A reanalysis of branching fractions of charmed mesonsD 0,D + andD s +

We combine highly complementary information on branching fractions of charmed mesonsD ⁰,D ⁺ andD _s ⁺ coming from two experiments both yielding doublecharm samples. The NA 32 experiment provided exclusive branching fractions for channels with at least two charged decay products while a recent Mark III paper provides results on inclusive charm decay properties. The knowledge of channels withK ⁰'s in the former is used to recalculate the charged multiplicity distribution in the latter. We obtain 〈n _ch〉=2.25±0.08 forD ⁰, 〈n _ch〉=1.96±0.08 forD ⁺ and 〈n _ch〉=2.41±0.38 forD _s ⁺ . In turn the knowledge of the charged multiplicity improves the overall normalization of exclusive branching fractions. This reanalysis yields model-independent results for charmed mesons. In particular we obtain branching fractions for 16D _s ⁺ decay channels including $$BF(D_s^ + \to \phi \pi ^ + ) = \left( {4.4\begin{array}{*{20}c} { + 2.3} \\ { - 1.8} \\ \end{array} } \right)\% .$$ .     

Unusual solid-state conformation of D-glucitol hexa(p-chlorobenzoate)

The carbon atom chain in the molecule ofd-glucitol hexa (p-chlorobenzoate) adopts a planar, zigzag conformation in the solid state, as determined by X-ray crystallography. The preference for such conformation in the crystal can be ascribed to the stacking interactions in which an infinite number of p-chlorobenzoyloxy substituents is involved.     

Blaschke-Süss type theorems for closed plane curves

A C¹-class of plane closed curves is considered, which contains all ovals and rosettes. This class is divided into some subclasses for which greatest lower bounds of numbers of antipodal and arc-antipodal sets are determined.     

Investigation of surface phenomena on solid catalysts by thermogravimetry

Thermogravimetry was applied to the investigation of the phenomena of adsorption, chemisorption, desorption and surface reactions on solid catalysts. The measurements were carried out with 13 NaX and NaY type zeolites and with silica gels treated with sodium hydroxide, in the presence of cumene and methanol. On the basis of the quantitative results it is possible to give an interpretation of surface phenomena and to establish the existence of various active centres on the surface of the catalysts.

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Zusammenfassung Adsorptions-, Chemisorptions- und Desorptionserscheinungen, sowie Oberflächenreaktionen an festen Katalysatoren wurden thermogravimetrisch untersucht. Die Messungen wurden an Zeoliten der Typen 13 NaX und NaY und an mit Natriumhydroxid behandelten Silikagelen in Gegenwart von Cumol und Methanol durchgeführt. Aufgrund der quantitativen Ergebnisse war es möglich, die Oberflächenerscheinungen zu deuten und das Vorhandensein von verschiedenen aktiven Zentren an der Katalysatoroberfläche nachzuweisen.

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Résumé On a appliqué la méthode thermogravimétrique à l'étude des phénomènes d'adsorption, de chemisorption et de désorption ainsi qu'aux réactions de surface sur des catalyseurs solides. Les mesures ont été effectuées sur zéolites de type 13 NaX et NaY et sur des silicagels traités par la soude en présence de cumène et de méthanol. Des résultats quantitatifs permettent de donner une interprétation des phénomènes de surface et d'établir l'existence de divers centres actifs à la surface des catalyseurs.

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, , , . , , , , . 13 NaX NaY , . .

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The authors express their gratitude to Prof. S. Malinowski for help and discussion and to Mr. W. Dziklinski for his technical help.     

Syntheses with organoboranes. IX. Vinyl- and 1-alkenyldichloroboranes as ethylene and 1-alkene equivalents for the Diels–Alder reaction

Vinyl- and 1-alkenyldichloroboranes were used as dienophiles for the Diels–Alder reaction with representative aliphatic and cyclic 1,3-dienes. The organoborane adducts were transformed into the corresponding olefins either by protonolysis or by oxidation–mesylation–reduction. Direct protonolysis of the adducts gave in most cases mixtures of olefins whereas the reduction of mesylates with lithium triethylborohydride produced pure olefins in good yields.     

