Palladium-catalysed intramolecular annulation of 2-haloanilines and ketones: enolate arylation vs. nucleophilic addition to the carbonyl group

Two alternative annulation pathways involving either the enolate arylation or the addition to the ketone carbonyl group can operate in the Pd-catalysed intramolecular coupling of 2-haloanilines and ketones.     

超弹性夹芯覆盖层的水下爆炸防护性能

对橡胶夹芯覆盖层在船模受水下爆炸时的防护作用进行了实验研究。以钢制加筋方盒模型为实验对象,针对有、无覆盖层2种情况开展了一系列5 kg当量的水下爆炸对比实验。对加速度、应变及壁压等物理量进行了分析对比。结果表明,超弹性覆盖层能有效降低结构受冲击波时的响应峰值。而壁压对比揭示了由于流固耦合,作用在结构上的总入射冲量大幅度降低。频域分析表明,覆盖层的作用可以用一个低通滤波器进行类比,对于50 Hz以上的高频信号衰减明显,但对于低于50 Hz的低频信号影响不大。     

模态分析和有限元分析相结合识别材料结构刚度

本文论述了利用模态分析和有限元分析相结合来识别复合材料板的刚度系数的方法。该方法取决于（１）正确的有限元模型；（２）可靠的实验模态分析数据和正确的相关准则；（３）快速而又稳妥的估算方法，该方法对有限元模型动力修正也是有用的     

Nucleophilic aryl fluorination and aryl halide exchange mediated by a Cu(I)/Cu(III) catalytic cycle

Copper-catalyzed halide exchange reactions under very mild reaction conditions are described for the first time using a family of model aryl halide substrates. All combinations of halide exchange (I, Br, Cl, F) are observed using catalytic amounts of Cu(I). Strikingly, quantitative fluorination of aryl-X substrates is also achieved catalytically at room temperature, using common F(-) sources, via the intermediacy of aryl-Cu(III)-X species. Experimental and computational data support a redox Cu(I)/Cu(III) catalytic cycle involving aryl-X oxidative addition at the Cu(I) center, followed by halide exchange and reductive elimination steps. Additionally, defluorination of the aryl-F model system can be also achieved with Cu(I) at room temperature operating under a Cu(I)/Cu(III) redox pair.     

Chemical reactivity of D3h C78 (metallo)fullerene: regioselectivity changes induced by Sc3N encapsulation

We report here for the first time a full comparison of the exohedral reactivity of a given fullerene and its parent trinitride template endohedral metallofullerene. In particular, we study the thermodynamics and kinetics for the Diels-Alder [4 + 2] cycloaddition between 1,3-butadiene and free D3h'-C78 fullerene and between butadiene and the corresponding endohedral D3h-Sc3N@C78 derivative. The reaction is studied for all nonequivalent bonds, in both the free and the endohedral fullerenes, at the BP86/TZP//BP86/DZP level. The change in exohedral reactivity and regioselectivity when a metal cluster is encapsulated inside the cage is profound. Consequently, the Diels-Alder reaction over the free fullerene and the endohedral derivative leads to totally different cycloadducts. This is caused by the metal nitride situated inside the fullerene cage that reduces the reactivity of the free fullerene and favors the reaction over different bonds.     

Influence of the phase behavior on the properties of ionic nanoemulsions prepared by the phase inversion composition method

The low-energy emulsification method phase inversion composition (PIC) was used to prepare O/W nanoemulsions in the W/oleylammonium chloride-oleylamine-C12E10/hexadecane ionic system, where the oleylammonium acted as a cationic surfactant. The results obtained, in terms of phase diagrams and emulsion characteristics, were compared with those obtained in the system W/potassium oleate-oleic acid-C12E10/hexadecane [I. Solè, A. Maestro, C. González, C. Solans, J.M. Gutiérrez, Langmuir 22 (2006) 8326], in which the oleate acted as an anionic surfactant. This study was done in order to extend the application range of the ionic nanoemulsions, not only in anionic systems but also in cationic ones, and in order to deep further into the nanoemulsion formation mechanism. The results show again that to obtain small droplet-sized nanoemulsions it is necessary to cross a direct cubic liquid crystal phase along the emulsification path, and it is also crucial to remain in this phase enough time and to use a proper mixing rate to incorporate all the oil into the liquid crystal. Then, when nanoemulsion forms, the oil is already intimately mixed with all the components, and the nanoemulsification is easier. Structural studies made with both cationic and anionic systems confirmed that the size of the "micelles" that form the cubic phase is the same or slightly smaller than the size of the nanoemulsion droplets obtained, depending on the emulsification path, which seems to point out that the nanoemulsions are formed in both cases by a dilution process of this cubic phase. When further watery solution is added to the cubic liquid crystal, these micelles separate, disrupting the cubic structure, and a small fraction of the surfactant migrates to the water. Moreover, due to the change in pH, the spontaneous curvature increases. Then, the phases in equilibrium are an oil-in-water microemulsion (W(m)) and the oil in excess. However, through this emulsification method, the surfactants can be "trapped" in a lower curvature than the spontaneous one, retaining all the oil nanoemulsified.     

