Structures and mechanical properties of electrospun cellulose nanofibers/poly(ε-caprolactone) composites

Poly(ε-caprolactone) (PCL) is one of the ecofriendly biodegradable polymers with excellent moldability but with rather low mechanical properties especially for the industrial and biomedical use. In this research, to overcome the problem, the two types of cellulose nanofibers, the cellulose acetate nanofibers (CA-NF) and the cellulose nanofibers (C-NF), were composited into PCL for the enhancement of the mechanical properties of PCL. CA-NF were prepared by electrospinning and converted into C-NF afterward by deacetylation. It was found that the Young's modulus of the CA-NF/PCL composite at the fiber concentration of 35 wt% significantly increased by ~3 times as compared with that of neat PCL, whereas C-NF/PCL of the same fiber concentration also increased by ~4.5 times. It was also found that the Young's moduli of CA-NF/PCL nearly reached the theoretical values calculated by the equation suggested by Tsai, but that the Young's moduli of C-NF/PCL could not reach the theoretical values. It indicates that CA-NF possessed better compatibility with PCL than C-NF, agreeing well with the fracture-surface analyses of the two composites by the scanning electron microscopy.     

Preparation of bismuth nanowire encased in quartz template for Hall measurements using focused ion beam processing

ABSTRACT: Forming electrodes on opposite sides of an individual bismuth nanowire was attempted to prepare for Hall measurements. Although a 1-mm-long bismuth nanowire which is completely covered with a quartz template has been successfully fabricated to prevent oxidation, it is very difficult to attach Hall electrodes on the opposite sides of the nanowire due to the quartz covering. One side of the cylindrical quartz template was removed by polishing without exposure of the nanowire to the atmosphere; the thickness between the polished template surface and the nanowire was estimated to be several micrometers. Focused ion beam processing was successfully employed to expose both surfaces of the nanowire under high vacuum by removing part of the quartz template. A carbon thin film was then deposited in situ on the wire surface to fabricate an electrical contact on the bismuth nanowire sample. Furthermore, the energy dispersive X-ray analysis was performed to the area processed by focused ion beam, and the bismuth component of the nanowire was successfully detected. It was confirmed that the focused ion beam processing was applicable to attach electrodes to bismuth nanowire for Hall measurement.     

Robust Linear Interpolation and Extrapolation of Stationary Time Series in Lp

To deal with uncertainty of the spectral distribution, we consider minimax interpolation and extrapolation problems in L^p for stationary processes. The interpolation and extrapolation problems can be regarded as a linear approximation problem on the unit disk in the complex plane. Although the robust one-step-ahead predictor and interpolator has already been considered separately in the previous literature, we give two conditions for the uncertainty class to find the minimax interpolator and extrapolator in the general framework from both the point of view of the observation set and the point of view of evaluation on the interpolation and extrapolation error under the L^p-norm. We show that there exists a minimax interpolator and extrapolator for the class of spectral densities ε-contaminated by unknown spectral densities under our conditions. When the uncertainty class contains spectral distribution functions which are not absolutely continuous to the Lebesgue measure, we show that there exists an approximate interpolator and extrapolator in L^p such that its maximal interpolation and extrapolation error is arbitrarily close to the minimax error when the spectral distributions have densities. Our results are applicable to the stationary harmonizable stable processes.     

Models for circular data from time series spectra

Circular data are those for which the natural support is the unit circle and its toroidal extensions. Numerous constructions have been proposed which can be used to generate models for such data. We propose a new, very general, one based on the normalization of the spectra of complex-valued stationary processes. As illustrations of the new construction's application, we study models for univariate circular data obtained from the spectra of autoregressive moving average models and relate them to existing models in the literature. We also propose and investigate multivariate circular models obtained from the high-order spectra of stationary stochastic processes generated using linear filtering with an autoregressive moving average response function. A new family of distributions for a Markov process on the circle is also introduced. Results for asymptotically optimal inference for dependent observations on the circle are presented which provide a new paradigm for inference with circular models. The application of one of the new families of spectra-generated models is illustrated in an analysis of wind direction data.     

Synthesis and optical properties of the [2.2]paracyclophane-containing π-conjugated polymer with a diacetylene unit

Summary Novel through-spaceπ-conjugated polymer based on poly(p-henyleneethynylene)/poly(p-phenylenebutadiynylene) hybrids containing a [2.2]paracyclophane unit in the main chain was synthesized by copper-catalyzed alkyne coupling reaction. The structure of the polymer was supported by ¹H NMR and IR spectra. The obtained polymer was soluble in common organic solvents such as THF, CH₂C1₂, CHC1₃ and toluene. The number-average of molecular weight of the polymer was estimated to be 63000 by GPC. The polymer emitted a bluish green light in solution and in the solid state. Received:24 September 2002/Revised version: 19 November 2002/Accepted: 19 November 2002 Correspondence to Yoshiki Chujo     

