Effect of α‐cyclodextrin on the crystallization of poly (3‐hydroxybutyrate)

The effect of α‐cyclodextrin (α‐CD) on the crystallization behavior of poly(3‐hydroxybutyrate) (PHB) was investigated with polarized optical microscopy, differential scanning calorimetry, and wide‐angle X‐ray diffraction. We found that the addition of α‐CD can greatly accelerate the crystallization of PHB and that α‐CD has a potential not only to enhance the nucleation but also to accelerate the crystallization of PHB. Compared to a conventional nucleation agent, such as talc, α‐CD is a natural product and has many advantages because it is environmentally friendly and safe to humans. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3461–3469, 2004     

Design and synthesis of labeling reagents (MS probes) for highly sensitive electrospray ionization mass spectrometry and their application to the detection of carbonyl, alcohol, carboxylic acid and primary amine samples.

Novel labeling reagents, called MS probes, which possess a positively charged quaternary amine moiety and can transform a neutral analyte into a charged compound by simply mixing with the analyte and allowing the mixture to stand from several minutes to 30 min at room temperature or while heating to 50 degrees C, were designed and synthesized for the highly sensitive detection of carbonyl, alcohol, carboxylic acid and primary amine samples by electrospray ionization mass spectrometry (ESI-MS). The positively charged products can be detected with high sensitivity in an ESI-MS system, which is the most popular liquid MS instrument. All of the labeled products showed a remarkably large increase in the molecular-ion peak abundance detection sensitivity of over 500-fold at picomolar concentration levels compared to that of unlabeled analytes in an ESI-MS system. These MS probes, used together with liquid MS detection, are widely applicable as a convenient method for the highly sensitive detection of less than picomolar levels of analytes, and therefore greatly enhance the power of ESI-MS analysis.     

Interfacial adsorption state of protonated lipophilic porphyrins in a liquid-liquid system by using reflection spectrometry.

Analysis by reflection spectrometry was performed to clarify the interfacial adsorption of protonated lipophilic tetraphenylporphyrin derivatives in a dodecane-aqueous sulfuric acid system, and to confirm the utility of partial reflection spectroscopy. Interfacial adsorption was not observed for porphyrins substituted at the 2,6 positions of meso-phenyl groups, suggesting that the substituents prevent porphyrins from forming aggregates by steric hindrance. Polymorphous J-aggregates of acid dications were produced by tetra-p-tolylporphyrin with a saturated interfacial molecular density of 1.0 x 10(-10) mol cm(-2), which could yield 48 degrees as a mean tilting angle of the pyrrole ring plane from the interface normal. Partial-reflection spectrometry can provide sensitive detection and molecular orientation analysis of interfacial adsorbates.     

Cellulose dimethylphenylcarbamate-bonded carbon-clad zirconia for chiral separation in high performance liquid chromatography.

Porous zirconia particles are very robust material and have received considerable attention as a stationary phase support for HPLC. We prepared cellulose dimethylphenylcarbamate-bonded carbon-clad zirconia (CDMPCCZ) as a chiral stationary phase (CSP) for separation of enantiomers of a set of 14 racemic compounds in normal phase (NP) and reversed-phase (RP) liquid chromatography. Retention and enantioselectivity on CDMPCCZ were compared to those on CDMPC-coated zirconia (CDMPCZ) to see how the change in immobilization method of the chiral selector affects the retention and chiral selectivity. In NPLC, retention was longer and the number of resolved racemates was smaller on CDMPCCZ than on CDMPCZ. However, chiral selectivity factors for some resolved racemates were better on CDMPCCZ than on CDMPCZ. The longer retention on CDMPCCZ is likely due to strong, non-chiral discriminating interactions with the carbon layer on CDMPCZ. In RPLC only two racemates were resolved on CDMPCCZ, but retention times were shorter than, and resolutions were comparable to, those in NPLC, indicating a potential for improving chromatographic performance of the CDMPCCZ column in RPLC with optimized column preparation and separation conditions.     

Validation of a method for predicting the precision, limit of detection and range of quantitation in competitive ELISA.

The mathematical model for predicting the precision, limit of detection (LOD) and range of quantitation (ROQ) in a competitive enzyme-linked immunosorbent assay (ELISA) proposed by Hayashi et al. (Anal. Chem., 2004, 76, 1295) was validated. The model describes the relative standard deviation (RSD) of concentration estimates by the RSDs of pipetting volumes of analyte, enzyme-conjugated antigen, antibody and substrate solutions, and the standard deviation (SD) of inherent absorbances between the wells in an ELISA plate. For 6 kinds of direct competitive ELISA kits, the LOD and ROQ predicted by the model agreed well with those obtained by experiments with real samples. It was also confirmed that the model is applicable to the prediction of uncertainty that depends on the pipetting error of the viscous antiserum solution. The model was demonstrated to be useful for estimating the LOD and ROQ of competitive ELISA.     

Photo-Absorption and photochemical decomposition of copper and alkaline-earth ß-diketonates as source gases of high-Tc superconducting films

For low-temperature deposition of oxide films relating to Bi-Sr-Ca-Cu-O superconductors, photo-absorption and -decomposition properties were examined with respect to copper and alkaline-earth ß-diketonates. It was confirmed that all ß-diketonates examined were promising as source materials for photochemical vapour deposition (photo-CVD) using a low-pressure mercury lamp, in view of their large light absorption coefficients at wavelength 254 nm. The light irradiation was effective for the formation of highly crystalline oxide films at temperatures below 600 °C. By combining two sources, Ca₂CuO₃ and SrCuO₂ films were prepared. Photo-CVD of c-axis oriented Bi₂Sr₂CuO_x film was achieved by the irradiation of ternary sources of Bi(C₆H₅)₃ and strontium and copper ß-diketonates at 500 °C.     

Mesomorphic properties of orthopalladated complexes of laterally substituted azobenzene derivatives, 2-alkoxycarbonyl-4-(4-ethoxyphenylazo)phenyl 4-methoxybenzoates

Homologous series of 2-alkoxycarbonyl-4-(4-ethoxyphenylazo)phenyl 4-methoxybenzoates (L) and their orthopalladated μ-chloro dimers (Pd₂Cl₂L₂) have been synthesized and their thermotropic phase transition behaviour has been characterized. The ligands, L, are three-ring nematogens with their central rings substituted in the 2-position by n-alkyl chains of varied length. The thermal stability of the nematic phases decreases rapidly with increasing side chain length and then levels off as the series is ascended. In every case the mesomorphic phase appears only over a small temperature range (less than 20° C). The orthopalladated species also proved to be nematogenic. Melting and clearing points rise on the average by 87° C and 126° C, respectively, and thus the temperature ranges of the nematic phases are enlarged considerably upon metallation. In relation to the observed stabilization of the nematic phases, particularly of higher homologues, a lath-like molecular structure, in which the side chains of the ligands fill up the clefts of the core part, has been deduced for a Pd2Cl2L2 homologue from its solution ¹H-NMR spectrum.     

Crystal structure of the clathrate of 5,12-dihydro-5,12-o-benzenonaphthacene-1,4-dione with benzene (2:1).

In the crystal of the title compound, the quinone fragment of the host (1) participates in weak D-A interactions with a neighboring naphthalene moiety of 1 and with the guest molecule via fairly short intermolecular face-to-face contacts. An intermolecular electrostatic interaction between a quinone-oxygen atom and a neighboring quinone ring is suggested by short O...C contacts. There exist several C-H...O hydrogen bonds, one of which seems to contribute to the formation of a centrosymmetric dimer of 1.