A ligand-free, copper-catalyzed cascade sequence to indole-2-carboxylic esters

A variety of indole-2-carboxylic esters are accessible in yields up to 61% through a ligand-free, copper-catalyzed reaction of a series of commercially available 2-halo aryl aldehydes with benign glycine amidoesters, including the common reagent ethyl acetamidoacetate. This one-pot, three-reaction format allows ready entry to the desired heterocycles from starting substrates in the reactivity order of iodo > bromo ? chloro substituents. An assortment of functional groups is tolerated, adding to the generality of this methodology.     

Different copper oxide nanostructures: Synthesis,characterization, and application for C‐N cross‐coupling catalysis

Cupric oxide and cuprous oxide micro‐/nanomaterials with well‐controlled sizes and morphologies have been synthesized via different crystal growth techniques. Structural and morphological characterizations of these copper oxide micro‐/nanomaterials were performed by X‐ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). After that, these copper oxide micro‐/nanomaterials were used as catalysts for a typical C‐N cross‐coupling reaction directly. The catalytic results showed that different copper oxide micro‐/nanomaterials had different catalytic activities in C‐N cross‐coupling reaction. The particle size of cupric oxide and the oxidation state of copper played vital roles in the catalytic process. Cupric oxide with small particle size has the best catalytic activity, while cupric oxide with different morphologies has almost the same yields and cuprous oxide has very poor yields. Further, the possible catalytic mechanism for copper oxide nanomaterials catalyzed cross‐coupling reaction was proposed. And the influence of particle size and oxidation state was carefully discussed. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

偶氮苯类衍生物材料性质及其研究进展

光可在不接触的条件下作用于材料,因此光是一种理想的触发机制并可以选择性、非破坏性和远程激活的施加外部刺激.偶氮苯类化合物作为一种芳香偶氮化合物染料分子,能够在不同光照下产生异构效应,并且芳香偶氮化合物分子具有可逆的异构体,这种基于不同波长导致的构型变化可使偶氮苯类化合物产生微观与宏观上的运动.基于这种宏观机械变形和可逆...     

An unconventional role of ligand in continuously tuning of metal-metal interfacial strain

We show that embedding of a surface ligand can dramatically affect the metal-metal interfacial energy, making it possible to create nanostructures in defiance of traditional wisdom. Despite matching Au-Ag lattices, Au-Ag hybrid NPs can be continuously tuned from concentric core-shell, eccentric core-shell, acorn, to dimer structures. This method can be extended to tune even Au-Au and Ag-Ag interfaces.     

Reversibly switching the surface porosity of a DNA tetrahedron

The ability to reversibly switch the surface porosity of nanocages would allow controllable matter transport in and out of the nanocages. This would be a desirable property for many technological applications, such as drug delivery. To achieve such capability, however, is challenging. Herein we report a strategy for reversibly changing the surface porosity of a self-assembled DNA nanocage (a DNA tetrahedron) that is based on DNA hydridization and strand displacement. The involved DNA nanostructures were thoroughly characterized by multiple techniques, including polyacrylamide gel electrophoresis, dynamic light scattering, atomic force microscopy, and cryogenic electron microscopy. This work may lead to the design and construction of stimuli-responsive nanocages that might find applications as smart materials.     

Communication: Engineered tunable decay rate and controllable dissipative dynamics

We investigate the steering dissipative dynamics of a two-level system (qubit) by means of the modulation of an assisted tunneling degree of freedom which is described by a quantum-oscillator spin-boson model. Our results reveal that the decoherence rate of the qubit can be significantly suppressed and simultaneously its quality factor is enhanced. Moreover, the modulated dynamical susceptibility exhibits a multi-peak feature which is indicative of the underlying structure and measurable in experiment. Our findings demonstrate that the interplay between the combined degrees of freedom and the qubit is crucial for reducing the dissipation of qubit and expanding the coherent regime of quantum operation much large. The strategy might be used to fight against deterioration of quantum coherence in quantum information processing.     

Generation of singlet oxygen from fragmentation of monoactivated 1,1-dihydroperoxides

The first singlet excited state of molecular oxygen ((1)O(2)) is an important oxidant in chemistry, biology, and medicine. (1)O(2) is most often generated through photosensitized excitation of ground-state oxygen. (1)O(2) can also be generated chemically through the decomposition of hydrogen peroxide and other peroxides. However, most of these "dark oxygenations" require water-rich media associated with short (1)O(2) lifetimes, and there is a need for oxygenations able to be conducted in organic solvents. We now report that monoactivated derivatives of 1,1-dihydroperoxides undergo a previously unobserved fragmentation to generate high yields of singlet molecular oxygen ((1)O(2)). The fragmentations, which can be conducted in a variety of organic solvents, require a geminal relationship between a peroxyanion and a peroxide activated toward heterolytic cleavage. The reaction is general for a range of skeletal frameworks and activating groups and, via in situ activation, can be applied directly to 1,1-dihydroperoxides. Our investigation suggests the fragmentation involves rate-limiting formation of a peroxyanion that decomposes via a Grob-like process.     

Construction of functionalized B/C/D ring system of C19-diterpenoid alkaloids via intramolecular Diels–Alder reaction followed by Wagner–Meerwein rearrangement

A concise strategy for construction of B/C/D ring system of C₁₉-diterpenoid alkaloids was described, which features a highly diastereoselective intramolecular Diels–Alder reaction of masked o-benzoquinone and an efficient Wagner–Meerwein 1,2-shift rearrangement. The functional group transformations of rearrangement product 19 demonstrate a potential for stereoselective installation of oxygen functions on D-ring of many type of C₁₉-diterpenoid alkaloids.     

Synthesis, characterization and flame retardant of UV-curable hybrid coatings containing SiO2–P2O5–B2O3 via sol–gel method

A ternary sol containing silicon, phosphorus and boron modified by ??-methacryloxypropyltrimethoxysilane was synthesized by sol?Cgel method. The ternary sol was incorporated into the organic matrix and UV-curable organic/inorganic hybrid coating materials were obtained. Hardness, transmittance, haze, cross-cut adhesion and abrasion resistance results showed that the mechanical properties of the hybrid coatings improved effectively with no comprising on optical properties by increasing sol content. Scanning electron microscopy and Energy Dispersive X-ray spectrometer studies indicated that inorganic particles were homogenously dispersed in the organic matrix. The flame retardancy of the UV-curable coatings was investigated by thermogravimetric analysis and microscale combustion calorimeter. The results showed that the incorporation of sol into the organic network led to an improvement in the thermal stability and flame retardancy of the hybrid coating materials. It is a desirable achievement to improve simultaneously both flame retardancy and mechanical properties of the coatings.