meso-四(对甲氧基苯基)卟啉钴在货币金属单晶表面的吸附与自组装研究

利用超高真空低温扫描隧道显微镜系统研究了meso-四对甲氧基苯基卟啉钴分子在Au（111）、Ag（111）和Cu（111）表面的吸附与自组装.该分子在金属表面可以形成两种组装结构A和B.在结构A中,分子间的相互作用主要为π-π堆叠,仅在Au（111）和Ag（111）表面被实验观察到;在结构B中,分子间的相互作用为氢键,仅在Ag（111）和Cu（111）表面被实验观察到.分子-衬底相互作用的差异所引起的分子吸附构象变化被认为是导致不同衬底上的分子形成不同组装结构的原因.研究发现在不同衬底上,分子形成自组装结构的行为存在明显差异.在相近覆盖度下,未参与组装的分子的比例在Cu（111）表面最高,Au（111）次之,Ag（111）最低.表面上参与形成两种组装结构的分子与未参与组装的分子的比例还可通过覆盖度和退火来进行调控.     

Synthesis of triaryls: hydroxy and amine dinaphthyl and diphenanthryl aryls by one-pot electron-transfer nucleophilic substitution reactions

A new one-pot synthetic route to achieve the preparation of hydroxy and amine binaphthyl and biphenanthryl aryls is here reported. This approach involves the reaction of 1,4-bromoiodobenzene, 4,4′-diiodobiphenyl, and 1,4- and 1,5-diiodonaphthalene with the anions of 2-naphthylamine, 2-naphthol, and 9-phenanthrylamine under irradiation in liquid ammonia. The reactions proceed to afford triaryl derivatives in moderate to good yields (∼45% of 1,4-phenylene- and 1,4-naphthylene-1,1′-dinaphthalen-2-ols as well as 1,4-phenylene-1,1′-dinaphthalen-2-amine and 10,10′-diphenanthren-9-amine). Lower yields (27%) of polyaryl derivatives are obtained by reaction of 4,4′-diiodobiphenyl with anions of 2-naphthol and 9-phenanthrylamine.     

Thermally favourable gauge mediation

We discuss the thermal evolution of the spurion and messenger fields of ordinary gauge mediation models taking into account the Standard Model degrees of freedom. It is shown that for thermalized messengers the metastable susy breaking vacuum becomes thermally selected provided that the susy breaking sector is sufficiently weakly coupled to messengers or to any other observable field.     

双吡啶盐（PQ^＋＋）与异丙醇的光化还原反应研究

本文用自由基捕捉技术与ESR相结合的方法对五种PQ~( )—异丙醇体系的光激发均相电子转移过程的研究结果表明PQ~( )可被异丙醇自由基单电子还原生成PQ~ ·自由基,如体系中有二苯酮存在,则电子转移反应速率大大增加.     

Phase Transitions in Polypeptide Liquid Crystals: A Reentrant Isotropic Phase

Optical and C-13 NMR examinations of concentrated solutions of poly-γ-benzyl-L-glutamate (PBLG) in a mixed solvent system containing a denaturant acid, show that this polymer liquid crystal has both a low and high temperature isotropic phase. The latter is due to thermal disruption of long range orientational order of the elongated macromolecules. The former reentrant isotropic phase is a result of an intramolecular helix to random coil transition, which leads to a macromolecular conformation inconsistent with liquid crystallinity.     

非桥基配体对配合物的电子转移反应的影响——Cis-[Co(en)_2Cl_2]~+和Cis-[Co(en)_2(OH)_2Cl]~(2+)与Fe(Ⅱ)间电子转移反应

在成桥活化配合物反应机理基础上,Ogarl,P.Benson等人,根据中心离子的结构和成桥基配体的性质,用配位场理论,研究报导了水中配合物间电子转移反应的动力学行为。本文,在混合溶剂中配合物间电子转移反应机理研究的基础上,探索了非桥基配体Cl~-和H_2O,对H_2O、H_2O—McOH、H_2O—DMF等溶剂中Cis-[Co(cn)_2Cl_2]~+和Cis-[Co(cn)_2(OH_2)Cl]~(2+)和Fe(Ⅱ)间电子转移反应的影响。实验发现:相同条件下,无论在     

Unusual microstructures formed during the mediated electrodeposition of polypyrrole on Al 2024-T3 at low current densities

We have recently described the direct electrodeposition of polypyrrole on aluminum alloy 2024-T3 using electron transfer mediation. While studying the nucleation and growth phases of this deposition process using atomic force microscopy, we observed the formation of unusual polypyrrole structures. These structures formed only at low current density (10–100 A/cm²), only in the presence of the mediator (4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt), and only in cells employing a small-area counter electrode (relative to the working electrode area). In this report, we present some of these interesting polypyrrole structures and the conditions of their formation.     

