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.     

Interaction Between HMG Proteins (1+2) and the Negative Regulatory Region 1(NCR1) in the 5''''-flanking Sequence of the Human β-globin Gene

The pattern of high mobility group proteins 1 and 2 (HMG1,2) interaction with the 5'-flanking sequence of the human β-globin gene has been analyzed by scanning tunnelling microscopy (STM). A 200 bp negative regulatory region in the 5'-flanking sequence of the human β-globin gene can be folded by HMG proteins 1 and 2 into a circular structure (diameter 70±6) with a linear tail which seems to be a left-handed double helix structure.     

Co处理的γ-Fe2O3薄膜的界面研究

本文中对CoO与Fe₂O₃的界面进行了研究,结果表明,简单的CoO-γ-Fe₂O₃界面对于磁性能基本无影响。分析表明,“复杂的扩散界面”不大可能象以往认为的那样是矫顽力增长的主要原因。矫顽力的增长可能是由掺Co造成的一种体效应而不是界面效应。 关键词：     

Preparation and swelling properties of hydrolysis-resistant superabsorbent composite based on acrylic acid and sodium bentonite

Abstract

A novel hydrolysis-resistant superabsorbent composite was prepared via the solution polymerization based on acrylic acid (AA) and sodium bentonite (SBT) as monomers, tetraallylammonium bromine (TAAB) as crosslinker and ammonium persulfate (APS) as initiator. The mechanism of polymerization and the structure of the superabsorbent polymer (SAP) were studied by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (X-ray), and scanning electron microscopy (SEM). The reaction conditions such as different mass ratios of APS to AA, TAAB to AA, SBT to AA, neutralization degree of AA were optimized by orthogonal experiment, and the influence of each reaction condition on the capacity of water absorption at 150?°C was investigated via single-factor controlled experiment. The hydrolysis resistance and swelling kinetics of the SAP were studied in different solutions at 150?°C. Compared to traditional SAPs, the SAP synthesized with TAAB as crosslinker performed a more excellent hydrolysis resistance and water absorbency capacity at high temperatures. The water absorbency in distilled water or 0.1?mol L^?1 NaCl solution could reach 392.6 and 145.2?g g^?1at 150?°C, respectively. The SAP maintaining high swelling capacity in the pH range of 5–9 indicated its wide application values in the acidic or alkaline environment at high temperature. In addition, the SAP exhibited good reusability which could still retain about 73% of its initial water absorbency after reswelling six times at 150?°C.     

稀土金属作用下芳香醛、酮的还原偶联反应

由Ln/ROH/TMSCl组成的体系能选择性地使芳香族醛、酮还原偶联形成频哪醇, 产率优良, 而对脂肪族醛酮呈惰性。     

2,2';9',2''-Ter[1,10]phenanthroline

The title molecule, 2,2';9',2'-ter[1,10]phenanthroline can be prepared from 2,9-dichloro-1,10-phenanthroline in three steps through the corresponding diacetyl intermediate. The ligand acts as a hexadentate with K+, while two molecules form a trinuclear, helical complex with Cu(I), which evidences pi-stacking interactions and Cu-Cu distances of 3.01-3.04 A. Electrochemical analysis shows a strong interaction between the Cu(I) centers.     

Total synthesis of (−)-penicimutanin a and related congeners

The first total synthesis of penicimutanin A (1) was achieved within 10 steps (LLS). Key innovations in this synthesis consist of (1) a highly efficient electro-oxidative dearomatization; (2) an unprecedented bisoxirane-directed intermolecular aldol reaction from the sterically hindered face of the ketone and (3) the diastereoselective one-step Meerwein–Eschenmoser–Claisen rearrangement enabling the construction of vicinal quaternary stereocenters. Related family members e.g. penicimutanolone (3) and penicimutatin (5) have also been synthesized alongside, elucidating their absolute configurations, hence the absolute configuration of 1.

The first total synthesis of penicimutanin A (1) was achieved within 10 steps (LLS).     

D,L-1,2,2-三甲基环戊烷-1,3-二胺硝酸镍配合物的合成、结构及其和手性D-(+)-1,2,2-三甲基环戊烷-1,3-二胺氯化镍配合物的对比分析(英)

A nickel(Ⅱ) complex [Ni(La)₂](NO₃)₂ (1) with bidentate racemic 1,2,2-trimethylcyclopentane-1,3-diamine ligand has been synthesized and characterized by IR, EA, ES-MS, and its X-ray diffraction study reveals that the nickel(Ⅱ) center is tetra-coordinated by one D- and one L- diamine ligands, and a three-dimensional hydrogen-bond-sustained network is formed in the solid state by means of the eight-membered N-H…O hydrogen bond cycle. This compound also supplies a good comparison to the chiral complex [Ni(L_b)₂]Cl₂·2H₂O (2) (L_b=D-(+)-1,2,2-trimethylcyclopentane-1,3-diamine). CCDC: 218122.     

FREQUENCY DEPENDENCE OF THE DIELECTRIC RELAXATION OF 1,2-POLYBUTADIENES

The dielectric loss factor and permittivity of a series of 1, 2-polybutadienes with different contents of 1, 2-units and different contents of syndiotactie 1, 2-units were determined over a frequency range from 30Hz to 100KHz at different temperatures. The WLF equation was evaluated for various samples with T_θat 100KHz as a reference temperature and the master curves of various samples have been constructed, which are in accordance with those calculated by Havriliak-Negami equation. The frequency dependence of the dielectric relaxation of 1, 2-polybutadienes was investigated over a frequency range from 10~0 Hz to 10~(12) ZHz in terms of the experimental data and the master curves.     

THE SOLID STATE REACTIONS AND TRANSITIONS IN HIGH POLYMERIC SYSTEMS Ⅲ. THE BULK CRYSTALLIZATION OF LANTHANIDECATALYTICALLY POLYMERIZED POLYDIENES

For the mechanism of isothermal bulk crystallization of high polymers, beside the nucleation and growth steps, the unimpingement of growing crystal aggregates should be taken into account for the modification of the Avrami equation. Starting from Poisson distribution function of growing crystal aggregates, the probability of the unimpinging ones should be P(0)+P(1), then the Q-modified Avrami equation thus derived can be expressed aswhere V0 represents the volume fraction of crystal aggregates at crystallization time t at a given temperature, while the exponent n on t relates to the mode of nucleation and growth, and K_q is the corresponding shape factor. This Q-modified one is verified satisfactory by the isothermal bulk crystallization of lanthanidecatalytically polymerized polybutadiene (Ln-PB), polyisoprene (Ln-PIR) and their copolymers (LnPB/IR). Furthermore, the proposed mechanism is well identified by the change of morphological state during the course of crystallization of the corresponding east film of Ln-PB TR (92/8) at-60°(Fig. 1).Upon examination of the influence of the number of entanglement on crystallization rate, it reveals the existence of two stages of entanglementation, the primary and the secondary ones (Fig. 19)The equation for dependence of molecular weight and entanglement on bulk crystallization rate has been derived as Eq. 13 or 18 for Ln-PB, and verified by the experimental rate data of well fractionated Ln-PB samples crystallized at -9.1 to -15℃(Fig.20).