Formation of metallic NbSe2 nanotubes and nanofibers

We succeed in synthesizing NbSe₂ nanotubes along with nanofibers by chemical vapor transportation. They are stable crystalline systems and can be synthesized reproducibly in a nearly equilibrium reacting process. We have investigated these nanosize structures of NbSe₂ by transmission electron microscopy and electron diffraction. Both of the structures have a similar size of 100–200 nm in diameter. While nanotubes consist of rolled-up NbSe₂ layers, nanofibers are a pile of thin flat layers. We propose a mechanism of the formation of NbSe₂ nanotubes and nanofibers on the basis of deseleniditive transition from a NbSe₃ fiber-shaped crystal. We also measured electrical resistance of the nanofibers with conductive atomic force microscopy and demonstrated that the material show metallic behavior at room temperature.     

掺Perylene的PVK薄膜荧光谱及发光机理

用高荧光效率的有机染料芘(perylene)掺杂聚乙烯咔唑(PVK),其荧光光谱与芘的发射光谱基本一致,而且亮度比纯芘发光提高十多倍,说明发光主要来自芘分子,并在PVK和perylene之间存在十分有效的能量传递或电荷转移过程,荧光谱强度随掺杂浓度的变化关系说明存在一个最佳的掺杂浓度比.分析PVK和perylene之间可能发生的能量转移过程,认为从PVK到perylene这种能量转移与实验不符;分析PVK和perylene薄膜的光致发光过程,认为从(PVK+)→(perylene+)和从(PVK-)→(p     

Quantum-Chemical Study of the Profiles of Reactions that Form Pyrrole Anion N-Adducts with CS<Subscript>2</Subscript> and CO<Subscript>2</Subscript>

The profiles of reactions leading to pyrrole anion N-adducts with CO₂ and CS₂ have been studied by the ab initio (RHF/6-31+G*, MP2/6-31+G*) and density functional (B3LYP/6-31+G*) methods. Addition of the pyrrole anion to the carbon disulfide molecule is accompanied by the appearance of a minimum corresponding to a pre-reaction complex. The transformation of the complex to the N-pyrrolyldithiocarboxylate anion occurs via a low activation barrier, which is due to repolarization of the C=S bonds. The profile of the reaction leading to the pyrrole anion N-adduct with CO₂ does not contain any intermediate stationary points throughout the whole route from reagents to products.Original Russian Text Copyright © 2004 by V. B. Kobychev, N. M. Vitkovskaya, I. L. Zaitseva, and B. A. Trofimov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 990–993, November–December, 2004.     

Mechanism of the thermal decomposition of nitrates from graphite furnace mass spectrometry studies

A basically new mechanism of the thermal decomposition of solids is proposed to explain the mass spectral observations of gaseous molecules of CoO, CuO, Cu₂O, NiO, PbO and Mg(OH)₂ during the low-temperature decomposition of the anhydrous and hydrated nitrates of these metals. The mechanism consists of two stages: congruent gasification of all reaction products irrespective of their saturated vapor pressure and subsequent condensation of the low-volatility species (oxides and hydroxides). The partial pressures of these species at the appearance temperatures calculated from this theory for the first stage of the process (1–50 mPa) are in agreement with the detection limits of the quadrupole mass spectrometers used in these experiments. The proposed mechanism is supported by other available data obtained by thermal analysis.     

Ge_x Si_(1-x)/Si超晶格中纵声学声子的喇曼散射强度研究

本文用光弹理论,在全面考虑了超晶格中两种材料的声速,质量密度和光弹常数存在差别的基础上,计算了Ge_xSi_(1-x)/Si超晶格中折迭纵声学声子的喇曼散射强度,在高达50cm~(-1)的频率范围内,理论值和实验符合得很好。     

铽－甲基吲哚乙酰丙酮三元配合物发光过程研究

测定和分析了ＲＥ．Ｌ１．Ｌ２（ＲＥ＝Ｔｂ（Ⅲ）、Ｇｄ（Ⅲ），Ｌ１＝３Ｍ（３甲基吲哚－１－乙酰基丙酮），Ｌ２＝ＴＰＰＯ、Ｐｈｅｎ、Ｄｉｐｙ）三元配合物的荧光光谱、磷光光谱、磷光寿命及变温荧光光谱等．讨论了Ｔｂ（Ⅲ）与配体之间的能级匹配和Ｌ１与Ｌ２的三重态之间传能的问题，说明了影响这些三元配合物荧光效率的主要因素及其发光过程．     

