Spectroscopic and Electrochemical Characterization of Cytochrome P450st‐DDAB Films on a Plastic‐Formed Carbon Electrode

We have studied the characterization of thermophilic cytochrome P450 (P450st)‐didodecyldimethylammonium bromide (DDAB) films by using UV‐vis absorption, resonance Raman spectroscopy, and electrochemical methods. The observed Raman spectrum indicated near‐native conformation of the heme iron in DDAB film on the surface of a glass slide, while on the surface of a plastic‐formed carbon (PFC) electrode, the conformation of P450st‐DDAB was very similar to that of heme‐DDAB film, suggesting the release of heme from P450st in DDAB films on PFC electrodes. When NaBr was added as salt to the casting solution, the result of Raman spectrum indicated near‐native conformation of P450st in DDAB film even on the PFC electrode, but no redox potential of P450st which has near native structure was observed. This study suggests the essential experimental conditions when working with heme protein‐DDAB films as, in some cases, heme iron from proteins is released on the surface of the electrode.     

Rapid ruthenium-catalyzed synthesis of pyranopyrandiones by reconstructive carbonylation of cyclopropenones involving C[bond]C bond cleavage

Pyranopyrandiones were prepared by a novel ruthenium-catalyzed carbonylative dimerization of cyclopropenones via C-C bond cleavage. For example, treatment of dipropylcyclopropenone with a catalytic amount of Ru3(CO)12 and NEt3 in THF under 15 atm of carbon monoxide at 140 degrees C for 20 h gave a novel functional monomer, 3,4,7,8-tetrapropylpyrano[6,5-e]pyran-2,6-dione, in an isolated yield of 81%. Unsymmetrically substituted pyranopyrandiones were also obtained by ruthenium-catalyzed carbonylative coupling of cyclopropenones with alkynes under similar reaction conditions.     

Adsorption characteristics of bisphenol A onto carbonaceous materials produced from wood chips as organic waste

A single-chain amphiphile containing a rigid Schiff base segment, 3-cyano-N-benzylidene hexadecylamine (CNBHB) in the polar head group was synthesized and studied for its vesicle-forming properties. The dependence of the aggregation behavior of the vesicles as such and in the presence of manganese ions were studied as a function of temperature using differential scanning calorimetry and turbidity measurements. Transmission electron microscopy (TEM) was used to analyze the morphology of the vesicles, showed interesting features with fusion of regular structures, and were quite stable. In the presence of manganese ions, fusion of vesicles takes place. This could be due to the metal ions that are bound to the surface of the vesicles that cause a partial destruction of the hydration shell on the surface of the vesicles. The reduction in the hydration force could thus be responsible for the fusion.     

Fluorometric determination of tin(IV) with 3-hydroxychromone

Summary 3-Hydroxychromone reacts with tin(IV) to produce 11 complex in a weakly acidic-neutral medium. The complex exhibits intense fluorescence. A sensitive method is described for the fluorometric determination of tin(IV) with 3-hydroxychromone. The calibration graph is linear in the range of 0.4–8.0g/25 ml of tin(IV) (pH 4.5–5.0, Excitation wavelength: 365 nm, Measured total fluorescence). Chloride which generally decreases the fluorescence intensity in the fluorometric determination of tin can be tolerated at 300-mg level.

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Fluorometrische Bestimmung von Zinn(IV) mit 3-Hydroxychromon

Zusammenfassung 3-Hydroxychromon reagiert mit Zinn(IV) in schwach saurem bis neutralem Medium unter Bildung eines 11-Komplexes. Dieser fluoresziert intensiv. Ein empfindliches Verfahren zur Bestimmung von Sn(IV) auf dieser Grundlage wurde ausgearbeitet. Die Eichkurve verläuft in dem Gebiet zwischen 0,4 und 8,0g Sn/25 ml bei pH 4,5, einer Wellenlänge von 365 nm und bei Messung der Gesamtfluoreszenz geradlinig. Chloride, die die Fluoreszenzintensität bei Zinnbestimmungen im allgemeinen herabsetzen, können bis zu 300 mg toleriert werden.

     

Mechanism of antioxidative activity of fluvastatin-determination of the active position

In order to clarify the mechanism of action for the antioxidative activity of fluvastatin sodium (FLV, (+/-)-sodium (3RS, 5RS, 6E)-7-[3-(4-fluorophenyl)-1-(1-methylethyl)-1H-indol-2-yl]-3, 5-dihydroxy-6-heptanoate) and its derivatives, reaction of the corresponding methyl ester of FLV with di-tert-butyl diperoxyoxalate was examined, and the corresponding keto derivative was isolated from the reaction mixture. On the basis of this result, it was concluded that the active site is the allylic carbon conjugated with the indole ring.     