Kinetic and Product Study of the S-oxidation vs HAT Chemoselectivity in Reactions Promoted by Nonheme Iron(IV)-oxo Complex/NHPI Mediator System

The chemoselectivity between S-oxidation and hydrogen atom transfer (HAT) from C−H bonds has been investigated in the oxidations of a series of aryl sulfides, alkyl aromatic compounds and benzylic alcohols promoted by the iron(IV)-oxo complex [(N4Py)Fe^IV(O)]²⁺ (N4Py: N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)-methylamine) either alone or in the presence of the N-hydroxyphthalimide (NHPI) mediator via kinetic and product studies. Kinetic analyses indicate a generally higher reactivity of [(N4Py)Fe^IV(O)]²⁺ for S-oxidation process while HAT is favored in the reactions promoted by phthalimide-N-oxyl radical (PINO) deriving from NHPI oxidation. Product analysis in intermolecular competitive oxidations confirms the kinetic results with sulfoxides obtained as major products in the oxidation promoted by [(N4Py)Fe^IV(O)]²⁺. Conversely, when NHPI is employed as a mediator, significant differences in terms of chemoselectivity are observed, and HAT-derived products are obtained in higher yields which translate into an inversion of selectivity in the case of the substrates containing activated C−H bonds like diphenylmethane, triphenylmethane and benzylic alcohols. A similar change of chemoselectivity is also observed in the oxidation of aromatic substrates containing both a sulfur atom and α to OH benzylic C−H bonds, with the sulfoxide product more abundant in the absence of NHPI and carbonyl products prevailing with the [(N4Py)Fe^IV(O)]²⁺/NHPI system.     

Synergistic effect between ultrasound and fierce mechanical activation towards mineral extraction: A case study of ZnO ore

Though the positive role of ultrasound has been confirmed in the mineral extraction, its potential towards fiercely mechanically-activated mineral was not yet mentioned. In this study, as a novel mechanical activation style, bead milling (BM) was presented and ZnO ore was selected to determine its effectiveness. Results showed that median particle size of ZnO ore could be pulverized to as low as 1/164 of its original value (from ∼29.2 μm to ∼178 nm), indicating much higher activation potential of BM than that of conventional ball milling. Besides, structure destruction, even phase transformation with the direct participation of airborne CO₂ occurred. All these processes rendered the superior activation capacity of BM. In view of the extraction promotion, the combination of ultrasound and BM exerted more pronounced effect than those of individual ones, indicating the synergistic effect between extra energy input (by ultrasound) and inner energy storage (by fierce BM). The classic shrinking core model with the product layer diffusion as the rate-controlling step was found to well model the extraction kinetics. The modeling disclosed high capability of ultrasound and BM combination in decreasing the activation energy (E_a) (from 54.6 kJ/mol to 26.4 kJ/mol), while ultrasound, BM could only decrease the E_a to 44.9 kJ/mol, 41.5 kJ/mol, respectively. The dual roles of ultrasound were specially highlighted: (i) participation in the extraction process via direct energy input, (ii) regulation of the aggregation that the activated ore suspension was confronted with.     

LHC reach of low scale gauge mediation with perturbatively stable vacuum

Very light gravitino scenario m_3/2?16 eV$m_{3/2}?16\text{eV}$ is very interesting, since there is no cosmological problem. However in such a scenario, stability of the vacuum is an important issue. Recently, Yonekura and one of the authors RS have investigated the parameter space of a low scale gauge mediation with a perturbatively stable vacuum and found that there are severe upper bounds on the gaugino masses. In this Letter, we show that such a model can be completely excluded/discovered at very early stage of the LHC run.