Synthesis and properties of conjugated copolymers having a tricarbonyl(arene)chromium and thiophene units in the main chain

Summary Palladium-catalyzed polymerization of η ⁶-(1,4-diethynylbenzene)tricarbonyl chromium (1) with 3-alkyl-2,5-dibromothiophene (2a-c) was carried out to give the corresponding alternating conjugated copolymers (5a-c) in good yields. The structures of the polymers were supported by ¹H NMR and IR spectra. The polymers obtained were soluble in common solvents such as THF, CH₂Cl₂, CHCl₃ and toluene. The molecular weights of the polymers were determined by GPC. Their thermal, optical and electrical properties were investigated in detail. Received: 18 March 2002 /Accepted: 1 April 2002     

N-Alkylation of chitin and some characteristics of the novel derivatives

Summary Introduction of simple alkyl groups at the C-2 nitrogen of chitin and some properties of the resulting N-alkyl-chitins have been examined. Chitosan was fully deacetylated and treated with three kinds of aldehydes, formaldehyde, acetaldehyde, and pentanal. The Schiff bases of chitosan, whose extents of substitution were dependent on the amount of aldehydes, were reduced with sodium cyanoborohydride to N-alkylated chitosans. The N-alkyl-chitosans were then transformed into the corresponding N-alkyl-chitins by acetylation with acetic anhydride followed by transesterification to remove partly formed O-acetyl groups. The resulting N-methyl-, ethyl-, and pentyl-chitins were amorphous and showed improved affinity for organic solvents. Received: 13 December 2001/Revised version: 11 January 2002/Accepted: 17 January 2002     

Synthesis and Properties of Novel Poly(p-phenylenevinylene)s Containing a Tricarbonyl(arene)chromium Unit in the Main Chain

Summary Novel π-conjugated polymers based on poly(p-phenylenevinylene)s (PPVs) containing a tricarbonyl(arene)chromium unit in the main chain were synthesized by Horner-Wadsworth-Emmons olefination. The structures of the polymers were supported by ^lH NMR and IR spectra. The polymers obtained were soluble in common solvents such as THF, CH₂Cl₂, CHCl₃ and toluene. The molecular weights of the polymers were determined by GPC. Their thermal, optical, and electrochemical properties were investigated in detail. Received: 18 November 2002/Revised version: 10 February 2003/ Accepted: 11 February 2003 Correspondence to Yoshiki Chujo     

Radical polymerization of butyl acrylate and random copolymerization of styrene and butyl acrylate and styrene and methyl methacrylate mediated by monospiro- and dispiropiperidinyl-N-oxyl radicals

Radical polymerization of butyl acrylate (BA) and random copolymerizations of styrene (St) and BA and St and methyl methacrylate (MMA) in the presence of 7-aza-15-hydroxydispiro[5.1.5.3]hexadecane-7-yloxyl (1) and 1-aza-2,2-dimethyl-4-hydroxyspiro[5.6]dodecane-1-yloxyl (2) were carried out. Radical polymerization of BA at 120 °C in the presence of 1 gave poly(BA) with M_n=20200 and M_w/M_n=1.30 at 23% conversion. The termination of polymerization observed around ∼20% conversion was solved to a certain extent by an addition of small amounts of dicumyl peroxide, and poly(BA) with M_n=37400 and M_w/M_n=1.33 was obtained in 46% yield. Random copolymerizations of St and BA and St and MMA in the presence of 1 and 2 at 80 °C gave the corresponding random copolymers with narrow polydispersities of 1.12-1.38 at the molar fraction above 0.30 of St in feed. The kinetic study for the NO-C bond homolysis of the corresponding alkoxyamines prepared from 1 and 2 were carried out, and evaluation of the preexponential factors (A_act) and the activation parameters (E_act) showed that the steric factors of the nitroxides are reflected mainly on E_act.     

Kinetically Stable Bicelles with Dilution Tolerance,Size Tunability,and Thermoresponsiveness for Drug Delivery Applications

Mixtures of a phospholipid (1,2‐dipalmitoyl‐sn‐glycero‐3‐phosphatidylcholine, DPPC) and a sodium‐cholate‐derived surfactant (SC‐C₅) at room temperature formed phospholipid bilayer fragments that were edge‐stabilized by SC‐C₅: so‐called “bicelles”. Because the bilayer melting point of DPPC (41 °C) is above room temperature and because SC‐C₅ has an exceptionally low critical micelle concentration (<0.5 mm ), the bicelles are kinetically frozen at room temperature. Consequently, they exist even when the mixture is diluted to a concentration of 0.04 wt %. In addition, the lateral size of the bicelles can be fine‐tuned by altering the molar ratio of DPPC to SC‐C₅. On heating to ≈37 °C, the bicelles transformed into micelles composed of DPPC and SC‐C₅. By taking advantage of the dilution tolerance, size tunability, and thermoresponsiveness, we demonstrated in vitro drug delivery based on use of the bicelles as carriers, which suggests their potential utility in transdermal drug delivery.