Phase transition in dilute solution of poly(γ-benzyl-L-glutamate) in dichloromethane at a low temperature

The dielectric constant of solutions of poly(γ-benzyl-L -glutamate) (PBLG) in dichloromethane shows a jump near 195°K, irrespective of frequency. Therefore, the discontinuity is not a dispersion phenomenon but a phase transition in the thermodynamic sense. The transition temperature is independent of the concentration in the range from 0.01 to 10% by weight, but it increases linearly with the logarithm of the molecular weight of PBLG. The height of the jump depends strongly on frequency, concentration, and molecular weight. The viscosity also changes abruptly at 195°K. These results suggest that the PBLG molecule forms a cluster like a liquid crystal or is in a random coil state below the transition point.     

Studies on the syntheses of heterocyclic compounds. Part DCXLIV . Catalytic reduction of homoproaporphine related compounds

Hydrogenation of the homoproaporphine (IV) over platinum oxide gave a mixture of the cyclohexanols VIIa and VIIb. In contrast, reduction of IV on palladium provided the cyclo-hexanone VI, which was also obtained from VIIb by oxidation. Treatment of the cyclohexanols VIIa and VIIb under hydrogen on platinum oxide afforded the same mixture of VIIa and VIIb.     

Negative-ion counting techniques for gas chromatography—mass spectrometry

Negative-ion counting techniques for gas chromatography—electron-impact ionization quadrupole mass spectrometry (g.c.—m.s.) are described. Signal-to-noise performance is good and data acquisition is fast. Digital processing of the negative ion signals is done with an ion-counting device and data acquisition with a multi-channel analyzer. The negative-ion mass spectra from g.c.—m.s. measurements are shown for a mixture of tetrachloro-methane, 1,2,2-trichloroethane and 1,1,2,2-tetrachloroethane.     

Identification of the source of the crude drug Tu-zhu-ye using low-temperature plasma ashing

Tu-zhu-ye is a Korean crude drug for use as a diuretic but its plant source has not been identified. The present work has been attempted for identification of the original plant using specimens collected both at Seoul and Taegu, Korea, their mineral microstructures being examined after ashing the specimens by a low-temperature method with high-frequency oxygen plasma. A preliminary survey of the specimens with the naked eye suggested that the Tu-zhu-ye was near to Phyllostachys or its closely related bamboo species. Several specimens, namely, Phyllostachys heterocyclaMitf. var. pubescensOhwi, Phyllostachys nigraMunro var. henonisStapf, Phyllostachys bambusoidesSieb. et Zucc. and Bambusa multiplexRaeuschel were therefore ashed by the low-temperature method and the comparative microscopic studies with the resultant ashed tissues concluded that the “Tu-zhu-ye” from Seoul was perfectly identical with Phyllostachys nigraMunro var. henonisStapf. A further investigation is continued for the specimen from Taegu since it is different from any other specimens provided for the present work.     

Studies on the syntheses of heterocyclic compounds—DXXIII : Enzymic oxidation of homoorientaline with homogenised potato peelings

Homoorientaline 4 was oxidised with homogenised potato peelings along, followed by acetylation, to give 1-hydroxyhomoorientaline triacetate 9, the structure of which was determined by spectroscopic data and an alternative synthesis.     

Copolymerization of propylene with acrylate by a Ziegler-Natta type catalyst

Propylene was polymerized by using a Ziegler-Natta type catalyst in the presence of ethylchloroaluminum acrylate, which was formed by the reaction of diethylaluminum chloride with acrylic acid. The polymer obtained contained acrylic units which were proved to be copolymerized with propylene units by solvent extraction, infrared spectrum, and NMR spectrum. The copolymer showed much improved properties compared with the polypropylene homopolymer.     

Temperature dependence of Raman linewidth and shift in CuI

The temperature dependence of the optical phonon linewidth and frequency shift in CuI has been measured in the temperature range of 4.2 ～ 300 K. Utilizing phonon dispersion curves obtained from neutron scattering measurements, the linewidths and frequency shifts are calculated in terms of three-phonon interactions proposed by Pine and Tannenwald. The experimental results for the change in linewidth and frequency with temperature are in good agreement with this theory.     

Effect of the degree of polynomials in the Savitzky—Golay method for calculation of second-derivative spectra

The second-derivative spectra of absorption curves simulated by a Gaussian function were obtained by using Savitzky—Golay cubic (CPC) and quintic polynomial convolutions (QPC), based on 17 points assumed to be at 0.25-nm intervals. For data obtained directly from the simulated curves (real-type data), the second derivatives agreed with the true values if the widths at half height of the peaks were > 15 nm for CPC and 5 nm for QPC. But when integer values obtained from the real-type data were used to simulate a 12-bit A/D conversion, considerable noise appeared on the second-derivative spectra of peaks wider than the above values, obtained by both CPC and QPC. This occurred because the rounding errors introduced by the A/D conversion formed small shoulders on the digitally reproduced absorption curves, which were enhanced by the differentiation to generate noise. The noise was more intense in QPC than in CPC, thus CPC is preferable for peaks that are not very narrow.