Asymmetric phase-transfer reactions under base-free neutral conditions

Although quaternary onium salt-catalyzed phase-transfer reactions are generally believed to require base additives, we discovered even without any base additives conjugate additions of 3-substituted oxindoles proceeded smoothly in the presence of lipophilic quaternary onium bromide under water-organic biphasic conditions. The mechanism of this novel base-free neutral phase-transfer reaction system was investigated, and the assumed catalytic cycle was presented together with interesting effects of water and lipophilicity of the phase-transfer catalyst. The base-free neutral phase-transfer reaction system could be applied to highly enantioselective conjugate additions, aldol reaction, sulfenylation, and chlorination under the influence of chiral bifunctional onium bromides as key catalysts.     

Silk‐Pectin Hydrogel with Superior Mechanical Properties,Biodegradability, and Biocompatibility

A new method is developed to prepare silk hydrogels and silk‐pectin hydrogels via dialysis against methanol to obtain hydrogels with high concentrations of silk fibroin. The relationship between the mechanical and biological properties and the structure of the silk‐pectin hydrogels is subsequently evaluated. The present results suggest that pectin associates with silk molecules when the silk concentration exceeds 15 wt%, suggesting that a silk concentration of over 15 wt% is critical to construct interacting silk‐pectin networks. The silk‐pectin hydrogel reported here is composed of a heterogeneous network, which is different from fiber‐reinforced, interpenetrated networks and double‐network hydrogels, as well as high‐stiffness hydrogels (elastic modulus of 4.7 ± 0.9 MPa, elastic stress limit of 3.9 ± 0.1 MPa, and elastic strain limit of 48.4 ± 0.5%) with regard to biocompatibility and biodegradability.     

A Base‐Free Neutral Phase‐Transfer Reaction System

Although phase‐transfer reactions catalyzed by using quaternary ammonium salts are generally believed to require base additives, we discovered that, even without any base additives, conjugate additions of 3‐substituted oxindoles to nitroolefins proceeded smoothly in the presence of lipophilic quaternary ammonium bromide under water–organic biphasic conditions. The mechanism of this novel base‐free neutral phase‐transfer reaction system is investigated and the assumed catalytic cycle is presented together with interesting effects of water and lipophilicity of the phase‐transfer catalyst. The base‐free neutral phase‐transfer reaction system can be applied to highly enantioselective conjugate addition and aldol reactions under the influence of chiral bifunctional ammonium bromides as key catalysts. The structure of the chiral ammonium enolate intermediate is discussed based on the single‐crystal X‐ray structures of relevant ammonium salts and the importance of bifunctional design of catalyst is clearly explained in the model of intermediate.     

Application of the single comparator method to instrumental photon activation analysis

Journal of Radioanalytical and Nuclear Chemistry - Instrumental photon activation analysis (IPAA) is nondestructive and multi-elemental analysis method like instrumental neutron activation...     

Electrochemical Fluorination of Dithiocarbonates Using a Triarylamine Mediator

Electrochemical oxidation of O-(4-chlorobenzyl) S-methyl dithiocarbonate using tris(2,4-dibromophenyl)amine as a redox mediator was studied by cyclic voltammetric measurements. The triarylamine mediated anodic fluorodesulfurization of O-(4-chlorobenzyl) and O-(4-bromobenzyl) S-methyl dithiocarbonates provided 4-chloro- and 4-bromobenzyl fluorides, respectively in moderate yields. On the other hand, similar anodic fluorination of O-(2-phenethyl) S-octyl dithiocarbonate and O-(4-bromophenyl) S-methyl dithiocarbonate afforded 2-phenethyl trifluoromethyl ether and difluoro(methylthio)methyl 4-bromophenyl ether, respectively. Mechanistic aspects are also discussed.     

Evolution of the electronic structure of 1T-Cu(x)TiSe(2)

The electronic structure of a new charge-density-wave system or superconductor, 1T-Cu(x)TiSe(2), has been studied by photoemission spectroscopy. A correlated semiconductor band structure is revealed for the undoped case, which resolves a long-standing controversy in the system. With Cu doping, the charge-density wave is suppressed by the raising of the chemical potential, while the superconductivity is enhanced by the enhancement of the density of states, and possibly suppressed at higher doping by the strong scattering.     

Multiple Ca(2+) environments in silicate glasses by high-resolution (43)Ca MQMAS NMR technique at high and ultra-high (21.8 T) magnetic fields

We here show the (43)Ca 5QMAS NMR spectra at high field (16.4 T) and the first 7QMAS spectrum at ultra-high field (21.8 T) for geologically important Ca-containing glasses. The high-resolution MQMAS spectra present a clear evidence of multiple Ca sites in the amorphous structures that have never been identified by other analytical methods. The present study suggests that the Ca(2+) ions are mainly in 7- and 8-fold coordination sites. This will offer valuable insights for dynamic properties of magmatic liquids. The MQMAS NMR technique at high magnetic field is a unique tool to understand the detailed structural information on a specific element in solids including organic and inorganic compounds.     

具有异质结的富勒烯C_(60)/酞菁纳米复合材料的可见光响应光催化应用（英文）

通过再沉淀法制备了富勒烯C60/酞菁的复合纳米微粒。这种复合纳米微粒由于C60分子和酞菁分子间的π-π相互作用而具有电子给体-受体(donor-acceptor)结构,而且这种微粒的尺寸可通过选择再沉淀过程中使用的溶剂来进行控制。此外,这种微粒与Nafion结合后,表现出去除三甲胺的光催化性能,而且其光催化活性优于C60微粒/Nafion或酞菁微粒/Nafion复合物。该结果表明电子给体-受体结构可通过促进有机半导体的电荷分离来增强光催化的性能,从而揭示了一种新颖的基于电子给体-受体结构的有机光催化剂。     

Rational Design and Identification of a Non‐Peptidic Aggregation Inhibitor of Amyloid‐β Based on a Pharmacophore Motif Obtained from cyclo[‐Lys‐Leu‐Val‐Phe‐Phe‐]

Inhibition of pathogenic protein aggregation may be an important and straightforward therapeutic strategy for curing amyloid diseases. Small‐molecule aggregation inhibitors of Alzheimer’s amyloid‐β (Aβ) are extremely scarce, however, and are mainly restricted to dye‐ and polyphenol‐type compounds that lack drug‐likeness. Based on the structure‐activity relationship of cyclic Aβ16–20 (cyclo‐[KLVFF]), we identified unique pharmacophore motifs comprising side‐chains of Leu², Val³, Phe⁴, and Phe⁵ residues without involvement of the backbone amide bonds to inhibit Aβ aggregation. This finding allowed us to design non‐peptidic, small‐molecule aggregation inhibitors that possess potent activity. These molecules are the first successful non‐peptidic, small‐molecule aggregation inhibitors of amyloids based on rational molecular design.