EPR study of melanin-protein interaction: photoinduced free radicals and progressive microwave power saturation.

The photo-induction of free radicals in synthetic L-dihydroxyphenylalanine (L-DOPA) melanin in the presence of bovine serum albumin (BSA) was studied by electron paramagnetic resonance (EPR) spectroscopy. By monitoring the signal intensities and progressive microwave power saturation it was shown that L-DOPA melanin in solution behaves as a single macromolecule, interacting with BSA and molecular oxygen. In the absence of oxygen, the EPR signal of L-DOPA melanin was homogeneously broadened; the magnetic interaction with oxygen induced inhomogeneous broadening. In aqueous solution, the presence of BSA decreased the accessibility of oxygen to paramagnetic centres in the melanin. On UV-visible illumination, the presence of BSA modified the rates of formation and decay of photoinduced free radicals, resulting in a net enhancement of the EPR signal compared with that observed in pure L-DOPA melanin.     

Quantitative determination of benzalkonium chloride in treated wood by solid-phase extraction followed by liquid chromatography with ultraviolet detection

Ammoniacal copper quat (ACQ) compound wood preservative is comprised of copper and quaternary ammonium compounds with benzalkonium chloride (BAC) as the active ingredient. Solid-phase extraction (SPE) followed by liquid chromatography with ultraviolet detection (LC-UV) was developed for quantitative determination of BAC in treated wood. Five species of wood were used, Japanese cedar (Cryptomeria japonica), Japanese larch (Larix leptolepis), Yezo spruce (Picea jezoensis), Sakhalin fir (Abies sachalinensis), and western hemlock (Tsuga heterophylla). BAC used in the present study was composed of 66% C12, 33% C14 and less than 1% C16. BAC was added to each wood species (500 mg) then extracted with HCl-ethanol (20 ml) and quantitatively determined with LC-UV (262 nm). Wood extractives from the heartwood of each species, except western hemlock, interfered with quantitative determination of BAC, but SPE with an Oasis MCX cartridge was effective in preventing this. Using the present methods, BAC homologue peaks were clearly confirmed without interference. Recoveries from wood ranged from 92 to 101% and the limit of quantitation was approximately 240 microg/g wood for the C12 and C14 homologues.     

Cross-axis synchronous flow-through coil planet centrifuge (type XLL). I. Design of the apparatus and studies on retention of stationary phase

The fourth prototype holds a pair of column holders in the lateral position at 15 cm from the center of the rotary shaft horizontally mounted on the rotary frame at 7.6 cm from the central axis of the apparatus. Using short coils of 2.6 mm I.D. PTFE (polytetrafluoroethylene) tubing with 7.6 cm and 24 cm helical diameters, retention of the stationary phase was measured in ten pairs of two-phase solvent systems under various experimental conditions. Satisfactory retention was obtained by choosing proper combinations of three factors, i.e., the direction of planetary motion, head-tail elution mode, and inward-outward elution mode. The polar butanol solvent systems showed excellent retention from 65 to 80% in the 7.6 cm helical diameter left-handed coil.     

Novel acyl alpha-pyronoids, dictyopyrone A, B, and C, from Dictyostelium cellular slime molds

For the elucidation of the diversity of secondary metabolites of Dictyostelium cellular slime molds, we investigate the constituent of three species of slime molds. From the methanol extract of their fruit bodies, we obtained three novel compounds, dictyopyrone A (1) and B (2) from D. discoideum and D. rhizoposium and dictyopyrone C (3) from D. longosporum. They possess a unique alpha-pyrone moiety with a side chain at the C-3 position. Their relative structures were elucidated by spectral means, and the absolute configuration was confirmed by asymmetric synthesis of 1. Since these compounds were obtained from different species of Dictyostelium slime molds, they may be a type of compound common to this genus.     

Synthesis of the new chiral tridentate ligand bis(pyrid-2-ylethyl) menthylphosphine and its use in the palladium-catalyzed allylic alkylations

We describe the synthesis of a new asymmetric P,N,N′-tridentate ligand (bis(pyrid-2-ylethyl) menthylphosphine, BPEMP), containing two pyridyl rings and (1S,2R,5S)-menthylphosphino group. The ligand is obtained in five steps from natural abundant l-menthol. The coordination behavior of the ligand toward cationic (allylic)Pd(II) moiety and its first application in palladium-catalyzed asymmetric allylic alkylation are presented. Crystallographic and spectroscopic analyses reveal that [(η³-allylic)Pd(BPEMP)]⁺ complex forms only one isomer in the solid state as well as in solution.     