具有新光学性质的Zn-Zn2SiO4纳米同轴线阵列

采用气相沉积技术在Si衬底上生长了Zn-Zn₂SiO₄芯-壳结构纳米同轴线阵列。根部呈笋状的纳米同轴线,直径约100nm,长度可以超过10μm;同轴线芯直径约50nm、壳层厚约25nm。通过X射线衍射的表征以及能量色散谱的线扫描,确定纳米同轴线的芯为Zn,壳层为Zn₂SiO₄。我们提出了一种新的生长机制,同时也为生长均匀的纳米同轴线提供一种新的技术。观察阴极荧光谱发现,纳米同轴线有三个主要发光带:强度最大的中紫外300nm发光、较弱的可见光区560nm以及红外谱区865nm的发光。对纳米同轴线截面的300nm发光峰观测发现,中紫外发光来源于Zn₂SiO₄壳层。正是这种同轴线的结构,使得其具备特殊的光学性质。     

Synthesis and characterization of poly(ethylene oxide‐co‐ethylene carbonate) macromonomers and their use in the preparation of crosslinked polymer electrolytes

Methacrylate‐functionalized poly(ethylene oxide‐co‐ethylene carbonate) macromonomers were prepared in two steps by the anionic ring‐opening polymerization of ethylene carbonate at 180 °C, with potassium methoxide as the initiator, followed by the reaction of the terminal hydroxyl groups of the polymers with methacryloyl chloride. The molecular weight of the polymer went through a maximum after approximately 45 min of polymerization, and the content of ethylene carbonate units in the polymer decreased with the reaction time. A polymer having a number‐average molecular weight of 2650 g mol^?1 and an ethylene carbonate content of 28 mol % was selected and used to prepare a macromonomer, which was subsequently polymerized by UV irradiation in the presence of different concentrations of lithium bis(trifluoromethanesulfonyl)imide salt. The resulting self‐supportive crosslinked polymer electrolyte membranes reached ionic conductivities of 6.3 × 10^?6 S cm^?1 at 20 °C. The coordination of the lithium ions by both the ether and carbonate oxygens in the polymer structure was indicated by Fourier transform infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2195–2205, 2006     

On the behavior of ECN/RED gateways under a large number of TCP flows: Limit theorems

We consider a discrete-time stochastic model of an ECN/RED gateway where competing TCP sources share the link capacity. As the number of competing flows becomes large, the asymptotic queue behavior (normalized by the number of flows) at the gateway can be described by a simple recursion and the throughput behavior of individual TCP flows becomes asymptotically independent. A Central Limit Theorem complement is also presented, yielding a more accurate characterization of the asymptotic queue size. These results suggest a scalable yet accurate model of this complex large-scale stochastic feedback system, and crisply reveal the sources of queue fluctuations. This work was prepared through collaborative participation in the Communications and Networks Consortium sponsored by the U.S. Army Research Laboratory under the Collaborative Technology Alliance Program, Cooperative Agreement DAAD19-01-2-0011. This work was also supported by the Space and Naval Warfare Systems Center—San Diego under Contract No: N66001-00-C-8063. The views and conclusions contained in this document are those of the authors and should not be interpreted as representing the official policies, either expressed or implied, of the Army Research Laboratory or the U.S. Government.     

Recent studies on phosphorus-bridging carbonyl derivatives: organophosphorus analogs of aldehydes and ketones

Reactions of disodium tetracarbonylferrate, Na₂Fe(CO)₄, with sterically hindered dialkylaminodichlorophosphines, R₂NPCl₂ (R₂N=diisopropylamino, dicyclohexylamino, and 2,2, 6, 6-tetramethylpiperidino) in diethyl ether lead to the air-stable phosphorus-bridging carbonyl derivatives (R₂NP)₂COFe₂(CO)₆ as the major products. The phosphorus-bridging carbonyl group in (i-Pr₂NP)₂COFe₂(CO)₆ has been found to undergo the following types of reactions: 1)Reduction, 2)Acylation, 3)Extrusion of the carbonyl group. The mechanisms of the reactions have been considered.This work was presented at the Workshop «The Modern Problems of Heteroorganic Chemistry» held on the ship «Nikolai Bauman» during the period May 8–13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1858–1867, November, 1993.