Synthesis of poly-yne polymers containing transition metals,disilane, disiloxane and phosphine groups in the main chain

The synthesis and characterization of metal poly-yne polymers containing disilane, disiloxane and phosphine groups in the main chain are described. The platinum and palladium poly-yne polymers were synthesized by polycondensation reactions between a metal chloride and an α, ω-bisethynyl complex in amines in the presence of cuprous iodide as a catalyst. The nickel poly-yne polymers were synthesized by an alkynyl ligand exchange reaction between a nickel acetylide and an α, ω-bisethynyl complex in diethylamine in the presence of cuprous iodide as a catalyst. The reaction of the platinum poly-yne polymer, containing disiloxane groups in the main chain, with copper (I) salts afforded adducts of η-²-bonded σ-acetylide polymer complexes. The reactions of the palladium poly-yne polymer, containing phosphine groups in the main chain, with transition-metal carbonyl complexes afforded polymer complexes which have phosphorus in the main chain-transition-metal bonds. A concentrated solution of the platinum poly-yne polymer containing disiloxane groups in the main chain forms a lyotropic liquid crystal in dichloromethane or 1, 2-dichloroethane.     

Size distribution of fractured areas in one-dimensional systems

We study a one-dimensional model for fracture, identifying fractured areas with intervals on which a stress field exceeds a threshold value. When is a diffusion process, the cumulative numberN(l) of fractured areas whose length is greater thanl obeys a power lawCl ^–p asl0 with probability one. The exponentp and the constantC are determined. The exponentp agrees with the Hausdorff dimension of the end points of fractured areas, i.e., ^–1(). Even if is self-similar with parameterH>0, i.e.,(cx)– is equivalent toc ^H {(x)–} for anyc>0, the exponentp does not depend solely onH;p=H, where(0, 1/H) is another parameter characterizing. Non-diffusion processes are given whereN(l) does not follow a power law.     

Evaluation of Photocatalytic Activity of Transparent Anatase Nanocrystals-Dispersed Silica Films Prepared by the Sol-Gel Process with Hot Water Treatment

Anatase nanocrystals were precipitated mainly at the surface of the silica-titania gel films with hot water treatment, whereas the addition of poly(ethylene glycol) (PEG) in the films led to the dispersion of anatase nanocrystals in the whole of the films after the treatment. Both films with and without PEG showed high photocatalytic activities for acetaldehyde, NO _x and stearic acid in the gas-solid system, and for methylene blue and potassium iodide in the liquid-solid system. The addition of PEG improved the photocatalytic activities of the resultant films due to the smaller anatase crystallites and the porous film structure. The residual silica under-layer of the superficially anatase-precipitated films is expected to act as a protective one for an organic polymer substrate against the photocatalytic degradation.     

Valency states of radioactive antimony in hydrochloric acid solutions. Preparation and stability of antimony tracer for radioanalytical use

Variations of¹²⁵Sb valency states in HCl solutions were investigated by the use of the N-benzoyl-N-phenyl-hydroxylamine (BPHA) extraction method.¹²⁵Sb(V) is completely reduced to Sb(III) by one hour refluxing in conc. HCl.¹²⁵Sb(III) is gradually oxidized to Sb(V) in solutions of low HCl concentrations by the effects of their own radiations. Natural light promotes such oxidation reactions. By utilizing such oxidation-reduction effects¹²⁵Sb(V) can be easily prepared from¹²⁵Sb(III) and also¹²⁵Sb(III) can be prepared by the reduction of Cl _aq ⁻ . Their valency states were stable on keeping them in brown-colored bottles at 6M HCl concentrations.     

Molecule-Responsive Fluorescent Sensors of α-Helix Peptides Bearing α-Cyclodextrin, Pyrene and Nitrobenzene Units in Their Side Chains

-Helix peptides bearing one unit of -cyclodextrin (-CD), one unit of pyrene and one unit of nitrobenzene (NB) in their side chains have been designed and synthesized as novel molecule-responsive devices.In both the CD-peptides, -PR17 and -PL17, the NB unit is separated from the CD unit by two turns of the helix. Two reference peptides (PL17, and -P17,) have also been synthesized. The circular dichroism studies in the peptide absorption region (200–250 nm)of -PR17 and -PL17 suggestthat the CD-peptides form stable-helixstructures (83–77%), which was destabilized by accommodating guest molecules (e.g., n-pentanol) into the CD cavity. It suggests that formation of intramolecular host–guest(CD–NB) complex stabilized thehelical structure and exogenous guest molecule excluded the appending NB moiety from inside to outside of the CD cavity, thereby causing destabilization of the helical structure and increasing the random coil content. The ICD spectra of the peptides in the pyrene and nitrobenzene absorption region (250–40 nm) suggest that NB forms inclusion complex with CD. The fluorescence studies revealed that the fluorescence of the pyrene unit is quenched by the NB unit in -PR17 and -PL17. The fluorescence intensity increases with increasing guest concentration for the CD-peptides.This guest-responsiveenhancement in the fluorescence intensity can be explained in terms of increased distance between the pyrene and NB moieties, which is caused by exclusion of the NB moiety from the CD cavity by guest accommodation. Using the guest-responsive fluorescence quenching properties of the CD-peptides, we have obtained binding constants for various short chain alkanols. -PL17 has higher binding affinity to the guest molecules than its isomer, -PR17, indicating that the location of functional groups on the peptide scaffold is important in molecule detection.     

