Some partially fluorinated cyclic and acyclic compounds of sulphur (II) and (IV) and partially fluorinated cyclic compounds of phosphorus (III) and (V)

Sulfinyl fluoride and N-(F-isoprophyl)iminosulfur difluoride form the compounds, O$\text{SN(CH}{}_3\text{)CH}{}_2\text{CH}{}_2\text{N}$(CH₃) and i-C₃F₇N$\text{SN(CH}{}_3\text{CH}{}_2\text{CH}{}_2\text{N}$(CH₃ with symdimethylethylenediamine (1). In contrast, CF₃C(O)NSF₂ and (R_f)₂SF₂ (R_f = CF₃, i-C₃F₇ form only acyclic compounds, CF₃C(O)N(CH₃)CH₂CH₂N(CH₃)C(O)CF₃ and R_fSN(CH₃)CH₂CH₂N(CH₃)SR_f with (1). With PF₃, PF₅ and OPF₃, cyclic compounds $\text{N(CH}{}_3\text{)CH}{}_2\text{CH}{}_2\text{N(CH}{}_3\text{)P}$F, $\text{N(CH}{}_3\text{)CH}{}_2\text{CH}{}_2\text{N(CH}{}_3\text{)P}$F₃, and $\text{N(CH}{}_3\text{)CH}{}_2\text{CH}{}_2\text{N(CH}{}_3\text{)P}$-(O)F result. When the latter two compounds are reacted further with LiNC(CF₃)₂, N(CH₃)CH₂CH₂N(CH₃)PF₂NC(CF₃)₂ and $\text{N(CH}{}_3\text{CH}{}_2\text{CH}{}_2\text{N(CH}{}_3\text{)P}$(O)NC(CF₃)₂) form.     

Chemical structure of cow kappa-casein: study of the soluble tryptic peptides

The sequences of 13 tryptic peptides of cow ?_A-casein (accounting for about one half of the amino acid residues present in the protein) were established. The rennin sensitive linkage could be located in a large fragment (36 residues). ?-casein consists of a hydrophilic part (?-caseino-glycopeptide) and of a hydrophobic moiety (para-?-casein); in this latter, however, several quite hydrophilic sequences were characterized. Another feature of the ?-casein structure is the frequent duplication or triplication of certain amino acids (Pro-Pro; Phe-Phe; Gln-Gln-Gln-Asn-Glu-Glu-Glu; Pro-Pro-Lys-Lys-Asn-Gln-; etc. …).     

Substitution effects enhancing the lasing ability of organic compounds

Simple calculations can help to predict which derivatives in a series of organic compounds are potential lasing material. In conjugated systems, a necessary condition for lasing is that there is not less than a specific minimum energy difference between a first excited allowed and a second excited forbidden transition. This order of transition and energy spacing can be obtained by judicious substitutions even in molecules that do not meet these conditions. Lasing action in the near UV has been observed in five new compounds.     

Functional dynamics of ion channels: modulation of proton movement by conformational switches

Detailed comparative studies of proton relay in native and chemically modified gramicidin channels provide a unique opportunity to uncover the structural basis of biological proton transport. The function of ion channels hinges on their ability to provide surrogate solvation in narrow pore filters so as to overcome the dielectric barrier presented by biological membranes. In the potassium channel KcsA and in the cation channel gramicidin, permeant selectivity and mobility are determined by the proteinaceous matrix via hydrogen bonding, charge-dipole, and dipole-dipole interactions. In particular, main-chain carbonyl groups in these pore interiors play an essential role in the solvation of alkali ions and of protons. In this study, molecular dynamics simulations reveal how the translocation of H(+) is controlled by nanosecond conformational transitions exchanging distorted states of the peptidic backbone in the single-file region of a dioxolane-linked analogue of the gramicidin dimer. These results underline the functional role of channel dynamics and provide a mechanism for the modulation of proton currents by fluctuating dipoles.     

