Synthesis of all stereoisomers of sulfinylcalix[4]arenes

All four stereoisomers of p-tert-butylsulfinylcalix[4]arene [4(rccc), 4(rcct), 4(rctt), and 4(rtct)], arising from the disposition of the four sulfinyl groups with respect to the mean plane of the four bridging sulfur atoms, have been prepared via oxidation of p-tert-butylthiacalix[4]arene (2) or its tetra-O-benzyl ethers 5 of defined conformations. Thus, treatment of 2 with 4.4 molar equiv of NaBO(3).4H(2)O gave the rtct and rctt isomers in 27% and 17% yields, respectively, while oxidation of cone 5 (5(C)) and partial cone 5 (5(PC)) proceeded stereoselectively to give, after debenzylation of the resulting tetrasulfoxides 12 and 15, the rccc and rcct isomers in 56% and 28% yields, respectively, based on 5. The sulfinylcalix[4]arenes 4 were treated with iodomethane in the presence of a base to give the corresponding tetramethyl ethers 16, the structures of which in regard to the disposition of the sulfinyl groups and the conformation of the phenol units were determined by X-ray crystallography. Also reported is the synthesis of all four conformational isomers of tetra-O-benzyl ether of 2 (5(C), 5(PC), 5(1,2-A), and 5(1,3-A)).     

Crystal Structures of Mono-, Di-, and Tri(p-tert-butyl)-thiacalix[4]arenes: Dimeric Self-inclusion Behavior

X-Ray crystal structures of the mono-, di-, and tri(p-tert-butyl)-substituted thiacalix[4]arenes (TC4As; 1, 2, and 3, respectively) have beendetermined. TC4As 1–3 adopt a cone conformation and form dimeric self-inclusion units in such a manner that phenol moieties are inserted into the cavity of each molecule. In all the crystal structures of 1–3, lateralface-to-face interactions exist between the phenol rings that do not bear a tert-butyl substituent, and seemingly, this molecular assembly stabilizes the formation of self-inclusion. TC4As 1 and 2 adopt a cone conformation with C₂ symmetry, leading to the formation of rim-to-rim intermolecular hydrogenbonds so as to link the dimeric units up and down. On the other hand, 3 adopts a regular cone conformation with C₄ symmetry to form cyclic hydrogen bonds withinthe rim part of TC4A.     

A simplified optical method for measuring residual stress by rapid cooling in thermosetting resin strip

This paper presents a simplified optical method for measuring the residual stresses by rapid cooling in thermosetting resin strips. First, the fundamental equations for calculating the residual stress from the residual birefringence were obtained by the linear photoviscoelastic theory. The specimens were then subjected to rapid cooling. After rapid cooling, the residual stress was measured by two methods, the simplified optical method mentioned above and the well-known layer-removal method. The effectiveness of the simplified optical method was discussed by comparing results of the two methods.     

Dynamic properties of combustion instability in a lean premixed gas-turbine combustor

We experimentally investigate the dynamic behavior of the combustion instability in a lean premixed gas-turbine combustor from the viewpoint of nonlinear dynamics. A nonlinear time series analysis in combination with a surrogate data method clearly reveals that as the equivalence ratio increases, the dynamic behavior of the combustion instability undergoes a significant transition from stochastic fluctuation to periodic oscillation through low-dimensional chaotic oscillation. We also show that a nonlinear forecasting method is useful for predicting the short-term dynamic behavior of the combustion instability in a lean premixed gas-turbine combustor, which has not been addressed in the fields of combustion science and physics.     

Decryption characteristics in message modulation type chaos secure communication system using optical fiber ring resonators

Message modulation type chaos secure communication system using optical fiber ring resonators is analyzed numerically. It is found that the decryption characteristics degrades monotonically as the differences in parameters which are not included in the linear phase term becomes large, while they degrade periodically with a period of 2π as the differences in parameters included in the linear phase term increase. When a noise is added in the input light, the error dispersion in the message demodulation is determined by the noise level in the small parameter difference region, while the parameter differences it dominates in the large parameter difference region. Best decryption characteristics are always obtained at the minimum input power for the chaos generation, i.e., at the lowest Lyapnov exponent in chaos state in the message modulation type chaos secure communication system using optical fiber ring resonators.     

Spectrophotometric determination of uric acid based on fading of o-hydroxyhydroquinonephthalein-palladium(II)-hexadecyltrimethyl-ammonium complex.