Preparation and separation of all possible rotamers of a stereochemical analog of meso-tartaric acid: optically inactive and optically active isomers of (R,S)-2,2′-bis(methoxycarbonyl)-6,6′-dimethyl-9,9′-bitriptycyl

All the three possible rotamers of the title compound were separated by chromatography, and unambiguously identified by NMR and X-ray analysis. One of the isomers was optically inactive C_i conformation. The other optical active forms were resolved to give a pair of enantiomers, which were characterized by optical rotation and CD spectra. Thus the optical inactivity of a compound such as meso-tartaric acid that can take C_i conformation in solution, is now ascribed to that the molecule has an optically inactive C_i conformer and equal amounts of optically active conformers, that are enantiomers, in solution.     

Partial degradation and biological activities of an antitumor polysaccharide from rice bran.

A rice bran polysaccharide designated RON was subjected either to partial hydrolysis with formic acid or to partial degradation by ultrasonic irradiation. A significant change in the molecular size was also observed during simple chromatography of RON on a strongly acidic ion exchange resin, although the apparent molecular weight of RON had been assumed to be more than 1 x 10(6) daltons (Da). This fact indicates that RON exists as molecular aggregates, presumably mediated by metal cations. Degradation products with average molecular weights above ca. 1 x 10(4) Da which were obtained by any of the three methods still retained the following activities of RON: in vivo antitumor activity against Meth-A fibrosarcoma in mice by oral administration, and in vitro macrophage stimulatory effects to induce tumoricidal activity and interleukin 1 production. This molecular size was proven to be the minimum requisite for these activities because smaller fragments were scarcely active. The aggregation was characteristic of RON but not essential for its antitumor activity because definite, though slightly reduced, activity was exhibited even by the smaller fragments obtained after the ion exchange resin treatment.     

Analysis of the release process of phenylpropanolamine hydrochloride from ethylcellulose matrix granules

The release properties of phenylpropanolamine hydrochloride (PPA) from ethylcellulose (EC, ethylcellulose 10 cps (EC#10) and/or 100 cps (EC#100)) matrix granules prepared by the extrusion granulation method were examined. The release process could be divided into two parts, and was well analyzed by applying square-root time law and cube root law equations, respectively. The validity of the treatments was confirmed by the fitness of the simulation curve with the measured curve. At the initial stage, PPA was released from the gel layer of swollen EC in the matrix granules. At the second stage, the drug existing below the gel layer dissolved, and was released through the gel layer. Also, the time and release ratio at the connection point of the simulation curves was examined to determine the validity of the analysis. Comparing the release properties of PPA from the two types of EC matrix granules, EC#100 showed more effective sustained release than EC#10. On the other hand, changes in the release property of the EC#10 matrix granule were relatively more clear than that of the EC#100 matrix granule. Thus, it was supposed that EC#10 is more available for controlled and sustained release formulations than EC#100.     

Release from or through a wax matrix system. V. Applicability of the square-root time law equation for release from a wax matrix tablet

To obtain basic and clear release properties, wax matrix tablets were prepared from a physical mixture of drug and wax powder at a fixed mixing ratio. Properties of release from the single flat-faced surface, curved side surface, and/or whole surface of the wax matrix tablet were examined. Then tortuosity and the applicability of Higuchi's square-root time law equation were examined. The Higuchi equation well analyzed the release processes of different release manners. However, the region fitted to the Higuchi equation differed with the release manner. Tortuosity obtained with release from the single flat-faced surface and curved side surface was comparable with that obtained with the release from a reservoir device tablet, whereas tortuosity obtained with release from the whole surface was larger. As the wax matrix tablets were prepared at a fixed mixing ratio, their internal structures should be similar. Therefore changes in the matrix volume or volume fraction with release were examined, and an extra volume where dissolved drug stray becomes large with release time in the case of release from the whole surface. These factors should be taken into account for evaluation of applicability and release properties. Furthermore, the entire release process should be analyzed using a combination of the square-root time law and other suitable equations in accordance with release manner or condition.     

Prediction of measurement precision of apparatus using a chemometric tool in electrochemical detection of high-performance liquid chromatography

The relative standard deviation (RSD) of measurements in high-performance liquid chromatography with electrochemical detection (HPLC-ECD) was predicted by a chemometric tool based on the 1/f fluctuation model which is made up of white noise and a Markov process, called the Function of Mutual Information (FUMI) theory. FUMI theory can provide aprecise and reliable detection limit from a single measurement of noise and signal in HPLC-ECD. To obtain RSD (n = 5) for determination of (-)-epicatechin at five concentrations required 12.5 h, while the predicted RSD by FUMI theory required only 0.5 h (one measurement). Moreover, to trace the source of instrumental noise, power spectra of chromatographic baseline were used. Selection of a suitable apparatus in HPLC-ECD system, acquisition of RSD, and detection limits for determination of catechins by HPLC-ECD were simply and easily made by this chemometric tool within a very short time. The use of the FUMI theory for the prediction of measuring precision was more efficient and the optimization was less time-consuming to be suited for determination.