甲基丙烯酸甲酯悬浮聚合实验教学的改进

选用氢氧化镁为分散剂,甲基丙烯酸甲酯(MMA)为单体,进行悬浮聚合反应,研究了分散剂用量、引发剂用量、水和单体比、搅拌速度、反应温度及反应时间对聚合物珠粒大小、均匀程度和产率的影响。结果表明:与目前高分子实验教材普遍选用的以聚乙烯醇(PVA)为分散剂的悬浮聚合反应相比,以氢氧化镁为分散剂,具有操作简单、聚合时间短、体系稳定性高等优点,可代替原有的悬浮聚合反应实验,作为高分子化学实验的教学课程内容。     

Recent Advances in Rare‐Earth Polypnictides

The polypnictide complexes of rare earth cations have drawn the attention of the scientific community for their uncommon bonding modes and potential applications. Herein, we present a systematic and comprehensive summary on recent advances in the field of rare earth polypnictides, focusing on their synthesis, structures, and reactivities. The structural stabilizing effects imposed by the electropositive rare earth cations as well as the reducing capability of rare earth precursors in the synthesis of these polypnictide complexes are described in this review. We also disscuss in detail the bonding interactions and coordination modes between rare earth cations and polypnictide clusters as well as the similarities and the peculiarity of some structures.     

三(2-苯并咪唑亚甲基)胺硝酸镍(Ⅱ)配合物的合成及结构

三（２－苯并咪唑亚甲基）胺简称ＮＴＢ与Ｎｉ（Ⅱ）的硝酸盐形成配合物Ｃ２８Ｈ３５Ｎ９Ｏ９Ｓ２Ｎｉ。本文报道其合成，红外光谱及晶体结构。该化合物为三斜晶系，空间Ｐ１↑－，ａ＝９．６５０（３），ｂ＝１２．７１６（２），ｃ＝１４．４３６Ａ，α＝１１．４６（２），β＝９１．６６（３），γ＝９７．５５（２）°，Ｖ＝１７１８（２）Ａ＾３，Ｚ＝２，Ｆ（０００）＝７９３，Ｄｃ＝１．４８ｇ／ｃｍ＾３，Ｍｒ＝７６４．１     

Comparative X-ray photoelectron spectroscopic study on the desulfurization of thiophene by Raney nickel and rapidly quenched skeletal nickel

The desulfurization of thiophene on Raney Ni and rapidly quenched skeletal Ni (RQ Ni) has been studied in ultrahigh vacuum (UHV) by X-ray photoelectron spectroscopy (XPS). The Raney Ni or RQ Ni can be approximated as a hydrogen-preadsorbed polycrystalline Ni-alumina composite. It is found that thiophene molecularly adsorbs on Raney Ni or RQ Ni at 103 K. At 173 K, thiophene on alumina is desorbed, while thiophene in direct contact with the metallic Ni in Raney Ni undergoes C-S bond scission, leading to carbonaceous species most probably in the metallocycle-like configuration and atomic sulfur. On RQ Ni, the temperature for thiophene dissociation is about 100 K higher than that on Raney Ni. The lower reactivity of RQ Ni toward thiophene is tentatively attributed to lattice expansion of Ni crystallites in RQ Ni due to rapid quenching. The existence of alumina and hydrogen may block the further cracking of the metallocycle-like species on Raney Ni and RQ Ni at higher temperatures, which has been the dominant reaction pathway on Ni single crystals. By 473 K, the C 1s peak has disappeared, leaving nickel sulfide on the surface.     

Zweikernige silylenverbrückte Cyclopentadienylrhodiumbis(ethen)-Komplexe,photochemische Reaktion mit Benzolderivaten und selektiver Einschluß von Methylcyclopentan in das Kristallgitter von [Me2Si{3-But-C5H3Rh(C2H4)2}2]