Vtbrational spectra of the triclinic K3[ReO2(CN)4] single crystal

Infrared spectra of K₃[ReO₂(CN)₄] have been recorded using polarized radiation and oriented single crystals. The dichroic behaviour of the bands is analyzed and discussed on the basis of molecular geometry and the oriented molecular model. Experimentally determined dichroic ratios are used to obtain a full set of vibrational frequencies. By combining these data with those obtained from Raman spectra, the fundamental internal and lattice vibrations are assigned.     

Orthorhombic polymorphs of two trans‐4‐aminoazoxybenzenes

The two isomeric compounds 4‐amino‐ONN‐azoxy­benzene [or 1‐(4‐amino­phenyl)‐2‐phenyl­diazene 2‐oxide], i.e. the α isomer, and 4‐amino‐NNO‐azoxy­benzene [or 2‐(4‐amino­phenyl)‐1‐phenyl­diazene 2‐oxide], i.e. the β isomer, both C₁₂H₁₁N₃O, crystallized from a polar solvent in orthorhombic space groups, and their crystal and molecular structures have been determined using X‐ray diffraction. There are no significant differences in the bond lengths and valence angles in the two isomers, in comparison with their monoclinic polymorphs. However, the conformations of the mol­ecules are different due to rotation along the Ar—N bonds. In the α isomer, the benzene rings are twisted by 31.5 (2) and 14.4 (2)° towards the plane of the azoxy group; the torsion angles along the Ar—N bond in the β isomer are 24.3 (3) and 23.5 (3)°. Quantum‐mechanical calculations indicate that planar conformations are energetically favourable for both isomers. The N—H?O hydrogen bonds observed in both networks may be responsible for the deformation of these flexible mol­ecules.     

Spectral and Thermal Studies of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) Complexes with 3-methylglutaric Acid

Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) 3-methylglutarates were prepared as solids with general formula MC₆ H₈ O₄ ×n H₂ O, where n =0–8. Their solubilities in water at 293 K were determined (7.0×10⁻² −4.2×10⁻³ mol dm⁻³ ). The IR spectra were recorded and thermal decomposition in air was investigated. The IR spectra suggest that the carboxylate groups are mono- or bidentate. During heating the hydrated complexes lose some water molecules in one (Mn, Co, Ni, Cu) or two steps (Cd) and then mono- (Cu) or dihydrates (Mn, Co, Ni) decompose to oxides directly (Mn, Cu, Co) or with intermediate formation of free metals (Co, Ni). Anhydrous Zn(II) complex decomposes directly to the oxide ZnO. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermolytic carbonates for potential 5'-hydroxyl protection of deoxyribonucleosides

Thermolytic groups structurally related to well-studied heat-sensitive phosphate/thiophosphate protecting groups have been evaluated for 5'-hydroxyl protection of deoxyribonucleosides as carbonates and for potential use in solid-phase oligonucleotide synthesis. The spatial arrangement of selected functional groups forming an asymmetric nucleosidic 5'-O-carbonic acid ester has been designed to enable heat-induced cyclodecarbonation reactions, which would result in the release of carbon dioxide and the generation of a nucleosidic 5'-hydroxyl group. The nucleosidic 5'-O-carbonates 3-8, 10-15, and 19-21 were prepared and were isolated in yields ranging from 45 to 83%. Thermolytic deprotection of these carbonates is preferably performed in aqueous organic solvent at 90 degrees C under near neutral conditions. The rates of carbonate deprotection are dependent on the nucleophilicity of the functional group involved in the postulated cyclodecarbonation reaction and on solvent polarity. Deprotection kinetics increase according to the following order: 4 < 5 < 10 < 6 < 12 < 7 < 13 < 8 < 14 congruent with 19-21 and CCl4 < dioxane < MeCN < t-BuOH < MeCN:phosphate buffer (3:1 v/v, pH 7.0) < EtOH:phosphate buffer (1:1 v/v, pH 7.0). Complete thermolytic deprotection of carbonates 7, 8, 13, and 14 is achieved within 20 min to 2 h under optimal conditions in phosphate buffer-MeCN. The 2-(2-pyridyl)amino-1-phenylethyl and 2-[N-methyl-N-(2-pyridyl)]aminoethyl groups are particularly promising for 5'-hydroxyl protection of deoxyribonucleosides as thermolytic carbonates.