EC-backward-E electrochemistry supported by an alkoxyphenyl group

EC-backward-E electrochemistry through electrocatalytic formal [2+2] cycloaddition reaction between anodically activated aliphatic enol ethers and unactivated olefins possessing an alkoxyphenyl group was clearly described by using cyclic voltammetric studies and spin density observation with B3LYP/6-31G(d) calculations. The alkoxyphenyl group was found to regulate the electron transfer, which operates as an electron donor during the formation of the cyclobutane ring and as an electron acceptor from the anode to give the final product (EC-backward-E).     

Catalytic Asymmetric Total Synthesis of Exiguolide

The catalytic asymmetric total synthesis of (−)-exiguolide, a complex 20-membered macrolide embedded with a bis(tetrahydropyran) motif, is reported. The convergent synthesis involves the construction of the C1–C11 tetrahydropyran segment via catalytic asymmetric allylation and Prins cyclization, and the formation of the C12–C21 phosphonate segment via catalytic asymmetric cyclocondensation reaction and Johnson–Claisen rearrangement. The synthesis of 15-epi-exiguolide is also described.     

Push–Pull Bisnaphthyridylamine Supramolecular Nanoparticles: Polarity-Induced Aggregation and Crystallization-Induced Emission Enhancement and Fluorescence Resonance Energy Transfer

Emissive push–pull-type bisnaphthyridylamine derivatives ( BNA-X : X=Me, Et, Bzl, Ph, BuBr, and BuTEMPO) aggregate in aqueous methanol. Furthermore, a two-step emission and aggregation process is controllable by varying the methanol-to-water ratio. At 2:3 MeOH/H₂O, crystallization-induced emission enhancement (CIEE) occurs via formation of an emissive crystal phase, whereas, at 1:9 MeOH/H₂O, aggregation-induced emission enhancement (AIEE) occurs, induced by emissive supramolecular nanoparticles (NPs). For BNA-Ph , the emission quantum yield was 25 times higher in aqueous methanol than that in pure methanol. Despite the high hydrophobicity of BNA-X (C log P=6.1–8.0), the spherical NPs were monodisperse (polydispersity indices <0.2). Moreover, the emissive NPs exhibited fluorescence resonance energy transfer (FRET) with pyrene; however, for BNA-X bearing the TEMPO radical ( BNA-BuTEMPO ), no FRET was observed because of quenching. In particular, the BNA-BuTEMPO NPs have a slow rotational correlation time (1.3 ns), suggesting applications as magnetic resonance imaging contrast agents with large relaxivity.     

Preparation of perfluoro‐1,3‐propanedisulfonic acid/Nafion/silica hybrid nanoparticles—thermally stable Nafion in these silica hybrid nanoparticles even after calcination at 800 °C

Perfluoro‐1,3‐propanedisulfonic acid (PFPS)/Nafion/silica hybrid particles were prepared by the sol–gel reactions of PFPS with tetraethoxysilane and silica nanoparticles in the presence of Nafion under alkaline conditions. These obtained composites exhibited a good dispersibility and stability in not only water but also traditional organic media such as methanol, ethanol, 1,2‐dichloroethane, tetrahydrofuran, and dimethyl sulfoxide. Dynamic light scattering measurements and field‐emission scanning electron microscopy show that these hybrid particles are nanometer size‐controlled fine particles before and even after calcination at 800 °C. Nafion/silica hybrid nanoparticles were also prepared in the absence of PFPS under similar conditions. The weight of original Nafion markedly dropped around 350 °C and decomposed gradually, reaching 0% around 450 °C, and Nafion in the Nafion/silica nanocomposites exhibited a similar weight loss behavior to that of the original one. However, Nafion/PFPS/silica hybrid nanoparticles were found to exhibit no weight loss corresponding to the contents of Nafion and PFPS in the silica gel matrices even after calcination at 800 °C. It was demonstrated that the pH value (3.77 at 25 °C) of Nafion/PFPS/silica hybrid nanoparticles after calcination is smaller than that (5.66 at 25 °C) before calcination, and this hybrid nanoparticles exhibited a higher proton conductivity (5.8 × 10^?3 S/cm at 85 °C) than that (4.1 × 10^?3 S/cm at 85 °C) before calcination. In addition, Nafion/PFPS/silica hybrid nanoparticles after calcination at 800 °C were applied to the Friedel‐Crafts acylation of thiophene with acetic anhydride to give the expected 2‐acetylthiophene, of whose yield was similar to that before calcination under similar conditions. These findings suggest that Nafion in PFPS/silica hybrid nanoparticle cores should exhibit a nonflammable characteristic even after calcination at 800 °C to act as an effective acid catalyst. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1869–1877     