A simple and highly sensitive spectrophotometric method for the determination of uric acid (UA) was established based on fading of the o-hydroxyhydroquinonephthalein-palladium(II)-hexadecyltrimethylammonium complex. In the determination of UA, Beer's law is obeyed in the range of 0.01-0.20 microg ml(-1), with an effective molar absorptivity at 635 nm, the relative standard deviation being 6.5 x 10(5) dm(3) mol(-1) cm(-1) and 1.5% (n = 5). This method is about 20-times more sensitive than the conventional methods. The method was successfully applied to the assay of UA in human urine.     

Residual stresses and warp generated by one-sided quench of an epoxy-resin beam

This paper discusses the warp and accompanying residual stress in a rectangular epoxy beam produced by water cooling its lower surface. First, the theoretical values of this warp and residual stress are obtained by the linear-viscoelastic theory. The specimen is then subjected to quenching. The variations in the warp are observed. After quenching, the residual stress is measured by a layer-removal method. The experimental and theoretical results are then compared and discussed.     

Determination of cyanide in blood by electrospray ionization tandem mass spectrometry after direct injection of dicyanogold

An electrospray ionization tandem mass spectrometric (ESI-MS-MS) method has been developed for the determination of cyanide (CN^–) in blood. Five microliters of blood was hemolyzed with 50 μL of water, then 5 μL of 1 M tetramethylammonium hydroxide solution was added to raise the pH of the hemolysate and to liberate CN^– from methemoglobin. CN^– was then reacted with NaAuCl₄ to produce dicyanogold, Au(CN)₂^–, that was extracted with 75 μL of methyl isobutyl ketone. Ten microliters of the extract was injected directly into an ESI-MS-MS instrument and quantification of CN^– was performed by selected reaction monitoring of the product ion CN^– at m/z 26, derived from the precursor ion Au(CN)₂^– at m/z 249. CN^– could be measured in the quantification range of 2.60 to 260 μg/L with the limit of detection at 0.56 μg/L in blood. This method was applied to the analysis of clinical samples and the concentrations of CN^– in the blood were as follows: 7.13 ± 2.41 μg/L for six healthy non-smokers, 3.08 ± 1.12 μg/L for six CO gas victims, 730 ± 867 μg for 21 house fire victims, and 3,030 ± 97 μg/L for a victim who ingested NaCN. The increase of CN^– in the blood of a victim who ingested NaN₃ was confirmed using MS-MS for the first time, and the concentrations of CN^– in the blood, gastric content and urine were 78.5 ± 5.5, 11.8 ± 0.5, and 11.4 ± 0.8 μg/L, respectively.     

Statistical Assessment of Tensile Static,Creep and Fatigue Strengths for Unidirectional CFRP

Background

The tensile strength along the longitudinal direction of unidirectional carbon fiber reinforced plastics (CFRPs) constitutes important data for the reliable design of CFRP structures. Our earlier reports proposed the formulations for the statistical static, creep, and fatigue strengths of CFRP based on Christensen’s model of the viscoelastic crack kinetics.

Objective

This study is concerned with the statistical assessment of the tensile static, creep, and fatigue strengths of unidirectional CFRPs by using the proposed formulations and the characterization of the long-term strengths of unidirectional CFRPs.

Method

First, the proposed formulations for the time-dependent and temperature-dependent statistical static, creep, and fatigue strengths of CFRP are introduced. Second, the tensile static, creep and fatigue strengths of unidirectional CFRP are measured statistically at various temperatures using resin-impregnated CFRP strands as tensile test specimens by measuring the viscoelasticity of the matrix resin. Finally, the master curves showing the long-term life of these strengths are constructed by substituting these measured data into the formulations.

Results

The results clarify that the formulations are applicable with high reliability over wide ranges of time and temperature for the statistical tensile static, creep and fatigue strengths of unidirectional CFRP except above the glass transition temperature of the matrix resin. Therefore, the fatigue strength degradation phenomena of unidirectional CFRPs can be expressed by the time- and temperature-dependent part due to the viscoelastic behavior of the matrix resin and the number of load cycle-dependent parts.

Conclusions

The long-term life prediction of unidirectional CFRPs under static, creep and fatigue tension loadings can be determined by ascertaining the mechanical properties of the CFRP and matrix resin in the proposed formulations.