Dinuclear Silylene Bridged Cyclopentadienylrhodiumbis(ethene) Complexes, Photochemical Reaction with Benzene Derivatives, and Selective Inclusion of Methylcyclopentane into the Crystal Lattice of [Me₂Si{3-Bu^t-C₅H₃Rh(C₂H₄)₂}₂] By reaction of [{(C₂H₄)₂RhCl}₂] with Na₂[Me₂Si(C₅H₄)₂] or with Li₂[Me₂Si(3-Bu^t-C₅H₃)₂] in THF the dinuclear silylene bridged complexes [Me₂Si{C₅H₄Rh(C₂H₄)₂}₂] 1 and [Me₂Si{3-Bu^t-C₅H₃Rh(C₂H₄)₂}₂] 2 , respectively, were synthesized. Due to the asymmetric substitution of the five-membered rings and their hindered rotation around the Si? C axes, 2 is formed as three isomers. The X-ray structure analysis of 2 obtained from hexane reveals the selective inclusion of methylcyclopentane, the content of which in the solvent is about 17%, into the crystal lattice. UV irradiation of 1 in hexane in the presence of benzene causes elimination of the ethene ligands yielding the μ-η³:η³ benzene complex [Me₂Si(C₅H₄Rh₂)₂C₆H₆] which cannot be separated from unreacted 1 . However, separation is possible in case of the hexamethylbenzene compound 4 analogous with 3 .     

Transient Spectroscopic Properties of [60] Fullerene—Containing Cyclic Sulphoxide

The properties of the triplet excited state of [60] fullerene-containing cyclic sulphoxide have been investigated by time-resolved absorption spectroscopy. Transient absorption bands of [60] fullerene-containing cyclic sulphoxide showed two decay-components, which wrer attributed to triplet excited states of different spin multiplicity. The properties of photoexcited states of [60] fullerene-containing cyclic sulphoxide are also reported.     

RE2CuO4的热力学稳定性（RE=La,Nd,Sm,Eu）

构筑了ＭｇＯ部分稳定的ＺｒＯ２基固体电解质电化学电池测量ＥＡＦ的实验装置，测定了Ｓｍ２ＣｕＯ４的标准Ｇｉｂｂｓ生成自由能。结果表明化合物ＲＥ２ＣｕＯ２３（ＲＥ＝Ｌａ，Ｎｄ，Ｓｍ，Ｅｕ）随着镧系元素离子半径减小，热力学稳定性下降，并用晶体场理论解释了这一规律。     

A self-assembly/disassembly two-photo ratiometric fluorogenic probe for bacteria imaging

A fluorogenic probe for bacteria imaging was reported. The binding with anionic bacterial surfaces disassembled the self-assembly probe to turn-on the fluorescence and shift pyrene monomer/excimer ratiometric signals.     

Selective binding of the cyano group in acrylonitrile adsorption on Si(100)-2 x 1

The covalent binding of acrylonitrile (CH(2)=CH-C triple bond N) and the formation of a C=C-C=N structure on Si(100) have been investigated using high-resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and density functional theory (DFT) calculations. For chemisorbed acrylonitrile, the absence of nu(C triple bond N) at 2245 cm(-1) and the appearance of nu(C=N) at 1669 cm(-1) demonstrate that the cyano group directly participates in the interaction with Si(100), which is further supported by XPS and UPS observations. Our experimental results and DFT calculations unambiguously demonstrate a [2 + 2] cycloaddition mechanism for acrylonitrile chemisorption on Si(100) through the binding of C triple bond N to Si dimers. The resulting chemisorbed monolayer with a C=C-C=N skeleton can serve as a precursor for further chemical syntheses of multilayer organic thin films in a vacuum and surface functionalization for in situ device fabrication.     

Synthesis and lysozyme adsorption of rod-like large-pore periodic mesoporous organosilica

Highly ordered rod-like large-pore periodic mesoporous organosilica (PMO) was successfully synthesized at low acid concentration with the assistance of inorganic salt using triblock copolymer P123 as a template. The roles of inorganic salt and acidity in the production of highly ordered mesostructure and the morphology control of PMOs were investigated. It was found that the inorganic salt can significantly widen the range of the synthesis parameters to produce highly ordered 2D hexagonal pore structure of p6mm symmetry. However, the uniform rod-like PMOs can only be synthesized in a narrow range of acid and salt concentrations, which were sensitive to induction time. The adsorption of lysozyme on PMO was studied at different pH values in comparison with adsorption on pure silica material under controlled morphology and pore structure. It was found that the adsorption capacity of lysozyme on the PMO was lower than that on pure SBA-15 silica material and the adsorption amounts are larger at pH 9.6 than at 7.0 for both materials. The results show that the electrostatic interaction between lysozyme and PMO/SBA-15 surface is more dominant than the hydrophobic forces and the interaction of neighboring lysozyme molecules also plays an important role.