Synthesis and two-electron redox behavior of diazuleno[2,1-a:1,2-c]naphthalenes

The Diels-Alder reaction of di-2-azulenylacetylene with tetraphenylcyclopentadienone afforded 7,8,9,10-tetraphenyldiazuleno[2,1-a:1,2-c]naphthalene in one pot via autoxidation of the presumed 1,2-di-2-azulenylbenzene derivative. In contrast, a similar reaction of bis(1-methoxycarbonyl-2-azulenyl)acetylene with tetraphenylcyclopentadienone gave the 1,2-di-2-azulenylbenzene derivative. The following cyclodehydrogenation reaction of the benzene derivative with iron(III) chloride afforded diazuleno[2,1-a:1,2-c]naphthalene 6,11-bismethoxycarbonyl derivative. The redox behavior of these novel diazuleno[2,1-a:1,2-c]naphthalenes was examined by cyclic voltammetry (CV). These compounds exhibited two-step oxidation waves at +0.22 to +0.71 V upon CV, which revealed the formation of a radical cation and dication stabilized by the fused two azulene rings under the electrochemical oxidation conditions. Since the 1,2-di-2-azulenylbenzene derivative was oxidized at higher oxidation potentials (+0.83 and +1.86 V), the fusion of the two azulene rings to naphthalene increased electron-donating properties because of the formation of a closed-shell dicationic structure. Formation of the radical cation was characterized by UV-vis spectroscopy under the electrochemical oxidation conditions, although no evidence was obtained for the presumed dication under the conditions of the UV-vis spectroscopy measurement.     

Experimental observations of the hydrodynamic behavior of solvent systems in high-speed counter-current chromatography. II. Phase distribution diagrams for helical and spiral columns

Extensive studies have been performed on hydrodynamic distribution of two immiscible solvent phases in helical and spiral columns by means of coil planet centrifugation. Under the Scheme IV [see Fig. 1 in Y. Ito, J. Chromatogr., 301 (1984) 377] planetary motion, the two phases display unilateral distribution in the coil, i.e., one phase travels toward the head and the other phase toward the tail. This hydrodynamic trend is sensitively affected by various factors such as physical properties of the solvent system, helical diameter of the column, revolutional radius, etc. Phase distribution diagrams obtained from a set of conventional two-phase solvent systems under various experimental conditions provide extremely useful information for both basic hydrodynamic studies and practical application in high-speed counter-current chromatography.     

Synthesis and characterization of flavylium salts having three types color depending on recrystallization conditions

Three types of flavylium salts (FVs, yellow, green and red) have been synthesized and the colors depended on recrystallization conditions. The existence of these color states was confirmed by diffuse reflectance spectra. The spectra were almost the same as the absorption spectra in ethanol solution. The molecular state of FVs in crystals will be the same as that in solutions. The crystal colors of the FVs are controlled by the recrystallization conditions.     

Esters of 5-carboxyl-5-methyl-1-pyrroline N-oxide: a family of spin traps for superoxide

Apparent rate constants, at acidic pH and neutral pH for the reaction of a family of ester-containing 5-carboxyl-5-methyl-1-pyrroline N-oxides with superoxide (O2*-) were estimated, using ferricytochrome c as a competitive inhibitor. It was of interest to note that the rate constants were similar among the different nitrones and not that significantly different from that found for 5-(diethoxyphosphoryl)-5-dimethyl-1-pyrroline N-oxide. At acidic pH, the rate constant for spin trapping O2*- was 3-fold greater than that at physiological pH. Subsequent experiments determined the half-life of aminoxyls, derived from the reaction of these nitrones with O2*-. The EPR spectra were modeled by using a global analysis method. The results clearly demonstrated that EPR spectra of all the aminoxyls were inconsistent with a model that included a single gamma-hydrogen splitting. A better interpretation modeled them as two diastereomers with identical nitrogen splittings and slightly different beta-hydrogen splittings. Detailed line width analyses slightly favored an equal line width-unequal population ratio for the two diastereomers.     

模式识别—人工神经网络在化学中的若干新应用

本文通过我们应用模式识别－人工神经网络方法预报新化合物、熔盐相图以及复杂化学反应体系的研究，展示应用模式识别－人工神经网络方法与物理化学理论相结合，研究化学现象的可能性和应用价值。