Synthesis of the southern furan segment of furanocembranoids

Abstract

A convergent synthesis of the southern furan segment of novel furanocembranoids from Croton oblongifolius has been accomplished involving silver-catalyzed cyclization of alkynyl diol as the key step towards 2, 5-disubstituted furan ring formation.     

2-巯基苯并咪唑保护的铜纳米团簇的制备及银离子检测

以2-巯基苯并咪唑为保护剂,聚乙烯吡咯烷酮为稳定剂,水合肼为还原剂,“一锅法”合成2-巯基苯并咪唑保护的,高稳定性、强荧光、大斯托克斯位移的铜纳米团簇(Cu NCs),并用于检测水样中的银离子含量。采用透射电子显微镜(TEM)和X射线光电子能谱(XPS)对铜纳米团簇的结构进行表征,通过荧光光谱和紫外可见光谱对其光学性能进行研究。研究表明:该铜纳米团簇的最大激发和发射波长分别为340和558 nm,在日光灯和紫外灯下分别为无色和橙色。Cu NCs具有较高的分散性,尺寸大小为2~3 nm。在最佳反应条件下,铜纳米团簇可以选择性地被银离子猝灭,且灵敏度高,线性范围为1~40μmol/L,检测限为0.5μmol/L。该方法用于检测实际水样(自来水、湖水)中银离子的浓度,结果令人满意,表明在环境监测中有非常高的应用价值。     

The ordered phase of methylammonium lead chloride CH3ND3PbCl3

The perovskite-structured compound methylammonium lead chloride orders into a low-temperature phase of space group Pnma, in which at 80 K each of the orthorhombic axes , and is doubled with respect to the room temperature disordered cubic phase (). The structure was solved by ab initio methods using the programs EXPO and FOX. This unusual cell basis for space group Pnma is not that of a standard tilt system. This phase, in which the methylammonium ions, are ordered shows distorted octahedra. The octahedra possess a bond angle variance of 60.663°² and a quadratic elongation of 1.018, and are more distorted than those in the ordered phase of methylammonium lead bromide. There is also an alternating long and short Pb-Cl bond along a, due to an off-center displacement of Pb within the octahedron. This suggests that the most rigid unit is actually the methylammonium cation, rather than the PbCl₆ octahedra, in agreement with existing spectroscopic data.     

A Simple Hydrothermal Route to Large‐Scale Synthesis of Uniform Silver Nanowires

This paper describes the preparation of uniform silver nanowires by reducing freshly prepared silver chloride with glucose at 180 °C for 18 hours in the absence of any surfactants or polymers. Scanning electron microscopy studies indicated that the silver nanowires are about 100 nm in diameter and up to 500 μm in length. High‐resolution transmission electron microscopy analyses showed that the silver nanowires grow perpendicularly to the Ag(200) plane. The silver nanowires are believed to grow through a solid–solution–solid process. Some influential factors on the growth of silver nanowires are also discussed.     

Insights on the origin of the structural phase transition in BaV10O15 from electronic structure calculations and the effect of Ti-doping on its structure and electrical transport properties

