A new organic semiconducting polymer from Cu2+ chelate of poly(vinyl alcohol)and iodine

A new, easily processed, organic semiconductor was prepared from poly(vinyl alcohol) (PVA). The Cu²⁺ chelate of PVA exhibited excellent surface resistivity around 10³ Ω cm^?2 when modified with iodine. Favorable conditions for preparing the chelate effective for the conduction were investigated. The resistivity was significantly affected by the amounts of cupric salts and iodine, satisfactory results being given by more than 15 wt% of cupric salts and about 4 wt% of iodine. Effects of molecular weight of PVA and the chelate structure were also studied.     

Reaction of (trimethylstannyl) copper reagents with α, β-acetylenic esters

The stereochemical course of the conjugate addition of various (trimethylstannyl)cuprate (or copper) reagents to α, β-acetylenic esters is dependent on the constitution of the reagent and on the structure of the substrate.     

碘催化合成环己酮1,2-丙二醇缩醛

研究了单质碘催化环已酮与1，2-丙二醇的缩醛化反应，考察了反应时间、醇酮摩尔比、催化剂用量、带水剂用量等因素对环已酮乙二醇缩醛收率的影响。结果表明，在回流条件下，醇酮摩尔比为1．3，催化剂用量为52mg(约占反应体系总摩尔数的0．007％)，带水剂环己烷用量为8mL，反应40min后缩醛收率可达79．2％。     

纳米多孔钯催化亚胺化合物加氢还原反应研究

本文首次研究了以H2为氢源、纳米多孔钯催化亚胺化合物的加氢还原反应.结果表明:在氢气压力为101.325 kPa,溶剂为无水乙醇,反应温度为30℃,反应时间24 h,催化剂物质的量分数为5%的条件下,纳米多孔钯可以高效催化亚胺化合物的加氢还原反应,高选择性、高产率地生成一系列仲胺,仲胺的产率在93%~96%之间.该反应官能团兼容性好,底物范围广,带有甲基、甲氧基、氰基和羟基等基团的亚胺都可以顺利发生还原反应生成相应的仲胺.催化剂重复使用5次后,活性未出现明显降低.     

Bond length alternation in cyclic polyenes. II. Unrestricted hartree–fock method

The problem of bond length alternation in cyclic polyene models as described by the Pariser–Parr–Pople π-electron Hamiltonian, together with an empirical quasi harmonic σ-core potential is investigated using the unrestricted Hartree–Fock wave function employing different spatial orbitals for different spins. It is shown that in contrast to the restricted Hartree–Fock method, which favors bond alternation in large cyclic polyenes, the unrestricted Hartree–Fock method stabilizes the symmetric structures with equidistant internuclear separation. An assessment of the amount of correlation error recovered by the unrestricted Hartree–Fock procedure is examined and the qualitatively different behavior of the cyclic polyene models when described by restricted and unrestricted Hartree–Fock wave functions is discussed from this viewpoint.     

Nanoscale molecular patterns fabricated by using scanning near-field optical lithography

Nanometer-scale patterns have been created in self-assembled monolayers by using a scanning near-field optical microscope coupled to an ultra-violet laser emitting light at a wavelength of 244 nm. Sharp, chemically well-defined features with dimensions as small as 40 nm have been created routinely, and on occasions line widths of 25 nm (lambda/10) have been achieved. Because of the wide range of photochemical methods available for surface derivatization, this approach promises to provide a flexible and versatile route to the generation of molecular and biological nanostructures for a wide range of applications.     

淀粉-醋酸乙酯-丙烯酸乙酯接枝共聚物

在硝酸铈铵(CAN)以及硫酸亚铁/过氧化氢两种引发体系中，进行了丙烯酸乙酯(EA)、醋酸乙烯酯(VAc)与玉米淀粉的接枝共聚。用质子核磁共振研究了接枝支链的化学组成、用X衍射研究接枝共聚物结晶结构的变化、用扫描电镜研究了材料的微观结构、并研究了共聚物的亲水性。制备了接枝淀粉、聚乙烯醇的生物降解塑料，测定了材料的力学性能以及疏水性。     

Styryl dyes derived from bis boron diketonates

Bis boron diketonates are prepared from β-diketones or o-acylphenols or naphthols with boron trichloride or boron tribromide. The bis boron diketonates that contain methyl groups reacted with some aromatic aldehydes, giving styryl dyes, most of which showed high extinction coefficients.     

Formation Mechanisms of Sol-Gel-Derived Hydroxyapatite Using Different Thermal Processings

Sol-gel-derived hydroxyapatite (HA) precursors were calcined by two thermal processings, a rapid-thermal-calcine (RTC) heating at 100–600°C/min and a conventional-furnace-calcine (CFC) heating at 1.67°C/min, respectively. X-ray diffraction patterns revealed that the onset temperature of HA crystallization is lower in RTC, 350°C, as compared to 600°C in CFC. Pyrolytic-GC/MS programs showed that the evolved gases out of a sample subjected to RTC are mainly H₂O, N₂O and ethylamine, while those of a sample subjected to CFC are CO₂ and small organic molecules. The results leads to models that RTC can quickly remove organic portion of the gel networks, leading to a porous surface morphology and a collapse of gel networks at local areas, so that HA crystallite nucleation is facilitated due to intimate contacts among inorganic species at lower temperatures. On the other hand, slow evolution of organics during CFC leads to carbonaceous residues that isolate the inorganic species and inhibit nucleation of HA crystallites until at a higher temperature.     

Structural insight into [Fe–S2–Mo] motif in electrochemical reduction of N2 over Fe1-supported molecular MoS2

The catalytic synthesis of NH₃ from the thermodynamically challenging N₂ reduction reaction under mild conditions is currently a significant problem for scientists. Accordingly, herein, we report the development of a nitrogenase-inspired inorganic-based chalcogenide system for the efficient electrochemical conversion of N₂ to NH₃, which is comprised of the basic structure of [Fe–S₂–Mo]. This material showed high activity of 8.7 mg_NH3 mg_Fe⁻¹ h⁻¹ (24 μg_NH3 cm⁻² h⁻¹) with an excellent faradaic efficiency of 27% for the conversion of N₂ to NH₃ in aqueous medium. It was demonstrated that the Fe₁ single atom on [Fe–S₂–Mo] under the optimal negative potential favors the reduction of N₂ to NH₃ over the competitive proton reduction to H₂. Operando X-ray absorption and simulations combined with theoretical DFT calculations provided the first and important insights on the particular electron-mediating and catalytic roles of the [Fe–S₂–Mo] motifs and Fe₁, respectively, on this two-dimensional (2D) molecular layer slab.

A nitrogenase-inspired inorganic-based chalcogenide system containing [Fe–S₂–Mo] motif is developed for the efficient electrochemical conversion of N₂ to NH₃.