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.     

Improvement in flow-sheet of extraction chromatography for trivalent minor actinides recovery

Journal of Radioanalytical and Nuclear Chemistry - Extraction chromatography flow-sheet employing octyl(phenyl)-N,N-diisobutylcarbonoylmethylphosphine oxide and bis(2-ethylhexyl) hydrogen phosphate...     

HPLC with fluorescence detection assay of perampanel,a novel AMPA receptor antagonist,in human plasma for clinical pharmacokinetic studies

Perampanel (Fycompa®), a novel α‐amino‐3‐hydroxy‐5‐methyl‐4‐isoxazolepropionic acid (AMPA) receptor antagonist, is registered for the adjunctive treatment of patients (aged ≥12 years) with refractory partial‐onset seizures. To support therapeutic drug monitoring, a simple high‐performance liquid chromatography (HPLC) assay with fluorescence detection was developed to determine perampanel concentrations in human plasma and validated to support clinical trials. Human plasma samples (1.0 mL) were processed by liquid extraction using diethyl ether, followed by chromatographic separation on a YMC Pack Pro C₁₈ column (150 × 4.6 mm i.d., 5 µm) with isocratic elution of acetonitrile–water–acetic acid–sodium acetate (840:560:3:1.8, v/v/v/w) at a flow rate of 1.0 mL/min. Column eluent was monitored at excitation and emission wavelengths of 290 and 430 nm, respectively. The assay was linear (range 1.0–500 ng/mL) and this could be extended to 25 µg/mL by 50‐fold dilution integrity. No endogenous peaks were detected in the elution of analytes in drug‐free blank human plasma from six individuals and no interference was observed with co‐medications tested. Intra‐ and inter‐batch reproducibility studies demonstrated accuracy and precision within the acceptance criteria of bioanalytical guidelines. Validation data demonstrated that our assay is simple, selective, reproducible and suitable for therapeutic drug monitoring of perampanel. Copyright © 2015 John Wiley & Sons, Ltd.     

Simultaneous determination of serotonin and 5-hydroxyindole-3-acetic acid in human urine by automated precolumn derivatization and semi-microbore column liquid chromatography with fluorescence detection.

An improved high-performance liquid-chromatographic (HPLC) assay for the simultaneous determination of serotonin (5-HT) and 5-hydroxyindole-3-acetic acid (5-HIAA) in human urine is reported. Following the automated precolumn derivatization of urinary 5-HT and 5-HIAA with benzylamine, the derivatives are separated by isocratic elution on a reversed-phase C18 semi-microbore column, and are fluorometrically detected at an excitation wavelength of 345 nm and an emission wavelength of 480 nm. The detection limits of 5-HT and 5-HIAA are 7 and 5 nmol/l in urine (0.7 and 0.5 fmol/20-microl injection). The proposed automatic method permits a highly selective and sensitive determination of 5-HT and 5-HIAA in human urine without any sample purification.     

Near-infrared photorefractivity in Cr-doped potassium sodium strontium barium niobate single crystal

We report on the photorefractive properties of a Cr-doped (K_1–x Na _x )_2A–2 (Sr _y Ba_1–y )_2–A Nb₁₀O₃₀ (x=0.586, y=0.659, A=1.12) single crystal in the near-infrared spectrum. The sample exhibits photorefractivity for wavelengths up to at least 840 nm where the steady-state two-beam coupling gain is found to be larger than 2 cm^–1. Photorefractive gain and decay rate are measured as a function of wavelength, grating spacing and intensity. The wavelength dependence of gain fluctuations in two-beam coupling are also measured.     

Scalar curvature of spheres

Financial support from the FRD is gratefully acknowledged     

Spherical dye-doped silica particles

Organic dyes such as water soluble porphyrins were incorporated into monodispersed SiO₂ particles using the sol-gel technique (the Stober synthesis) and their monomeric and dimeric properties were investigated by aiming at the microcavity effect. Doping efficiencies of dyes into SiO₂ particles depended on dye's hydrophilic properties. The doping efficiency of a porphyrin, TTMAPP, decreased with increasing the nominal content in the starting solution and the doping content showed the maximum value of 1.6×10^–5 mol/g SiO₂. With increasing the TTMAPP content, spectra of doped particles were changed from dimeric to monomeric nature; the absorption peak due to dimers disappeared and halfwidth of absorption at Soret band decreased. This unusual change was caused by the decrease of particle sizes by dye doping. The TTMAPP-doped sample having monomeric spectrum showed the fluorescence life time of 8.5 nsec and photochemical hole burning at about 5 K.     

Synthesis of all diastereomeric methyl 2,5-anhydro-3-deoxy-hexonates: precursors to C-2-deoxynucleosides and THF-templated γ- and δ-amino acids

Efficient syntheses of all diastereomers of methyl 2,5-anhydro-3-deoxy-hexonate from mannono- or gulono-lactones provide precursors for C-nucleosides of 2-deoxyribose and for THF-templated γ- and δ-amino acids.     

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