Reductive Amination/Cyclization of Keto Acids Using a Hydrosilane for Selective Production of Lactams versus Cyclic Amines by Switching of the Indium Catalyst

Described herein is that the catalytic construction of N‐substituted five‐ and six‐membered lactams from keto acids with primary amines by reductive amination, using an indium/silane combination. This relatively benign and safe catalyst/reductant system tolerates the use of a variety of functional groups, especially ones that are reduction‐sensitive. A direct switch from synthesizing lactams to synthesizing cyclic amines is achieved by changing the catalyst from In(OAc)₃ to InI₃. This conversion occurs by further reduction of the lactam using the indium/silane pair.     

Characterization of subdifferentials of a singular convex functional in Sobolev spaces of order minus one

Subdifferentials of a singular convex functional representing the surface free energy of a crystal under the roughening temperature are characterized. The energy functional is defined on Sobolev spaces of order ?1, so the subdifferential mathematically formulates the energy?s gradient which formally involves 4th order spacial derivatives of the surface?s height. The subdifferentials are analyzed in the negative Sobolev spaces of arbitrary spacial dimension on which both a periodic boundary condition and a Dirichlet boundary condition are separately imposed. Based on the characterization theorem of subdifferentials, the smallest element contained in the subdifferential of the energy for a spherically symmetric surface is calculated under the Dirichlet boundary condition.     

Sit-to-walk Task in Hemiplegic Stroke Patients: Relationship between Movement Fluidity and the Motor Strategy in Initial Contact

Purpose: Generally, stroke patients can walk and stand up fluidly but fulfill the sit-to-walk (STW) task with difficulty. The purpose of this study was to investigate the relationship between movement fluidity and motor strategy in the initial contact of the STW task. Method: Thirty stroke patients and ten healthy subjects performed the STW task from a sitting position, and their movement was measured by a motion analysis system. The differences in data between patients and healthy subjects were analyzed using the Mann-Whitney U test. The relationship between fluidity index (FI) and other indices (kinetic and kinematic data in STW, functional independence measure [FIM], and Fugl-Meyer Assessment [FMA]) were analyzed using Spearman''s rank correlation coefficient. Results: The stroke patients had lower FI values than the healthy subjects and exhibited shortened step length and prolonged duration from onset to the first stance leg off. FI values correlated with trunk flexure angle at initial contact, first step length, and maximum vertical floor reaction force. The independent level of the FIM of stair climbing and walking ability and the FMA of balance also correlated with FI. Conclusion: There is a possibility that poor balance is one of the reasons why stroke patients are unable to start walking fluently from the sitting position. To perform the STW fluidly, patients must start walking before the trunk extension is fully completed. The relationship between FI and indices of physical ability, namely stair climbing and balance, may have therapeutic benefits for coaching the STW task to stroke patients.     

Self-compensation of third-order dispersion for ultrashort pulse generation demonstrated in an Yb fiber oscillator

Compensation of the intracavity dispersion in the mode-locked oscillator is known to be one of the most important factors for ultrashort pulse generation. However, recent investigations of a Yb-doped fiber mode-locked oscillator revealed that precise third-order dispersion (TOD) compensation is not always necessary for ultrashort pulse generation, owing to the strong nonlinearity that compensates residual TOD without reducing its spectral bandwidth. The origin of the nonlinear TOD compensation has remained unclear. To investigate the process in detail, we studied the pulse evolution inside a 30 fs Yb-doped fiber mode-locked oscillator both experimentally and numerically, and we found that the nonlinear phase shift with a temporally asymmetric pulse shape introduces an appropriate amount of TOD that exactly cancels the residual cavity dispersion.