离子型膦配体及其离子型过渡金属配合物的合成和均相催化作用

与传统中性叔膦配体构建的过渡金属配合物相比,由离子型膦配体配位构建的过渡金属配合物具有典型的离子盐组成特点、独特的电子效应和几何构型。该类配合物中,不仅存在金属和配体间的配位作用,还存在正电荷的强吸电子效应和阴阳离子的静电作用,由此可以产生独特的催化性能。近年来,离子型过渡金属配合物的合成及其均相催化应用成为配位化学和均相催化研究中备受关注的领域。离子型过渡金属配合物的离子盐结构,使其在与室温离子液体溶剂结合使用时,离子型离子配体及其配合物能够严格被锁定在离子液体相,具有避免离子型离子配体及其配合物的流失、抑制其失活、并实现循环使用的优点,也成为均相催化固载化的绿色方法之一。本文综述了近十年发展的一类咪唑鎓基与膦配体中的磷原子毗邻的离子型膦配体的合成,及其相应Rh、Pd、Ru、Pt、Au、Ni、Cu等离子型配合物的构建,并介绍了它们在均相催化反应中的应用。     

Diterpenoid alkaloids from Aconitum brevicalcaratum as autophagy inducers

A new C₁₉ diterpenoid alkaloid, brevicanine (1) and six known ones (2–7) were isolated from Aconitum brevicalcaratum (Finet et Gagnep.) Diels. Their structures were elucidated on the basis of extensive spectroscopic analyses. The cytotoxicity of those compounds was investigated against HCT116 human cancer cell line, which showed none of them possessing considerable anti-proliferative activities. To evaluate the autophagy effect of compounds 1–7, Western blot was used to detect the expression of autophagic marker by stimulating human cancer HCT116 cells. The results showed that compound 6 induced protective autophagy in HCT116 cells. Mechanistic insight showed that compound 6 induced protective autophagy through p53 activation, ERK1/2 and p38 MAPK signaling cascade.     

Structural,spectroscopic, and reactivity comparison of xanthene- and dibenzofuran-bridged cofacial bisporphyrins

A comparison of the structure, spectroscopy, and oxygen atom-transfer reactivity of cofacial bisporphyrins anchored by xanthene (DPX) and dibenzofuran (DPD) pillars is presented. The synthesis and characterization of dicopper(II) and dinickel(II) complexes of DPD completes a homologous series of homobimetallic zinc(II), copper(II), and nickel(II) complexes for both cofacial platforms. X-ray crystallographic analysis of the parent free-base porphyrins H(4)DPX (1) and H(4)DPD (5) confirms the face-to-face arrangement of the two porphyrin macrocycles with a large available range of vertical pocket sizes: 1 (C(80)H(92)Cl(2)N(8)O), triclinic, space group P1 macro, a = 13.5167(12) A, b = 21.7008(18) A, c = 23.808(2) A, alpha = 80.116(2) degrees, beta = 76.832(2) degrees, gamma = 80.4070(10) degrees, Z = 4; 5 (C(80)H(83)N(8)O(2)), monoclinic, space group C2/c, a = 22.666(2) A, b = 13.6749(14) A, c = 42.084(4) A, beta = 94.554(2) degrees, Z = 8. EPR spectroscopy of dicopper(II) derivatives Cu(2)DPX (3) and Cu(2)DPD (7) complements the crystallographic studies by probing intramolecular metal-metal arrangements in frozen solution. Exciton interactions between the porphyrin subunits in fluid solution are revealed by steady-state and time-resolved electronic absorption and emission spectroscopy. The resulting compilation of structural and spectroscopic data provides a benchmark for the use of these and related platforms for the activation of small-molecule substrates. A structure-function relation is developed for the photoinduced oxygen atom-transfer reactions of bisiron(III) mu-oxo derivatives of DPX and DPD. The efficiency of the photochemical process is markedly dependent (approximately 10(4)-fold) on the vertical flexibility of cofacial architecture provided by the spacer.     