Polymer-supported approach for solution-phase synthesis of cysteine trap protease inhibitors: procedure for straightforward optimization of the P1-P1' pocket

Peptide-based reversible and irreversible cysteine proteases inhibitors are well reported in the literature. Many of these compounds have an electrophilic carbonyl group as a cysteine trap in the place of a scissile amide moiety of the natural substrate. As a common mechanism strategy, we have designed a probe library of a cysteine trap for rapid optimization of P1-P1' pockets of different cysteine proteases. The synthesis of this library using a straightforward methodology based on polymer-supported reagents and scavengers to avoid tedious purification steps has been achieved. For the selective monobromination of diazo ketones, preparation of a new supported reagent, piperidinoaminomethylpolystyrene hydrobromide, is also described.     

Weitere Vereinfachung der Mikrobestimmung von Jod in organischen Verbindungen

Zusammenfassung Die Mikromethode zur Jodbestimmung in organischen Substanzen durch Verbrennen nachSchöniger und nachfolgende Titration mit 0,005-n Quecksilberperchlorat wird dahingehend vereinfacht, daß die Jodabsorption nach der Verbrennung anstatt mit Natronlauge direkt mit Quecksilberperchlorat erfolgt.

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Summary The micro method for determining iodine in organic materials through combustion afterSchöniger and subsequent titration with 0.005N mercuric perchlorate is modified to the extent that after the combustion the iodine is absorbed directly in mercuric perchlorate rather than in sodium hydroxide.

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Résumé On a simplifié la microméthode pour le dosage de l'iode dans les substances organiques avec combustion suivantSchöniger et titrage consécutif par le perchlorate de mercure 0,005N. L'absorption de l'iode après la combustion s'effectue directement par le perchlorate de mercure à la place de la lessive de soude.

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Riassunto La microdeterminazione dello iodio nelle sostanze organiche per combustione secondoSchöniger e successiva titolazione con perclorato di mercurio 0,005-n, è stata semplificata riprendendo direttamente il prodotto di combustione in una soluzione di perclorato di mercurio invece di una soluzione di idrato sodico.

     

Etude des métastannates de cadmium par spectrographie d'absorption infrarouge entre 5 et 40μ. Solutions solides entre l'oxyde d'étain et Poxyde de cadmium

Résumé Par chauffage à 1000° de mélanges d'oxyde stannique et d'oxyde de cadmium en proportions diverses, comme par déshydratation de précipités mixtes des hydroxydes correspondants, il se forme une série de solutions solides de l'oxyde de cadmium dans l'oxyde d'étain. Elles sont solubles dans l'acide chlorhydrique et présentent un spectre d'absorption infrarouge caractéristique que l'on a comparé avec celui des 2 métastannates de cadmium CdSnO₃, l'un de type ilménite, l'autre de type perovskite.

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Summary By heating various mixture of stannic oxide and cadmium oxide to 1000° C, a series of solid solutions of cadmium oxide in stannic oxide results as is the case when mixed precipitates of the corresponding hydroxides are dehydrated. They are soluble in hydrochloric acid and yield a characteristic infrared absorption spectrum that was compared with that of the two cadmium métastannates CdSnO₃, one of the ilmenite type, the other of the perovskite type.

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Zusammenfassung Erhitzt man verschieden zusammengesetzte Gemische von Zinnoxid und Cadmiumoxid auf 1000° C oder werden Mischfällungen der entsprechenden Hydroxide dehydratisiert, so entsteht eine Reihe fester Lösungen von Cadmiumoxid in Zinnoxid. Sie sind in Salzsäure löslich und zeigen ein charakteristisches Absorptionsspektrum im IR. Dieses wurde mit dem Spektrum zweier Cadmium-Metastannate (CdSnO₃) vom Typus des Ilmenits bzw. Perovskits verglichen.

     

Zirconocene-mediated route to enantiopure 9-oxabicyclononanes functionalized on both carbon bridges

[reaction: see text] A zirconocene-mediated ring contraction of 4-vinylfuranosides generated either from d-arabinose or d-glucose is followed by sequential oxidation to the ketone and alkynyl Grignard addition. The resulting cis-cyclobutanediols are subjected in turn to thermal rearrangement and intramolecular oxymercuration-demercuration. The regiochemistry of the final ring closure is controlled by the nature of R.