Parity Alternation of Silicon-doped Ternary Cationic Clusters HC_nSi_2~+(n=1～9)

Systematic study on the electronic/geometrical structures and the parity alternation effect of silicon-doped ternary cationic clusters HCnSi2＋（n = 1 ~9） have been carried out at the coupled cluster level. The ground-state （G-S） isomers of the clusters have been defined. The C, chains of the G-S isomers display polyacetylene-like structures. The even-n cations are more stable than the odd-n ones. Such a trend of even/odd alternation has been elaborated based on concepts of the bond character, atomic charge, incremental binding energy, ionization potential, proton affinity and fragmentation energies of the systems. The findings accord with the relative intensities of HC,,Si2＋ species recorded in the related mass spectrometric experiments.     

A Promising Electrochemical Platform for Dopamine and Uric Acid Detection Based on a Polyaniline/Iron Oxide-Tin Oxide/Reduced Graphene Oxide Ternary Composite

A ternary polyaniline/Fe₂O₃-SnO₂/reduced graphene oxide (PFSG) nanocomposite was prepared using a simple two-step hydrothermal treatment. The composite was applied as a glassy carbon electrode modifier (GCE) to enhance dopamine (DA) and uric acid (UA) detection. The ternary PFSG composite was compared with its binary precursor Fe₂O₃-SnO₂/reduced graphene oxide (FSG). The influence of the modified GCE electrodes on their performance as a sensing platform was determined. GCE/PFSG showed better sensing parameters than GCE/FSG due to the introduction of polyaniline (PANI), increasing the electrocatalytic properties of the electrode towards the detected analytes. GCE/PFSG enabled the detection of low concentrations of DA (0.076 µM) and UA (1.6 µM). The peak potential separation between DA and UA was very good (180 mV). Moreover, the DA oxidation peak was unaffected even if the concentration of UA was ten times higher. The fabricated sensor showed excellent performance in the simultaneous detection with DA and UA limits of detection: LOD_DA = 0.15 µM and LOD_UA = 6.4 µM, and outstanding long-term stability towards DA and UA, holding 100% and 90% of their initial signals respectively, after one month of use.     

Stability of aqueous foam films and foams containing polymers: Discrepancies between different length scales

Polymer-stabilized foams and foam films have received considerable attention during the past years. This review paper gives an overview of recent studies dealing with polyelectrolyte/surfactant mixtures, proteins, and microgels adsorbed at single air/water interfaces, in foam films and in macroscopic foams. These polymeric systems have in common that their structure or shape changes when adsorbing at an air/water interface. These structural changes in comparison to their bulk behavior greatly influence the properties of foam films and foams. Regarding the foam stability, formation of adsorbed layers or aggregates plays an important role. The discrepancy between stabilization of macroscopic foams and destabilization of single foam films might be attributed to the blockage of Plateau borders and, therefore, slowed down drainage. Another important parameter is the interfacial viscoelasticity.     

Ionothermal Synthesis of Imide‐Linked Covalent Organic Frameworks

Covalent organic frameworks (COFs) are an extensively studied class of porous materials, which distinguish themselves from other porous polymers in their crystallinity and high degree of modularity, enabling a wide range of applications. COFs are most commonly synthesized solvothermally, which is often a time‐consuming process and restricted to well‐soluble precursor molecules. Synthesis of polyimide‐linked COFs (PI‐COFs) is further complicated by the poor reversibility of the ring‐closing reaction under solvothermal conditions. Herein, we report the ionothermal synthesis of crystalline and porous PI‐COFs in zinc chloride and eutectic salt mixtures. This synthesis does not require soluble precursors and the reaction time is significantly reduced as compared to standard solvothermal synthesis methods. In addition to applying the synthesis to previously reported imide COFs, a new perylene‐based COF was also synthesized, which could not be obtained by the classical solvothermal route. In situ high‐temperature XRPD analysis hints to the formation of precursor–salt adducts as crystalline intermediates, which then react with each other to form the COF.     

Properties of polymer blends and triblock copolymers obtained by neutron scattering

Static and dynamic scattering properties of polymer blends and block copolymers are examined within the random phase approximation (RPA). A self-consistent theoretical scheme for a simultaneous analysis of elastic and quasielastic scattering data is presented. The case of a triblock copolymer made of an ordinary central block and two deuterated lateral blocks in a matrix of deuterated homopolymers is considered in detail. The theoretical predictions of the RPA are compared with the experimental data obtained by elastic neutron scattering experiments using mixtures of deuterated poly(dimethylsiloxane) homopolymers and copolymers made of three blocks of approximately equal sizes. The lateral blocks are deuterated poly(dimethylsiloxane) and the central one is an ordinary poly(dimethylsiloxane). A good agreement is found in the whole range of wavevectors covered by the experiments. An extension of the RPA to the analysis of the dynamical scattering data for the same systems is put forward. It is shown how the time relaxations of the bare response functions obtained from the single chain dynamics are used to extract the intermediate scattering function characterizing the system of interacting chains. © 1996 John Wiley & Sons, Inc.     