Preparation of sulfur‐quinone polyurethanes and their use to inhibit the corrosion of iron particles

A sulfur‐quinone diol monomer, 2,5‐bis‐(2‐hydroxyethylthio)‐1,4‐benzoquinone (SQM‐2), was prepared by the reaction of 2‐mercaptoethanol with benzoquinone. SQM‐2 and polycaprolactone diol (number‐average molecular weight = 1250) were condensed with toluene diisocyanate to give sulfur‐quinone polyurethanes. Two compositions were prepared, SQPU‐1 containing 7 mol % SQM‐2 and SQPU‐2 containing 35 mol % SQM‐2. These thermoplastic polyurethanes were soluble in solvents used in magnetic tape coating processes. The polymers were used to prepare magnetic coatings containing state‐of‐the‐art commercial iron particles. The sulfur‐quinone polyurethanes protected the iron particles against corrosion from a pH 2.0 aqueous buffer. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3278–3283, 2000     

图的导出森林2-划分

对一个给定的简单图Ｇ，是否存在Ｖ（Ｇ）的一个２－划分（Ｖ１，Ｖ２）使得每个导出子图Ｇ［Ｖｉ］为森林？称该问题为导出森林２－划分问题．本文证明了对最大度为５的图该问题是ＮＰ－完全的，而对最大度≤４的图该问题多项式时间可解．     

Transmission and reflection navigated optical probe with depth-tuned surface corrugations

An optical probe with a single aperture flanked by depth-tuned surface corrugations is presented. It can generate enhanced optical transmission at the exit of a slit and lower reflection at the top side of the compound dielectric/metal structure. The probe is designed and discussed on the basis of enhanced surface plasmon resonance for the purpose of high-resolution inspection use. A multidielectric probe consisting of air/glass/C/Ag/air is put forward. The influence of the thickness of the carbon film on the reduction of reflection is analyzed in detail combined with the relevant funneling effect induced by waveguide mode propagation through a central slit. Our simulation results show that a carbon film with a thickness of 150 nm and a 200-nm Ag film with the designed parabolic corrugations can reach our design target of the enhanced optical transmission and minimum reflection. PACS 02.60.Cb; 02.70.Bf; 07.79.Fc; 42.25.Bs     

A unified evolution equation for the Cauchy stress tensor of an isotropic elasto-visco-plastic material

In the present study an evolution equation for the Cauchy stress tensor is proposed for an isotropic elasto-visco-plastic continuum. The proposed stress model takes effects of elasticity, viscosity and plasticity of the material simultaneously into account. It is ascribed with some scalar coefficient functions and, in particular, with an unspecified tensor-valued function N, which is handled as an independent constitutive quantity. It is demonstrated that by varying the values and the specific functional forms of these coefficients and N, different known models in non-Newtonian rheology can be reproduced. A thermodynamic analysis, based on the Müller–Liu entropy principle, is performed. The results show that these coefficients and N are not allowed to vary arbitrarily, but should satisfy certain restrictions. Simple postulates are made to further simplify the deduced general results of the thermodynamic analysis. They yield justification and thermodynamic consistency of the existing models for a class of materials embracing thermoelasticity, hypoelasticity and in particular hypoplasticity, of which the thermodynamic foundation is established successively for the first time in literature. The study points at the wide applicability and practical usefulness of the present model in different fields from non-Newtonian fluid to solid mechanics. In this paper the thermodynamic analysis of the proposed evolution-type stress model is discussed, its applications are reported later.      

控制断裂能量与爆破效果的分形分析

定向断裂爆破与普通光爆、预裂相比,爆破效果明显提高,爆破能量利用更为合理。文中根据爆破断裂的分形研究,阐述了控制断裂爆破改进周边成形质量,提高爆炸能量利用率的力学机制。     

A two-fluid model for reactive dilute solid–liquid mixtures with phase changes

Based on the Eulerian spatial averaging theory and the Müller–Liu entropy principle, a two-fluid model for reactive dilute solid–liquid mixtures is presented. Initially, some averaging theorems and properties of average quantities are discussed and, then, averaged balance equations including interfacial source terms are postulated. Moreover, constitutive equations are proposed for a reactive dilute solid–liquid mixture, where the formation of the solid phase is due to a precipitation chemical reaction that involves ions dissolved in the liquid phase. To this end, principles of constitutive theory are used to propose linearized constitutive equations that account for diffusion, heat conduction, viscous and drag effects, and interfacial deformations. A particularity of the model is that the mass interfacial source term is regarded as an independent constitutive variable. The obtained results show that the inclusion of the mass interfacial source term into the set of independent constitutive variables permits to easily describe the phase changes associated with precipitation chemical reactions.