Synthesis of indole-3-carboxylic acid derivatives by Pd(0)-catalyzed intramolecular alpha-arylation of beta-(2-iodoanilino) esters

beta-(2-Iodoanilino) esters undergo intramolecular alpha-arylation in the presence of Pd(PPh(3))(4) and potassium phenoxide. The reaction is a useful methodology for the preparation of indole-3-carboxylic acid ester derivatives.     

Mechanistic insights into the chemistry of RuII complexes containing Cl and DMSO ligands

Two new isomers trans,mer-[RuIICl2(bpea)(DMSO)], 2a, and cis,fac-[RuIICl2(bpea)(DMSO)], 2b, (bpea = N,N-bis(2-pyridylmethyl)ethylamine), as well as the bis-DMSO complex trans,fac-[RuIICl(bpea)(DMSO)2]Cl, 3, have been synthesized and characterized by cyclic voltammetry and UV-vis and 1D and 2D NMR spectroscopy in solution. Their solid-state structure has also been solved by means of single-crystal X-ray diffraction analysis. All the three complexes display a ruthenium metal center possessing a distorted-octahedral type of coordination, where the bpea ligand is coordinated in a meridional fashion in 2a and in a facial fashion in 2b and 3. The isomer 2a is the kinetically favored and thus can be thermally converted into 2b, that is the thermodynamically favored one. A thorough kinetic analysis strongly points toward a dissociative mechanism, where in the first step a chloro ligand is removed from the metal coordination sphere, followed by a geometric rearrangement before the chloro ligand coordinates again, generating the final complex. DFT calculations agree with the experimental data for the proposed mechanism and allow us to further characterize the mechanism of the 2a --> 2b rearrangement by obtaining the intermediates and transition state.     

Separation and investigation of structure-mobility relationship of gonadotropin-releasing hormones by capillary zone electrophoresis in conventional and isoelectric acidic background electrolytes

Capillary zone electrophoresis (CZE) has been applied to qualitative and quantitative analysis, separation and physicochemical characterization of synthetic gonadotropin-releasing hormones (GnRHs) and their analogs and fragments. Structurally related peptides were separated in conventional and isoelectric acidic background electrolytes (BGEs), pH 2.18-2.50. Best separation was achieved in isoelectric BGE composed of 200 mM iminodiacetic acid, pH 2.32. The effective electrophoretic mobilities, m(ep), of GnRHs in five BGEs were determined and four semiempirical models correlating effective mobility with charge, q, and relative molecular mass, M(r), (m(ep) versus q/M(r)(k), where k is related to the molecular shape) were tested to describe the migration behavior of GnRHs in CZE. None of the models was found to be quite definitively applicable for the whole set of 10 GnRHs differing in size (tetrapeptide-decapeptide) and positive charge (0.91-3.00 elementary charges). Nevertheless, for the dependence of m(ep) on q/M(r)(k), the highest coefficient of correlation, R=0.995-0.999, was obtained for k close to the value 0.5 in all five acidic BGEs. This indicates that the most probable structure of GnRHs in these BGEs can be predicted as a random coil.     

Free vibration of circular cylindrical shell with constrained layer damping

Free vibration characteristics of circular cylindrical shell with passive constrained layer damping (PCLD) are presented. Wave propagation approach rather than finite element method, transfer matrix method, and Rayleigh-Ritz method is used to solve the problem of vibration of PCLD circular cylindrical shell under a simply supported boundary condition at two ends. The governing equations of motion for the orthotropic cylindrical shell with PCLD are derived on the base of Sanders’ thin shell theory. Numerical results show that the present method is more effective in comparison with other methods. The effects of the thickness of viscoelastic core and constrained layer, the elastic modulus ratio of orthotropic constrained layer, the complex shear modulus of viscoelastic core on frequency parameter, and the loss factor are discussed.