+/-0.7x10(-6) mol/m(2) at 1 mM for LAM and 1.5+/-0.6x10(-6) mol/m(2) at 0.1 mM for C(6)(LA)(2), which are in fair agreement with the ellipsometry- and the surface-tension-based surface densities. Copyright 2001 Academic Press.     

由有机LB膜制备无机超薄膜

无机超薄膜的优异性能引起人们的广泛兴趣，本文介绍几种由有机ＬＢ膜制备无机超薄膜的方法。     

二氧化钛超薄膜的组装

近年来LB膜技术和超微粒子研究的发展，将两者有效地结合起来组装了与量子电子学、非线性光学、光电化学、化学生物传感器有关的纳米量级无机半导体材料［‘－‘j．其中TIO。纳米薄膜材料已在太阳能电池反射膜、压电铁电薄膜、电致显示器件［‘j、可逆光电池和超导薄膜［’］研究中都显示了广阔的应用前景．这类薄膜制备多采用化学气相沉积（CVD）技术和原子层外延．也有人把LB技术应用于纳米粒子的组装来制备TIO。超薄膜［”’j二本文利用烷氧基钛在水／空气界面上发生的溶胶一凝胶化反应制备TIO。基胶态粒子及其固态凝聚膜，将其与…     

Structure of Composite Films Containing Polyaniline Studied by DSC

A structural study of conductive composite films consisting of ethylene-co-vinylacetate (EVA) copolymer, polyaniline (PANI) and dodecylbenzenesulfonic acid (DBSA), a part of which being complexed with PANI, was performed by using differential scanning calorimetry (DSC) and presented for the first time. An additional crystalline phase is formed during the film formation by thickening EVA chain-folded lamellae with participation of‘free’ DBSA molecules at lower net PANI content (up to 5 mass%) and of both ‘free’ and complexed DBSA molecules (up to 7.5 mass%). At higher PANI content PANI-DBSA complex starts to form its own crystals and at 17.5 mass% of PANI mixed crystals of EVA with ‘free’ DBSA alkyl chains are preferably formed. It is also found that the Fox' equation correlating the glass transition temperature of a miscible blend system with its composition can be actually used in estimating the miscibility of EVA/PANI blends no matter the presence of DBSA. This revised version was published online in August 2006 with corrections to the Cover Date.