Segmented block copolyesters using click chemistry

Copper(I) catalyzed azide‐alkyne 1,3‐Huisgen cycloaddition reaction afforded the synthesis of triazole‐containing polyesters and segmented block copolyesters at moderate temperatures. Triazole‐containing homopolyesters exhibited significantly increased (～40 °C) glass transition temperatures (T_g) relative to high temperature, melt synthesis of polyesters with analogous structures. Quantitative synthesis of azido‐terminated poly(propylene glycol) (PPG) allowed for the preparation of segmented polyesters, which exhibited increased solubility and mechanical ductility relative to triazole‐containing homopolyesters. Differential scanning calorimetry demonstrated a soft segment (SS) T_g near ?60 °C for the segmented polyesters, consistent with microphase separation. Tensile testing revealed Young's moduli ranging from 7 to 133 MPa as a function of hard segment (HS) content, and stress at break values approached 10 MPa for 50 wt % HS segmented click polyesters. Dynamic mechanical analysis demonstrated an increased rubbery plateau modulus with increased HS content, and the T_g's of both the SS and HS did not vary with composition, confirming microphase separation. Atomic force microscopy also indicated microphase separated and semicrystalline morphologies for the segmented click polyesters. This is the first report detailing the preparation of segmented copolyesters using click chemistry for the formation of ductile membranes with excellent thermomechanical response. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A novel polymerization approach via thiol‐yne addition

The ability of thiyl radicals to add to terminal unsaturations in an efficient way made them considered being one of the click reactions. Recently, thiol‐yne addition reactions have been used extensively for the synthesis of crosslinked networks and dendrimers and postpolymerization functionalization protocols. Herein, we report a novel step‐growth type reaction for highly functional linear polymers using a monoalkyne and dithiol compound. First, we investigated the model reaction between 1‐octyne and 1‐octanethiol as well as 1,4‐butanedithiol compounds, which were initiated via self‐, thermal‐, and UV‐initiation; the UV‐initiation was found to be the most efficient method and completed within 2‐h reaction time. The same conditions were applied for the polymerization of four different functional alkynes bearing different functional groups with two dithiol compounds. All polymerizations resulted in highly functional linear polymers with number averaged molecular weights ranging from 5 to 30 kDa, except for propargylic acid and its methyl ester, where only oligomers formed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Performance of ring oscillators composed of gate-all-around FETs with varying numbers of nanowire channels using TCAD simulation

In this paper, we investigate the performance of ring oscillators composed of gate-all-around (GAA) silicon nanowire (NW) field-effect transistors (FETs) with four different numbers of NW channels, for sub-10-nm logic applications. Our simulations reveal that ring oscillators with double, triple, and quadruple NW channels exhibit improvements of up to 50%, 85%, and 97%, respectively, in the oscillation frequencies (f_osc), compared to a ring oscillator with a single NW channel, due to the large drive current, in spite of the increased intrinsic capacitance of a given device. Moreover, our work shows that the f_osc improvement ratio of the ring oscillators becomes saturated with triple NW channels with additional load capacitances of 0.1 fF and 0.01 fF, which are similar to, or less than the intrinsic device capacitance (∼0.1 fF). Thus, our study provides an insight for determining the capacitive load and optimal number of NW channels, for device development and circuit design of GAA NW FETs.     

COUPLING EFFECTS OF VOID SHAPE AND VOID SIZE ON THE GROWTH OF AN ELLIPTIC VOID IN A FIBER-REINFORCED HYPER-ELASTIC THIN PLATE

The growth of a prolate or oblate elliptic micro-void in a fiber reinforced anisotropic incompressible hyper-elastic rectangular thin plate subjected to uniaxial extensions is studied within the framework of finite elasticity. Coupling effects of void shape and void size on the growth of the void are paid special attention to. The deformation function of the plate with an isolated elliptic void is given, which is expressed by two parameters to solve the differential equation. The solution is approximately obtained from the minimum potential energy principle. Deformation curves for the void with a wide range of void aspect ratios and the stress distributions on the surface of the void have been obtained by numerical computation. The growth behavior of the void and the characteristics of stress distributions on the surface of the void are captured. The combined effects of void size and void shape on the growth of the void in the thin plate are discussed. The maximum stresses for the void with different sizes and different void aspect ratios are compared.     

Facile Fabrication of Nanorod‐Assembled Fluorine‐Substituted Hydroxyapatite (FHA) Microspheres

Nanorod‐assembled FHA microspheres with different F contents were for the first time prepared through a facile one‐step hydrothermal method. The effect of the reaction time and pH value of reaction solutions on the FHA morphology was investigated to elucidate the self‐assembly process of FHA microspheres. The results showed pH values had significant effect on the morphology of the formed FHA crystals, which were self‐assembled into sphere‐like sturctures at high pH conditions and rod‐like structures at low pH values. The results suggested that formation of FHA crystals with varied morphology may be directly related to Ca²⁺ release kinetics from EDTA‐Ca‐Na₂ at different pH conditions. Furthermore, it was found that the chemical stability of FHA microspheres was dependent on the F content in the materials, and high F contents in FHA microspheres lead to improved chemical stability. These results suggest that the prepared self‐assembled FHA microspheres may be used for teeth substitution materials due to their unique hierarchical structures and controllable chemical stability.     

The Kirchhoff type Schrödinger problem with critical growth

In this paper, we study the Kirchhoff type problem with critical growth. By using the variational method, the existence and multiplicity of solutions are obtained.     

Optical time-resolved study of the excitation dynamics*

Transient behaviour of the excited states originated from the neutral and the charged species is discussed using data from time-resolved experiments. Complex transient characteristics obtained for the slightly charged poly-(bithiophene) film during electrochemical doping were explained in terms of sequential molar fraction changes of the neutral species, the radical cation and the π-dimerized radical cations. Femtosecond transient absorption measurement carried out in time range of 0-4 ns for a two-photon excited dye reveals a multi-exponent decay with well separated relaxation times and the distinct relaxation mechanisms. At high irradiance and a sufficient fluence, the multi-photon excitation processes affect the subpicosecond response and lead to formation of the photo-products.     

Perfluorocyclohexenyl aryl ether polymers via polycondensation of decafluorocyclohexene with bisphenols

A novel class of semifluorinated perfluorocyclohexenyl (PFCH) aryl ether homo/copolymers was successfully synthesized with high yield through the step‐growth polymerization of commercially available bisphenols and decafluorocyclohexene in the presence of a triethylamine base. The synthesized polymers exhibit variable thermal properties depending on the functional spacer group (R). PFCH aryl ether copolymers with random and alternating architectures were also prepared from versatile bis‐perfluorocyclohexenyl aryl ether monomers. The PFCH polymers show high thermal stabilities with a 5% decomposition temperature ranging from 359 to 444 °C in air and nitrogen atmosphere. These semifluorinated PFCH aromatic ether polymers contain intact enchained PFCH olefin moieties, making further reactions such as crosslinking and application specific functionalization possible. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 232–238     

The fabrication of ReS2 flowers at controlled locations by chemical vapor deposition

Here we report a metal induced nucleation to realize the growth of ReS₂ flowers at controlled locations. The ordered arrays of ReS₂ flowers have been successfully prepared on SiO₂/Si substrate using Pt metal dots as nucleation sites and S, NH₄ReO₄ powders as precursors by a chemical vapor depostion method. The NH₄ReO₄ powders are used as the rhenium sources. The ReS₂ flowers are grown above the pre-patterned Pt dots, Raman and transmission electron microscopy measurements indicated that the prepared ReS₂ flowers have excellent crystalline quality.