Effectiveness of taurine in protecting biomembrane against oxidant

The effect of taurine in protecting biomembrane attacked by hypochlorous acid (HOCl) was examined using canine erythrocytes which had been pre-treated with HOCl. In the treatment, most of the HOCl was consumed as a result of its reaction with a number of electrophilic substances, such as free amino groups (-NH2) in the membrane, whereas hemoglobin inside the cells was not oxidized. The lysis of HOCl-treated erythrocytes was dependent on the concentration of HOCl and on the incubation time at 37 degrees C. Taurine inhibited the lysis at 37 degrees C in a dose dependent manner. During the incubation of HOCl-treated erythrocytes with taurine, an appreciable amount of monochlorotaurine (TauNHCl) was detected in the supernate. This suggests that taurine might remove the oxidized chlorine from HOCl-treated erythrocytes, resulting in the production of TauNHCl. The effect of taurine on the removal of Cl+ moiety was further examined using Sepharose gel with free amino groups. Taurine removed Cl+ moiety from HOCl-treated Sepharose gel, and the yield of TauNHCl depended on the concentration of taurine and the incubation time. These results indicate that taurine might inhibit the hemolysis by scavenging the oxidized chlorine moiety from the HOCl-treated erythrocytes. Inhibition of the HOCl-induced hemolysis was also observed with other amino acids.(ABSTRACT TRUNCATED AT 250 WORDS)     

Enantioselective ring cleavage of dioxane acetals mediated by a chiral Lewis acid: application to asymmetric desymmetrization of meso-1,3-diols

[reaction: see text]. Phenylalanine-derived B-aryl-N-tosyloxazaborolidinones selectively activate one of two enantiotopic oxygen atoms in prochiral anti dioxane acetals derived from meso-1,3-diols, leading to enantioselective formation of ring-cleavage products. The reaction is utilized as a key step in asymmetric desymmetrization of meso-1,3-diols.     

Regioselective allylzincation of alkenylboronate

[reaction: see text] Boryl substitution on an olefin activates the olefinic double bond toward addition of an organozinc reagent. Addition of an allylic zinc reagent to an alkenylboronate thus takes place smoothly to afford a variety of gem-zincio/boryl species. Theoretical studies with density functional calculations on the reaction pathway revealed that the reaction proceeds via a zincio-ene reaction rather than a bora-Claisen rearrangement.     

Transformation of arctiin to estrogenic and antiestrogenic substances by human intestinal bacteria

After anaerobic incubation of arctiin (1) from the seeds of Arctium lappa with a human fecal suspension, six metabolites were formed, and their structures were identified as (-)-arctigenin (2), (2R,3R)-2-(3',4'-dihydroxybenzyl)-3-(3",4"-dimethoxybenzyl)butyrolactone (3), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3",4"-dimethoxybenzyl)butyrolactone (4), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3"-hydroxy-4"-methoxybenzyl)butyrolactone (5), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3",4"-dihydroxybenzyl)butyrolactone (6), and (-)-enterolactone (7) by various spectroscopic means including two dimensional (2D)-NMR, mass spectrometry, and circular dichroism. A possible metabolic pathway was proposed on the basis of their structures and the time course of the transformation. Enterolactones obtained from the biotransformation of arctiin and secoisolariciresinol diglucoside (SDG, from the seeds of Linum usitatissium) by human intestinal bacteria were proved to be enantiomers, with the (-)-(2R,3R) and (+)-(2S,3S) configurations, respectively. Compound 6 showed the most potent proliferative effect on the growth of MCF-7 human breast cancer cells in culture among 1 and six metabolites, while it showed inhibitory activity on estradiol-mediated proliferation of MCF-7 cells at a concentration of 10 microM. These results indicate that the transformation of 1 by intestinal flora might be essential for the manifestation of the estrogenic and antiestrogenic activity of 1.     

Improved separation of alpha chains of collagen type I, type III, and type V by noninterrupted electrophoresis using thioglycolic acid as a negatively charged reducer

Improved separation of alpha chains of collagen type I (alpha 1 [I]2 alpha 2[I]), type III(alpha 1[III]3), and type V (alpha 1[V]alpha 3[V])was achieved by noninterrupted sodium dodecyl sulfate-polyacrylamide gel electrophoresis with a negatively charged reducer, thioglycolic acid. The thioglycolic acid, added to the running buffer of the cathodic reservoir, in the middle of electrophoresis quickly migrated in the gel anode, reducing interchain disulfide linkages in collagen type III and dissociating it into its alpha chain monomer, alpha 1[III], without an interruption of electrophoresis. The alpha chain, alpha 1[III], migrated more slowly than the alpha 1 [I] and alpha 2[I] chains of collagen type I, resulting in an excellent separation of alpha 1[III] from alpha 1[I]. The mobility of alpha 1[III] could be controlled by varying the time of thioglycolic acid addition to the running buffer. This enabled us not only to separate alpha 1[III] from alpha 1[I] and alpha 1[V], but also to precisely quantitate these alpha chains, even at low protein loading of mixed samples.