Combinatorial synthesis of MUC1 glycopeptides: polymer blotting facilitates chemical and enzymatic synthesis of highly complicated mucin glycopeptides

The chemoselective polymer blotting method allows for rapid and efficient synthesis of glycopeptides based on a "catch and release" strategy between solid-phase and water-soluble polymer supports. We have developed a heterobifunctional linker sensitive to glutamic acid specific protease (BLase). The general procedure consists of five steps, namely (i) the solid-phase synthesis of glycopeptide containing BLase sensitive linker, (ii) subsequent deprotections and the release of the glycopeptide from the resin, (iii) chemoselective blotting of the glycopeptide intermediates in the presence of water-soluble polymers with oxylamino functional groups, (iv) sugar elongations using glycosyltransferases, and (v) the release of target glycopeptides from the polymer platform by selective BLase promoted hydrolysis. The combined use of the solid-phase chemical syntheses of peptides and the enzymatic syntheses of carbohydrates on water-soluble polymers would greatly contribute to the production of complicated glycopeptide libraries, thereby enhancing applicative research. We report here a high-throughput synthetic system for the various types of MUC1 glycopeptides exhibiting a variety of sugar moieties. It is our belief that this concept will become part of the entrenched repertoire for the synthesis of biologically important glycopeptides on the basis of glycosyltransferase reactions in automated and combinatorial syntheses.     

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.     

Analytical high-performance affinity chromatography of ovalbumin-derived glycopeptides on columns of concanavalin A-and wheat germ agglutinin-immobilized gels

Concanavalin A (Con A) or wheat germ agglutinin (WGA) was immobilized on a silica-based support, and the chromatographic behaviours of a series of dansylated ovalbumin-derived glycopeptides on small columns of the resultant gels were compared. These columns had high contents of lectins, and allowed differentiation of these glycopeptides. This method was rapid and reproducible, and enabled sensitive detection of these fluorescent glycopeptides. The structural requirement of these glycopeptides to manifest affinity to the immobilized lectins is also discussed, based on binding constants obtained from their retention times.     

Microdetermination of fluorine in organic compounds by oxygen flask combustion and conductometric titration

For the conductometric titration of fluoride with calcium acetate, solvent system in sample solution and titrant, concentration, and acidity of sample solution were examined to establish the titration conditions. Results of these examinations were transferred to the microdetermination of fluorine in organic compounds using oxygen flask combustion method.Comparative examination between quartz and Pyrex flasks for the combustion of fluorine samples indicated that good results were obtained by the use of the former flask, whereas the use of the latter one gave negative values of 1.0–1.6% due to the formation of boron fluoride during the combustion.     

An intramolecular diels-alder approach to quassinoids—a stereoselective construction of a-aromatic klaineanone

Thermolysis of a benzocyclobutene derivative ($\text{20}$) prepared from norcamphor produced stereoselectively a tetracyclic compound ($\text{2}$), which was converted to a lactone ($\text{21}$) having correct stereochemistry at C₇, C₈, C₉, C₁₁, C₁₃, and C₁₄ positions of (±)-klaineanone.     

Analysis of carbohydrates in glycoproteins by high-performance liquid chromatography and high-performance capillary electrophoresis

We describe two methods for the analysis of oligosaccharide chains in glycoproteins by high-performance liquid chromatography (HPLC) and high-performance capillary electrophoresis (HPCE).O-andN-glycosidically linked oligosaccharides released from glycoproteins can be identified as their borohydride-reduced forms by anion-exchange HPLC with pulsed amperometric detection.N-Glycosidically linked oligosaccharides can also be analyzed as 2-aminopyridine derivatives by HPCE in direct zone electrophoresis mode in an acidic phosphate buffer and zone electrophoresis mode as borate complexes in an alkaline buffer. We also present a convenient procedure for the analysis of the constituent monosaccharides of these oligosaccharides chains by HPLC based on reversed-phase partition mode as 1-phenyl-3-methyl-5-pyrazolone derivatives.     

Preparation of 2-fluoromalonic esters and related compounds from hexafluoropropene

Dimethyl and diethyl fluoromalonates were prepared from hexafluoropropene by its exhaustive alcoholysis or alternatively its ammonolysis and alcoholysis. Fluoromalonates thus obtained or their alkylated derivatives were condensed with o-phenylenediamine or its substituted derivatives to give a number of 1H-3-fluoro-1,5-dibenzodiazepin-2,4(3H,5H)-diones.     

Progress toward the total synthesis of ciguatoxins: a convergent synthesis of the FGHIJKLM ring fragment

[structure: see text] A highly convergent synthetic route to the FGHIJKLM ring fragment of ciguatoxins has been developed, which relied on extensive use of the B-alkyl Suzuki-Miyaura coupling reaction.     

FLAVIN-PHOTOSENSITIZED MONOMERIZATION OF DIMETHYLTHYMINE CYCLOBUTANE DIMER IN THE PRESENCE OF MAGNESIUM PERCHLORATE

We have investigated the photosensitized monomerization of the cis,syn -cyclobutane dimer of 1,3-di-methylthymine using riboflavin tetraacetate and a 5-deazaflavin derivative as photosensitizer. Although little monomerization of the dimer is induced by photoexcitation of the flavins in the absence of any additives, the flavins can function as an efficient photosensitizer in the presence of magnesium perchlorate. Mechanistic studies involving spectroscopic, quantum-yield and flash-photolysis measurements demonstrated that the photosensitized monomerization exclusively proceeds through electron transfer from the dimer to the triplet flavins complexed with Mg²⁺. The effects of magnesium perchlorate are compared with those on the chloranil-photosensitized monomerization and also with the effects of HClO₄ on the flavin-photosensitized reaction.     

Selective reduction of tertiary alkyl,benzyl, and allyl halides to hydrocarbons using lithium 9,9-di-n-butyl-9-borabicyclo[3.3.1]nonanate

The title 9-borabicyclo[3.3.1]nonane(9-BBN) ate complex (1) brings about selective removal of tertiary alkyl, benzyl and allyl halides to give the corresponding hydrocarbons in excellent yields without concomitant attack on secondary, primary and aryl derivatives. The reduction of cis- and trans - 4 - t - butyl - 1 - methylcyclohexyl chlorides (2) with 1 gives 4 - t - butyl - 1 - methylcyclohexanes (3) with partial inversion of configuration in cyclohexane, while that in benzene gives thermodynamically stable trans-3 predominantly. The reactions of 1,1 - dimethyl - 5 - hexenyl chloride (4) and 1,7,7 - trimethylbicyclo[2.2.1]hept - 2 - yl chloride (8) with 1 proceed with the rearrangements characteristic to a carbonium ion intermediate. The reduction of 1 - ethyl - 1 - methylpentyl chloride with 1 follows a second-order rate equation.