Band structure calculations at the level of LMTO-ASA provide insight into the electronic structure of BaV₁₀O₁₅ and the origin of the structural phase transition. A crystal orbital Hamiltonian population/integrated crystal orbital Hamiltonian population analysis provides evidence that the crystallographic phase transition is driven by V-V bond formation. As well, the energy bands near the Fermi level are very narrow, <1 eV, consistent with the fact that the observed insulating behavior can be due to electron localization via either Mott-Hubbard correlation and/or Anderson disorder. The partial solid solution, BaV_10−xTi_xO₁₅, was examined to study the effect of Ti-doping at the V sites on the structure and electronic transport properties. In spite of the non-existence of “BaTi₁₀O₁₅”, the limiting x=8, as indicated by a monotonic increase in the cell volume and systematic changes in properties. This limit may be due to the difficulty of stabilizing Ti²⁺ in this structure. For x=0.5 both the first order structural phase transition and the magnetic transition at 40 K are quenched. The samples obey the Curie-Weiss law to x=3 with nearly spin only effective moments along with θ values which range from −1090 K (x=0.5) to −1629 K (x=3). For x>3 a very large, ∼2×10⁻³ emu/mol, temperature independent (TIP) contribution dominates. Conductivity measurements on sintered, polycrystalline samples show semiconducting behavior for all compositions. Activation energies for Mott hopping derived from high temperature data range from ∼0.1 eV for x=0-1 and fall to a plateau of 0.06 eV for x=3-7. Low temperature data for x=3, 5 and 7 show evidence for Mott variable range hoping (VRH) with a T^1/4 law and in one case between 5 and 17 K, a Efros-Shklovskii correlated hopping, T^1/2 law, was seen, in sharp contrast to BaV₁₀O₁₅ where only the E-S law was observed up to 75 K. Seebeck coefficients are small (<35 μV/K), positive, roughly TIP and increase with increasing x up to x=5. This may point to a Heikes hopping of holes but a simple single carrier model is impossible. The compositions for x>3 are remarkable in that local moment behavior is lost, yet a metallic state is not reached. The failure of this system to be driven metallic even at such high doping levels is not fully understood but it seems clear that disorder induced carrier localization plays a major role.     

乙醇 /水混合溶剂沉淀制备纳米BaF2及粒径控制

采用水和乙醇混合溶剂沉淀的方法制备了不同粒径的BaF₂纳米粉体。用XRD、TEM和FSEM表征了粉体的粒径和形貌。研究了陈化时间、水和乙醇的体积比对BaF₂纳米粉体的粒径和形貌的影响。结果表明，随混合溶剂中乙醇含量升高，沉淀粒径减小。BaF₂沉淀粒径的倒数和溶剂介电常数的倒数呈线性关系，据此关系可以控制BaF₂纳米粉体的粒径。     

地质样品中金,银,铊等元素的连续原子吸收光谱法测定

本文提出了一个一次称样连续测定金、银、铊的简便、快速的新方法。该法是以泡塑吸附金、铊，使银等定量地保留在溶液中。泡塑上的铊用ＥＤＴＡ解脱后，再用硫脲溶液继续解脱金，然后，采用原子吸收光谱法连续测定金、银、铊。方法用于黄铁矿、方铅等单矿矿物及岩石、土壤样品中ｘｎｇ／ｇ～ｘｘｘμｇ／ｇ金、银、铊的测定，获得满意结果。     

TiCl4-Cr还原偶联活泼卤化物及芳醛、芳酮的研究

低价钛化合物在有机合成和有机反应中有着广泛的应用。我们曾研究了低价钛对α,α,α-三卤甲基苯的脱卤偶联、对2,2-二芳     

Progress on phthalocyanine-conjugated Ag and Au nanoparticles: Synthesis,characterization, and photo-physicochemical properties

Phthalocyanine (Pc) complexes are an important class of dyes with numerous (e.g., biological, photophysical, and analytical) applications. Among the methods used to improve the properties of these complexes, one should mention the introduction of different substituents, variation of the central metal ion, ligand exchange, and conjugation to nanomaterials (e.g., carbon-based nanomaterials and metal nanoparticles (NPs)). This work briefly reviews Pc complex conjugation to Ag and Au NPs, highlights the different NP shapes, and discusses the diversity of conjugation approaches. Moreover, the use of UV–Vis spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, atomic force microscopy, dynamic light scattering and Fourier transform infrared spectroscopy to characterize Pc-NP hybrids is summarized. The effect of conjugation on Pc photo-physicochemical properties (fluorescence, singlet oxygen generation, triplet state formation, and optical limiting behavior) is discussed, and future perspectives for the synthesis and applications of new hybrids are provided.