Formation of Supramolecular Nanostructures through in Situ Self-Assembly and Post-Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging.     

Structural developments in synthetic rubbers during uniaxial deformation by in situ synchrotron X‐ray diffraction

The molecular orientation and strain‐induced crystallization of synthetic rubbers—polyisoprene rubber, polybutadiene rubber, and butyl rubber [poly(isobutylene isoprene)]—during uniaxial deformation were studied with in situ synchrotron wide‐angle X‐ray diffraction. The high intensity of the synchrotron X‐rays and the new data analysis method made it possible to estimate the mass fractions of the strain‐induced crystals and amorphous chain segments in both the oriented and unoriented states. Contrary to the conventional concept, the majority of the molecules (50–75%) remained in an unoriented amorphous state at high strains. Each synthetic rubber showed a different behavior of strain‐induced crystallization and molecular orientation during extension and retraction. Our results confirmed the occurence of strain‐induced networks in the synthetic rubbers due to the inhomogeneity of the crosslink distribution. The strain‐induced networks containing microfibrillar crystals and oriented amorphous tie chains were responsible for the ultimate mechanical properties. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 956–964, 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.     

Cerasome as an Organic-Inorganic Vesicular Nanohybrid: Characterization of Cerasome-Forming Lipids having a Single or a Dual Trialkoxysilyl Head

Morphological characterization of the organic-inorganic vesicular nanohybrids, Cerasomes, was performed in aqueous media from two aspects. Firstly, a novel Cerasome-forming lipid having two triethoxysilyl groups in the head moiety was synthesized and the physical property of the Cerasome was investigated. While the morphological stability of the Cerasomes, as evaluated from the vesicular collapse behavior against a micelle-forming nonionic surfactant, Triton-X 100, was extremely higher than that of the conventional phospholipid liposome, the stabilities were comparable to each other for the Cerasomes derived from the dual- and single-head lipids. On the other hand, the surface property of the Cerasome formed with the dual-head lipid more closely resembled the colloidal silica particles rather than that derived from the single-head lipid, as suggested by zeta-potential measurements. Secondly, the effect of the media pH on the morphological stability of the Cerasome formed with the single-head lipid was evaluated and appeared as a time difference in obtaining the morphological stability of the Cerasome. These morphological characteristics of the Cerasomes could be mainly owing to the development of the siloxane network on the vesicular surface.     

A new semiconducting organic-inorganic nanocomposite, 1,5-diaminonphthalene-saponite intercalation compound

We synthesized a new intercalation compound, 1,5-diaminonaphathalene(DAN)-saponite where intercalated DAN molecules were shown to have a formal charge of +0.67 The measurement of optical diffuse reflectance spectra revealed the formation of electronic bands with a gap of ca. 1 eV suggesting semiconducting behaviour of this system. From ESR measurements, the radical formation in DAN-saponite was confirmed and the spin concentration was determined to be 1 spin per 200 and 300 DAN-molecules at 290 and 7.9 K, respectively. This temperature dependence of the spin density also implies the semiconductive nature of DAN-saponite.     

Wavelength dependence in photochemical vapor deposition of aluminum film using dimethylaluminum hydride

In photochemical vapor deposition of aluminum film on silicon using dimethylaluminum hydride, (CH₃)₂AlH, a surface reaction dominated below a (CH₃)₂AlH pressure of 0.3 m Torr at 200°C, which was induced only with the 160 nm band emitted from a deuterium lamp. A gas-phase reaction occurred above 0.3 mTorr at 200°C, which could be induced by both 160 nm and 240 nm emission bands from the lamp. To distinguish between surface ad gas-phase reactions, a thickness profile was used. At 240°C the surface reaction could be induced even by the 240 nm band, while the deposits formed under illumination of the two bands were thinner than those obtained with only the 240 nm band, indicating occurrence of vacuum ultraviolet (VUV)-enhanced desorption. The mechanism responsible for the observed wavelength dependence in unclear. The electrical resistivity of the films deposited at 200°C was 4.5 μΩ cm, which did not change with wavelength.     

Electron paramagnetic resonance and optical absorption spectra of Cr ions in cadmium phosphate glass

EPR and optical absorption investigations of chromium doped cadmium phosphate glass are carried out. Crystal field, spin-Hamiltonian and bonding parameters are evaluated. From the results and analyses of the EPR and optical studies, the site symmetry of Cr³⁺ ion in the glass is ascribed to a distorted octahedron. The bonding parameters suggest the ionic nature of Cr³⁺ ion with the ligands.     

Synthesis of spherical and hemispherical sugar‐containing poly(ornithine) dendrimers

A novel sugar‐containing poly(ornithine) dendrimer is synthesized for possible antigen delivery and related applications. The dendrimer contains an ornithine dendron as interior scaffolding and oligosaccharides on the periphery, which provide an attachment site for a peptide antigen. Maltose or lactose is bound to both hemispherical and spherical poly(ornithine) dendrimer generation 3 (G3) by reductive amination between its reducing end and the peripheral amino group of the dendrimer using a borane‐pyridine complex in a buffer solution at 50 °C. The degree of substitution of sugar is changed by varying the molar ratio of sugar to dendrimer. When the surface of spherical poly(ornithine) dendrimer G3 is modified by binding β‐alanine to the 16 amino groups, highly substituted maltose‐ or lactose‐β‐alanine‐poly(ornithine) dendrimer G3 is obtained in high yield after 7 days of reaction. The structures of these sugar‐containing dendrimers are characterized by NMR and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analyses. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1400–1414, 2004     

Dynamics of muons in the ferroelectric material KDP

Muon spin relaxation in zero field and longitudinal field was measured in single crystal samples of KH₂PO₄ (KDP) and KD₂PO₄ (DKDP) over a temperature range of 5 K to 300 K. At low temperatures, diamagnetic muons and muon substituted radicals with nuclear hyperfine coupling can be observed. For both KDP and DKDP, a minor change was observed in the dynamics of the muon below 140 K. Above 140 K, the mobility of the muon appears to increase and the diffusion rate becomes faster with increasing temperature. Only a small increase in the relaxation rate is observed in KDP due to the presence of theH ⁺, suggesting that the relaxation effects probably originate from the³¹P.