SnSxSe2-x单晶纳米片的可控制备与表征

锡二硫族化合物可以通过改变硫和硒的含量来连续调控三元合金材料的带隙、载流子浓度等物理化学性质,在电子和光电子器件应用上具有巨大的潜力。本文采用化学气相沉积(CVD)技术可控地制备了不同元素组分的SnS_xSe_2-x(x=0,0.2,0.5,0.8,1.0,1.2,1.5,1.8,2.0)单晶纳米片。采用扫描电子显微镜(SEM)、原子力显微镜(AFM)、能量色散X射线光谱(EDS)、透射电子显微镜(TEM)以及拉曼光谱等手段对SnS_xSe_2-x纳米片进行了综合表征。结果表明本方法成功实现了元素百分比可调的SnS_xSe_2-x单晶纳米片的可控制备。重点研究了依赖于元素百分比的SnS_xSe_2-x的拉曼特征谱,实验结果与基于密度泛函理论(DFT)的第一性原理计算得到的SnS_xSe_2-x的拉曼仿真谱高度吻合,理论计算结果较好地诠释了实验拉曼光谱发生变化的原因。本研究提供了一种元素百分比可调的三元SnS_xSe_2-x单晶纳米片的可控制备方法,同时对锡二硫族化合物的明确、无损识别提供了方案。     

Metamorphic InAs(Sb)/InGaAs/InAlAs nanoheterostructures grown on GaAs for efficient mid-IR emitters

High-efficiency semiconductor lasers and light-emitting diodes operating in the 3–5?μm mid-infrared (mid-IR) spectral range are currently of great demand for a wide variety of applications, in particular, gas sensing, noninvasive medical tests, IR spectroscopy etc. III-V compounds with a lattice constant of about 6.1?Å are traditionally used for this spectral range. The attractive idea to fabricate such emitters on GaAs substrates by using In(Ga,Al)As compounds is restricted by either the minimum operating wavelength of ～8?μm in case of pseudomorphic AlGaAs-based quantum cascade lasers or requires utilization of thick metamorphic In_xAl_1-xAs buffer layers (MBLs) playing a key role in reducing the density of threading dislocations (TDs) in an active region, which otherwise result in a strong decay of the quantum efficiency of such mid-IR emitters. In this review we present the results of careful investigations of employing the convex-graded In_xAl_1-xAs MBLs for fabrication by molecular beam epitaxy on GaAs (001) substrates of In(Ga,Al)As heterostructures with a combined type-II/type-I InSb/InAs/InGaAs quantum well (QW) for efficient mid-IR emitters (3–3.6?μm). The issues of strain relaxation, elastic stress balance, efficiency of radiative and non-radiative recombination at T?=?10–300?K are discussed in relation to molecular beam epitaxy (MBE) growth conditions and designs of the structures. A wide complex of techniques including in-situ reflection high-energy electron diffraction, atomic force microscopy (AFM), scanning and transmission electron microscopies, X-ray diffractometry, reciprocal space mapping, selective area electron diffraction, as well as photoluminescence (PL) and Fourier-transformed infrared spectroscopy was used to study in detail structural and optical properties of the metamorphic QW structures. Optimization of the growth conditions (the substrate temperature, the As₄/III ratio) and elastic strain profiles governed by variation of an inverse step in the In content profile between the MBL and the InAlAs virtual substrate results in decrease in the TD density (down to 3?×?10⁷ cm^?2), increase of the thickness of the low-TD-density near-surface MBL region to 250–300?nm, the extremely low surface roughness with the RMS value of 1.6–2.4?nm, measured by AFM, as well as rather high 3.5?μm-PL intensity at temperatures up to 300?K in such structures. The obtained results indicate that the metamorphic InSb/In(Ga,Al)As QW heterostructures of proper design, grown under the optimum MBE conditions, are very promising for fabricating the efficient mid-IR emitters on a GaAs platform.     

Effect of the nature of the support for copper-cerium oxide catalysts on selective oxidation of CO in hydrogen-rich mixtures

We have studied the catalytic properties of copper-cerium oxide catalysts, supported on zirconium, aluminum, titanium, and manganese oxides, in the reaction of selective oxidation of CO in hydrogen-rich mixtures. We have shown that the high activity and selectivity of catalysts supported on zirconium and aluminum oxides is connected with the presence of (in addition to divalent copper) higher amounts of copper in the (+1) oxidation state in the catalysts. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 2, pp. 119–124, March–April, 2006.     

三元体系Y(ClO4)3·3H2O—B15C5—CH3OH(25℃)的半微量相平衡研究

采用半微量相平衡方法研究了三元体系Ｙ（ＣｌＯ４）３．３Ｈ２Ｏ－Ｂ１５Ｃ５－ＣＨ３ＯＨ在２５℃的溶解度，测定了各饱和溶液的折光率。该体系在２５℃生成三种化学计量的配合物，其组成分别为：４Ｙ（ＣｌＯ４）３．３Ｂ１５Ｃ５．１２Ｈ２Ｏ．１２Ｃｈ３ＯＨ（Ｉ），Ｙ（ＣｌＯ４）３．２Ｂ１２Ｃ５．３Ｈ２Ｏ．Ｃｈ３ＯＨ（Ⅲ），其中配合物（Ｉ）和（Ⅱ）是溶解不一致化合物。在甲醇溶剂中，分离制备了配合物（Ⅲ），在６９－     

Estimation of the Nitta-Chao Parameters for the ether-group. Ether + n-alkane mixtures

In this work we have estimated the structural and interactional parameters of the ether- group for the group-contribution model of Nitta-Chao using a extensive experimental database of thermodynamic properties of ethers (monoethers, polyethers and acetals) and ether + n-alkane and ether + ether mixtures. The results obtained by Nitta-Chao model with this parameters get closer to the experimental values than those obtained with parameters of Eckart et al. (1986). The thermodynamic properties obtained by the Nitta-Chao model with old and new parameters were compared to predictions by other models such as Flory (1965) theory, DISQUAC (Kehiaian, 1977) model and UNIFAC model (versions of Dang and Tassios, 1986, and Larsen et al., 1987).