Amino acid end-group in commercial heparin. III. Determination of the number of amino groups of amino acid and hexosamine residues per heparin molecule

The reactions of heparin with 2,4,6-trinitrobenzenesulfonic acid (TNBS) were studied spectrometrically. Seven different commercial heparins were used in this study. The amino groups react with TNBS to form equimolar amounts of trinitrophenylated (TNP) amino groups and bisulfite ions. The TNP-amino groups further react with bisulfite ions to form the monosubstituted anionic sigma complex. The absorption spectrum with two maxima at approximately 350 nm and approximately 420 nm, characteristic of either the TNP-amino groups or the complex, was analyzed for the reaction of TNBS with heparin. It was shown that the reactivities of TNBS with amino groups from α-amino acid and hexosamine residues are greatly different. By combining the results of the reaction kinetics and the reaction of heparin with Sanger's reagent, the number of the α-amino groups and the free amino groups in hexosamine residues were determined. These data have been performed with a range of heparins from different commercial sources, of different activities and physical characteristics. No correlation was found between the free amino contents of these heparins and biological potency. © 1993 John Wiley & Sons, Inc.     

Synthesis and self-aggregation of cyclic alkynes containing helicene

[structure: see text]. All stereoisomers of a cyclic alkyne containing three helicene units, 1,12-dimethylbenzo[c]phenanthrene, are synthesized using a building block. Isomeric [3 + 3]cycloalkynes aggregate in organic solvents. Vapor pressure osmometry reveals dimer formation of (M,M,M)-[3 + 3]cycloalkynes in chloroform and benzene at concentrations above 2 mM. No higher aggregation is observed. The chirality of helicenes plays an important role in self-aggregation, and diastereomeric (M,P,M)-[3 + 3]cycloalkyne forms a dimer only above 15 mM. Aggregation of racemic (M,M,M)-[3 + 3]cycloalkyne or (M,P,M)-[3 + 3]cycloalkyne is much weaker than that of a single enantiomer.     

Catalytic,asymmetric Mannich-type reactions of alpha-imino esters bearing readily removable substituents on nitrogen

[reaction: see text] Catalytic, enantioselective Mannich-type reactions of alpha-imino esters bearing readily removable substituents on nitrogen are described. Several N-carbamate-protected alpha-imino esters, which are readily prepared from 2-bromoglycine esters using a polymer-supported amine, reacted with silicon enolates to afford the desired adducts in high yields with high enantioselectivity using a copper(II)-diamine complex. Easy deprotection of the product amine and transformation to free alpha-amino acid derivatives have also been demonstrated.     

Enantioselective Strecker-type reaction to sulfonylimines having a 2-pyridylsulfonyl group as a novel stereocontroller

A catalytic enantioselective Strecker-type reaction to N-(2-pyridylsulfonyl)imines in the presence of chiral bis(oxazoline)s afforded the products with a high enantioselectivity. A dynamically induced new chiral center on the sulfur by discriminative coordination of a chiral Lewis acid to one of the sulfonyl oxygens efficiently controlled the enantioselectivity.     

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)