Anomalous properties of poly(γ-benzyl L-glutamate) film composed of unusual 7/2 helices

Poly(γ-benzyl L-glutamate) film composed of unusual 7-residue 2-turn (7/2) helices was prepared by slow casting from chloroform solution. The 7/2 helical conformation was irreversibly transformed at 84°C to the normal 18/5 conformation. In d.s.c. thermograms the transformation appeared as an endothermic first order transition with an enthalpy change of 3.4 cal g⁻¹. The viscoelastic and dielectric measurements indicated that the loss peak due to the side chain motion in this film was reduced to a great extent compared to the film of 18/5 helices. The dielectric relaxation strength dictated that there was a motional restriction in three quarters of the side chains. By comparison to a racemic mixture of poly(γ-benzyl glutamate), these anomalous properties were attributed to the stack of terminal benzyl groups of side chains (ormed in an alternating manner between neighbouring chains). The first order transition arises from the cooperative fusion of the stack and the side chains with their benzyl groups which are restricted in thermal motion. Such stacks may be facilitated by the precise ‘knob (side chain) and hole (space between side chains)’ packing which can be attained between neighbouring 7/2 helices.     

A theory of pseudo cross-link

Summary A theory of pseudo cross-link model suggests the existence of multiple links of various size composed of 116 segmental units. They possesses the heat and entropy of various magnitude giving various transition temperature, T_A for the cross-link composed of 4 segments and T_B for that of 16 segments. The glass-transition point T_g and the melting point T_m are defined by the different size of lateral multiple links. Relationships, T_m = 2 T_A and T_g = (2/3)T_m = (4/3)T_A, are derived. A wedge-type relaxation spectrum is obtained as a distribution of size of cross-links. For temperature dependence the WLF-equation is obtained.     

Measurement of heat of mixing for ammonium chloride + ammonia system at 25 °c

Heat of mixing for ammonium chloride in liquid ammonia at 25°C was determined in the concentration range 0-50 wt% NH₄Cl. It was calculated from the differential heat of solution observed in this work and the differential heat of dilution estimated from activities of solvent. A twin isoperibol calorimeter consisting of two stainless Dewar vessels was used at a relatively high pressure (up to 1.5 MPa). The accuracy of this calorimetry was examined by measuring the heat of solution for tris-(hydroxymethyl)aminomethane(THAM) in 0.1 kmol/m³ HCl at 25°C, and satisfactory agreement within 1.1% between experimental and literature value was obtained. The reproducibility for the experiment was within 2.8%.     

X-ray spectroscopy of highly ionised atoms of Ti through Zn in a dense plasma

X-ray spectra for several elements have been observed from a high-temperature plasma produced in a vacuum spark using a curved-crystal spectrometer. The transition wavelengths of the He-like resonance lines for Ti through Zn are determined for the first time under careful experimental treatments. The result is compared with theoretical predictions. The transition wavelengths of the Fe He-like resonance series lines up to 1s6p–1s² and the Kβ transition energies of Ti partially M-shell-ionised ions (Ti VI–XIII) are also determined. As a result, several satellite lines are found.     

Ozonization of amides

Ozonization of various amides was carried out as a model reaction for the degradation of polyamides with ozone. N-alkylamides and N,N-dialkylamides were found to be reactive compared with those amides which have no alkyl group on the nitrogen atom, and it was suggested that ozone attacks preferentially N-methylene or N-methyl group of amides in the first step of ozonization.     

In vivo pressure estimation using subharmonic contrast microbubble signals: proof of concept

Changes in ambient pressure affects the reflectivity of ultrasound contrast microbubbles leading to an excellent correlation between subharmonic signals and hydrostatic pressure. The aortas of two dogs were scanned with an experimental pulse-echo system to validate in vivo pressure estimation based on subharmonic microbubble signals. Results matched well with instantaneous pressure measurements (from 20-60 mmHg) obtained simultaneously with a pressure catheter (root mean square errors <27%).     

Anisotropy of styrene–butadiene rubber

Anisotropy of styrene–butadiene rubber (SBR) was investigated. The anisotropy of the copolymer varies linearly with the styrene content and the ultimate value coincides with that of polystyrene at elevated temperature. From these facts, the transverse configuration of the pendant phenyl group is estimated irrespective of the styrene content of SBR.     

Monitoring biofilm development in a microfluidic device using modified confocal reflection microscopy

The feasibility of a method to monitor biofilm development non-destructively in a microfluidic device was addressed. Here, we report that biofilm growth could be non-destructively monitored by an image analysis technique based on modification of confocal reflection microscopy.     

Synthesis of proton conductive membranes based on inorganic–organic hybrid structure bound with phosphonic acid

Proton conductive inorganic–organic hybrid membranes were synthesized from styrene derivatives of alkoxysilane and ethyl 2-[3-(dihydroxyphosphonyl)-2-oxopropyl] acrylate (EPA) through copolymerization followed by sol–gel reaction. Self-standing, homogeneous and transparent hybrid membranes with chemically bound phosphonic acid groups were synthesized. FT-IR analysis exhibited the hybrid membranes included phosphonic acid groups. ¹³C and ²⁹Si NMR studies indicated that alkoxysilyl functionalized styrene derivatives were not only copolymerized with EPA but also condensed yielding Si–O–Si linkages by sol–gel reaction. TG–DTA analysis revealed that these membranes were thermally stable up to 200 °C in dry O₂. The proton conductivities of the hybrid membranes increased with phosphonic acid content and temperature. The P/Si ratio of the membrane was dependent on the number of alkoxy group in the starting alkoxysilane. The hybrid membrane from (dimethylmethoxysilylmethyl)styrene (DMMSMS(M))/EPA = 1/6 revealed proton conductivities of 6.3 × 10⁻³ and 2.4 × 10⁻⁴ S cm⁻¹ at 68.0% relative humidity and 18.8% relative humidity, respectively, at 140 °C.     

BP神经网络权值初始值与收敛性问题研究

BP神经网络的收敛性问题是一直受到广泛关注的问题。本文针对BP网络在运算过程中陷入局部最小区，收敛速度慢的问题，从BP算法的原理出发，讨论了权值初始值对网络训练速度的强烈影响（仿真结果证明了这一点），并提出了解决方法。