A novel and efficient synthesis of porphine

meso-Tetra(n-hexyloxycarbonyl)porphyrin was found to be converted into porphine, the mother compound of porphyrins, in a 77% yield when heated in aqueous sulfuric acid at 180 °C over 30 min under an inert atmosphere. The observation demonstrates that the substituted porphyrin serves as a novel and useful precursor for porphine.     

On singularities arising from the contraction op the minimal section of a ruled surface

We will discuss the Gorenstein property of the singularity which is blown down from the minimal section of a ruled surface in terms of the extension class. In the case that the base field has positive characteristic, we find a new example (3.4) of Gorenstein singularity in connection with Theorem B.     

Mesomorphic properties of orthopalladated complexes of laterally substituted azobenzene derivatives, 2-alkoxycarbonyl-4-(4-ethoxyphenylazo)phenyl 4-methoxybenzoates

Homologous series of 2-alkoxycarbonyl-4-(4-ethoxyphenylazo)phenyl 4-methoxybenzoates (L) and their orthopalladated μ-chloro dimers (Pd₂Cl₂L₂) have been synthesized and their thermotropic phase transition behaviour has been characterized. The ligands, L, are three-ring nematogens with their central rings substituted in the 2-position by n-alkyl chains of varied length. The thermal stability of the nematic phases decreases rapidly with increasing side chain length and then levels off as the series is ascended. In every case the mesomorphic phase appears only over a small temperature range (less than 20° C). The orthopalladated species also proved to be nematogenic. Melting and clearing points rise on the average by 87° C and 126° C, respectively, and thus the temperature ranges of the nematic phases are enlarged considerably upon metallation. In relation to the observed stabilization of the nematic phases, particularly of higher homologues, a lath-like molecular structure, in which the side chains of the ligands fill up the clefts of the core part, has been deduced for a Pd2Cl2L2 homologue from its solution ¹H-NMR spectrum.     

Symmetry-Breaking Phenomena in an Optimization Problem for some Nonlinear Elliptic Equation

Let $\Omega$ be a bounded domain in ${\bf R^n}$ with Lipschitz boundary, $\lambda >0,$ and $1\le p \le (n+2)/(n-2)$ if $n\ge 3$ and $1\le p< +\infty$ if $n=1,2$. Let $D$ be a measurable subset of $\Omega$ which belongs to the class $ {\cal C}_{\beta}=\{D\subset \Omega \quad | \quad |D|=\beta\} $ for the prescribed $\beta\in (0, |\Omega|).$ For any $D\in{\cal C}_{\beta}$, it is well known that there exists a unique global minimizer $u\in H^1_0(\Omega)$, which we denote by $u_D$, of the functional \[\quad J_{\Omega,D}(v)=\frac12\int_{\Omega}|\nabla v|^2\, dx+\frac{\lambda}{p+1}\int_{\Omega}|v|^{p+1}\, dx -\int_{\Omega}\chi_Dv\,dx \] on $H^1_0(\Omega)$. We consider the optimization problem $ E_{\beta,\Omega}=\inf_{D\in {\cal C}_{\beta}} J_D(u_D) $ and say that a subset $D^*\in {\cal C}_{\beta}$ which attains $E_{\beta,\Omega}$ is an optimal configuration to this problem. In this paper we show the existence, uniqueness and non-uniqueness, and symmetry-preserving and symmetry-breaking phenomena of the optimal configuration $D^*$ to this optimization problem in various settings.     

Identification and determination of sulphamethazine and N4-acetylsulphamethazine in meat by high-performance liquid chromatography with photodiode-array detection

A simple and selective method for the determination of sulphamethazine (SMT) and its metabolite, N4-acetylsulphamethazine (N4-AcSMT), in meat by high-performance liquid chromatography (HPLC) with photodiode-array detection was developed. The drugs were extracted from meat with 0.2% metaphosphoric acid-methanol (6:4), followed by a Bond-Elut C18 clean-up procedure. The HPLC separation was carried out on a Supersphere RP-18e column (125 X 4.0 mm I.D.) using 0.05 M sodium dihydrogenphosphate (pH 4.5)-acetonitrile (8:2) as the mobile phase at a flow-rate of 0.5 ml/min, and monitored with a photodiode-array detector. The recoveries of SMT and N4-AcSMT from meat fortified at 0.5 micrograms/g were 90.1-93.3 and 93.0-94.4%, respectively, with coefficients of variation of 1.9-3.2 and 1.5-2.7%. The limits of detection were 0.02 micrograms/g for each drug. SMT was found in ten samples of imported meat (12.5%) at levels ranging from 0.05 to 1.05 micrograms/g.     

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.     

Application of intramolecular 1,3-dipolar cyclic addition of azide and olefin; construction of (pyrrolidine-2-ylidene)glycinate and glycinamides

Oxopropyl E-(pyrrolidine-2-ylidene)glycinamide (5c) and allyl E-(pyrrolidine-2-ylidene)glycinate (5d) were effectively synthesized from 2,3,5-tri-O-benzyl-4-O-tert-butyldimethylsilyl(TBDMS)-D-arabinal (7) using intramolecular 1,3-dipolar cyclic reaction of azide and olefin as a key reaction. These results proved this cyclic reaction should be applicable for the synthesis of various (pyrrolidine-2-ylidene)glycinate and glycinamide. In addition, the development of a synthetic route for the precursor of an unsaturated cyclic dehydro amino acid involved in azinomycins (carzinophilin) using relating glycinate, methyl E-(pyrrolidine-2-ylidene)glycinate (5a) was described.     

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.     

Capacitance-conductance detector for high-pressure liquid chromatography. Application to alkaloids and fatty acids

Summary A new type of detector for high-pressure liquid chromatography has been designed. This detector is equipped with a RC resonance circuit, and is similar to the capacitance detector previously reported. It is operated as a capacitance detector with nonpolar eluents; while with polar solvents, it behaves as a conductance detector. Electrolytes such as salts, acids and bases are sensitively detected. The detector was successfully used for the detection of fatty acids and alkaloids.

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Zusammenfassung Ein neuartiger Detektor für die Hochdruck-Flüssigchromatographie wurde entwickelt. Dieser ist mit einem Resonanzstromkreis ausgestattet und ähnelt dem kürzlich beschriebenen Kapazitanz-Detektor. Als solcher funktioniert er mit nichtpolaren Eluenten, während er sich mit polaren Lösungsmitteln wie ein Leitfähigkeitsdetektor verhält. Salze, Säuren und Basen werden empfindlich nachgewiesen. Das Gerät wurde zum Nachweis von Fettsäuren und Alkaloiden verwendet.