Selective determination of tryptophan-containing peptides through precolumn derivatization and liquid chromatography using intramolecular fluorescence resonance energy transfer detection.

A selective and sensitive fluorometric determination method for native fluorescent peptides has been developed. This method is based on intramolecular fluorescence resonance energy transfer (FRET) detection in a liquid chromatography (LC) system following precolumn derivatization of the amino groups of tryptophan (Trp)-containing peptides. In this detection process, we monitored the FRET from the native fluorescent Trp moieties (donor) to the derivatized fluorophore (acceptor). From a screening study involving 10 fluorescent reagents, we found that o-phthalaldehyde (OPA) generated FRET most effectively. The OPA derivatives of the native fluorescent peptides emitted OPA fluorescence (445 nm) through an intramolecular FRET process when they were excited at the excitation maximum wavelength of the Trp-containing peptides (280 nm). The generation of FRET was confirmed through comparison with the analysis of a non-fluorescent peptide (C-reactive protein fragment (77 - 82)) performed using LC and a three-dimensional fluorescence detection system. We were able to separate the OPA derivatives of the Trp-containing peptides when performing LC on a reversed-phase column. The detection limits (signal-to-noise ratio = 3) for the Trp-containing peptides, at a 20-microL injection volume, were 41 - 180 fmol. The sensitivity of the intramolecular FRET-forming derivatization method is higher than that of the system that takes advantage of the conventional detection of OPA derivatives. Moreover, native non-fluorescent amines and peptides in the sample monitored at FRET detection are weaker than those of conventional fluorescence detection.     

Vassiliev invariants of type two for a link

We show that any type two Vassiliev invariant of a link can be expressed as a linear combination of the second coefficients of the Conway polynomials of its components and a quadratic expression of linking numbers.

     

Nuclear spin dynamics of nuclear-ordered solid<Superscript>3</Superscript>He in the low field phase

Pulsed NMR was used to investigate nuclear spin dynamics of nuclear-ordered solid³He in the low field phase. The nuclear spin motion became unstable under certain conditions. Under stable conditions the spin motion can be described by the OCF equations. The tipping-angle-dependent frequency shift and multiple spin echoes were observed, which are similar to the case of superfluid³He. The onset of the instability of spin motion is attributed to the stimulated emission mechanism through the three-magnon relaxation process, which is similar to the Suhl instability in electronic magnetism. We derived the magnon life time from the analysis of the instability. During the instability, a largenegative frequency shift was observed. This negative shift is explained by the extension of Fomin-Ohmi's theory to include the state of decayed magnon and this explanation is consistent with the instability model.     

The reaction of perfluorobicyclic ethers and perfluorospiro-ethers with anhydrous aluminum chloride

Perfluorobicyclic ethers and perfluorospiroethers, all containing an oxolane skeleton, were treated with AlCl₃ in a heterogeneous manner to give the corresponding α,α,α′-trichlorinated and α,α-dichlorinated products, respectively. From perfluoroacetal compounds, for example, perfluoro(8-methoxy-7-oxabicyclo- [4.3.0]nonane), mono- and di-chlorinated products, i.e. perfluoro- (8-chloro-8-methoxy-7-oxabicyclo[4.3.0]nonane) and perfluoro- (8,8-dichloro-7-oxabicyclo[4.3.0]nonane) were obtained in good yields. The action of fuming sulfuric acid on these polychlorinated products led to the formation of the corresponding lactones. Perfluoro(6-chloro-7-oxa-8-oxobicyclo[4.3.0]nonane) was treated with (CH₃)₂NLi to give N,N-dimethylundecafluoro-2-oxocyclohexyl- acetamide.     

Microemulsions in separation sciences

Fundamental properties of microemulsions in relation to their utilization in liquid state separation methods of ionic and non-ionic compounds are briefly reviewed. Discussions are focused on some characteristics functions of o/w (L₁) and w/o (L₂) single-phase microemulsions and the two-phase microemulsion systems of Winsor I and Winsor II from the viewpoint of their use as separation media in solvent extraction, liquid chromatography and capillary electrophoresis. Through reviewing, practical advantages of the microemulsion media in the separation of metal ions and biological compounds are assessed.     

Modification in cell structure for better performance of spray pyrolysed CuInS2/In2S3 thin film solar cell

We report a new structure for CuInS₂/In₂S₃ solar cell, in which both absorber and buffer layers were deposited using chemical spray pyrolysis (CSP) technique. The usual superstrate structure, having buffer layer just above ITO, was not functioning mainly due to diffusion of Cu into In₂S₃ layer as seen from X-ray photoelectron spectroscopy (XPS) results. However, when the configuration of the cell was ITO/CuInS₂/In₂S₃/Ag, cell parameters obtained were V_oc=0.45 V, J_sc=44.03 mA/cm², fill factor (FF) = 29.5% and η=5.87%. Good results could be obtained by using indium sulfide thin films having maximum photosensitivity. The cell was characterized using X-ray diffraction, optical absorption, current–voltage and spectral response measurements. PACS 81.15.Rs; 82.45.Mp; 84.60.Jt     

Interfacial hydrolysis in the mu-oxo dimer formation of tetraphenylporphinatomanganese(III) in the toluene/water system.

The interfacial adsorption and dimerization behavior of tetraphenylporphinatomanganese(III)chroride (Mn(TPP)Cl) in the toluene/water two phase system was studied. The absorption spectra of the porphyrin complex in the organic phase were blue shifted with increasing of pH in the aqueous phase, suggesting the formation of the mu-oxo dimer. The interfacial species in these systems were examined by means of UV/vis external reflection (ER) spectrophotometry. ER spectral maxima were also blue shifted with the increase in pH, whereas the shape of the ER spectra in the basic conditions was different from that of the mu-oxo dimer. The observed results suggest that the hydroxide-coordinated monomer, Mn(TPP)OH, was generated from the Mn(TPP)(H2O)+ at the interface under the basic conditions and that was further converted to the mu-oxo dimer, which was soluble into the toluene phase.