Radical formation during tensile deformation of highly drawn crystalline poly[p-(2-hydroxyethoxy)benzoic acid] fibers

The micromechanism of tensile deformation of poly[p-(2-hydroxyethoxy)benzoic acid] fibers is discussed on the basis of a detailed esr study of radical formation. The concentration of primary phenoxy radicals, which were detected during deformation at room temperature as a direct indicator of main-chain rupture, was determined by extrapolating the radical decay curves at various strains to zero time. The relation between the initial radical concentration and the strain is well expressed by the cumulative normal distribution curve. By use of this relation and a model of fiber structure, the distribution of the contour length of tie chains was determined. No radicals were detected during a second stretching cycle until the maximum strain in the first run was exceeded. The deformation model which includes alternating crystalline and amorphous regions connected by tie chains, a distribution of contour lengths of tie chains, and a phase transformation of molecular chains in the crystalline region accounted fairly well for the observed stress–strain behavior of monofilaments in first and second stretching cycles. The comparison between the observed and the calculated radical concentration suggests that statistical factors and other deformation mechanisms have to be taken into account.     

Preparation of chiral 5-deazaflavin derivatives and their asymmetric reduction of ethyl benzoylformate

1,5-Dihydro-5-deazaflavin derivatives possessing a chiral substituent at N(3) position were synthesized, with which moderate asymmetric induction was observed in the reduction of ethyl benzoylformate.     

Chemical reactivities of the cation and anion of M@C82 (M = Y, La, and Ce)

The chemical reduction and oxidation of M@C82 (M = Y, La, and Ce) afford the corresponding anion and cation, respectively, which show unique and interesting chemical reactivities. It is found that the successful reversible gain or loss of electrons by ionization is useful for controlling the stability and reactivity of M@C82 toward both nucleophiles and electrophiles.     

Iodobenzene-catalyzed alpha-acetoxylation of ketones. in situ generation of hypervalent (diacyloxyiodo)benzenes using m-chloroperbenzoic acid

Reported here for the first time is the iodobenzene-catalyzed alpha-oxidation of ketones, in which diacyloxy(phenyl)-lambda3-iodanes generated in situ act as real oxidants of ketones and m-chloroperbenzoic acid serves as a terminal oxidant. Oxidation of a ketone with m-chloroperbenzoic acid in acetic acid in the presence of a catalytic amount of iodobenzene, BF3.Et2O, and water at room temperature under argon affords an alpha-acetoxy ketone in good yield. p-Methyl- and p-chloroiodobenzene also serve as efficient catalysts in this direct oxidation. We found that when the reaction was carried out in the absence of a catalytic amount of iodobenzene, Baeyer-Villiger oxidation of a ketone took place. It is noted that use of water and BF3.Et2O is crucial to the success of this alpha-acetoxylation.     

A basic study of column adsorption chromatography : Part I. Standardization of adsorbent

The method of measuring f(I) values is proposed as a measure of the adsorption capacity of adsorbents. The f(I) value, a characteristic figure for a particular system, can be obtained chromatogiaphically by measuring the progression rate of zone and the degree of packing of the column. For a system involving a unit concentration of trasns-p-methoxyazobenzene in benzene as standard solution and alumina as adsorbent, optimum conditions for the measurement of f(I) were established. The effects of day-light, pretreatment of column, temperature, flow rate of solution, amount of adsorbent and degree and mode of packing were studied Under optimum conditions, the value of f(I) was reproducible within ±2%.     

1,3,4,6-Tetrakis(isopropylthio)thieno[3,4-c]thiophenium bis(tetrafluoroborate): X-ray crystal structure of a stable thieno[3,4-c]thiophene dication

The structure of the 1,3,4,6-tetrakis(isopropylthio)thieno[3,4-c]thiophene dication ( 2 ) prepared from 1,3,4,6-tetrakis(isopropylthio)thieno[3,4-c]thiophene ( 1 ) by two-electron oxidation was investigated by X-ray crystallographic analysis. The results revealed that the positive charges are largely delocalized on the two i-PrS-C-C-C-SPr-i moieties.     

A facile synthesis of [3ncyclophanes,in which aromatic rings are connected with -CH2CO-CH2- bridges

The title compounds, I, were synthesized by the dialkylation of TosMIC, II, with appropriate bis (halomethyl) compounds, III, under phase-transfer condition, followed by acid hydrolysis.     

Bidirectional and colorimetric recognition of sodium and potassium ions

Host 1 based on the phenolphthalein skeleton and two crown ether moieties demonstrated opposite behaviors toward sodium and potassium cations caused by bidirectional complexation. [reaction: see text]     

In situ observation of cell-detachment process initiated by femtosecond laser-induced stress wave

When a stress wave generated by focusing a femtosecond laser is loaded on an animal cell adhered on a substrate, the cell is detached from the substrate. There are two possible mechanisms for the cell detachment: (a) The cell is detached from a scaffold coated on a glass plate, and (b) the cell is detached from the glass plate with the scaffold. In this work, we have studied the cell-detachment mechanism by visualizing the scaffold with a fluorescence probe of quantum dots. When the cell was detached from the substrate, fluorescence from the scaffold simultaneously disappeared from the glass plate, although the scaffold was not irradiated by the laser. This indicates that detachment due to the stress wave is attributed to mechanism (a). On the other hand, when the cell was detached from the substrate by a trypsin treatment, the fluorescence from the scaffold remained, suggesting mechanism (b). By comparing both results, it is considered that physiological damage of the cell membrane during the detachment process by femtosecond laser-induced stress wave is less than that due to the trypsin treatment.