Organic quantitative ultramicroanalysis by pyrolysis,and diffusion of hydrogen through quartz,and by carbonization

Summary Quantitative ultramicro determination of hydrogen, based on the diffusion of hydrogen set free by complete thermal destruction of an organic compound through the wall of a silica glass flask, in which the sample is sealed, has been achieved. Both the percentage of hydrogen and of the molecule residue can be determined. By crushing the flask and weighing, after complete diffusion of hydrogen, the determination of carbon and oxygen ought to be possible.

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Zusammenfassung Auf der Grundlage der Pyrolyse einer organischen Substanz und der Diffusion des dabei freigesetzten Wasserstoffs wurde eine Ultramikromethode zur Bestimmung dieses Elementes ausgearbeitet. Die Probe wird in ein Quarzkölbchen eingeschmolzen, durch dessen Wandung der Wasserstoff diffundiert. Sowohl die Bestimmung des Wasserstoffgehaltes wie des Molekülrestes ist möglich. Nach vollständiger Diffusion des Wasserstoffes und Öffnen des Kölbchens sollten sich Kohlenstoff- und Sauerstoffgehalt durch Wägung bestimmen lassen.

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Résumé On a réalisé la détermination quantitative de l'hydrogène à l'échelle ultramicro, en se fondant sur la diffusion de l'hydrogène mis en liberté par destruction thermique complète d'un composé organique à travers la paroi d'un récipient en silice contenant l'échantillon scellé. On peut doser à la fois les pourcentages de l'hydrogène et du résidu moléculaire. On a pu doser le carbone et l'oxygène en cassant le récipient et en le pesant, après la diffusion complète de l'hydrogène.

     

Conformationally Restricted Analogues of Tryptophan: Synthesis of Chiral 3-Amino-4-indolyl-2-piperidones

Abstract

The {Trp-phenylglycinol} pseudodipeptide (αR,3R?,4R?)-N-(2-acetoxy-1-phenylethyl)-3-amino-4-indolyl-2-piperidone 33 has been synthezised by condensation of the 3-amino-substituted anhydride 30 with (R)-(-)-phenylglycinol followed by reduction of the resulting imide.     

Leptogenesis from neutralino decay with nonholomorphic R-parity violation

In supersymmetric models with lepton-number violation, hence also R-parity violation, it is easy to have realistic neutrino masses, but then leptogenesis becomes difficult to achieve. After explaining the general problems involved, we study the details of a model which escapes these constraints and generates a lepton asymmetry, which gets converted into the present observed baryon asymmetry of the Universe through the electroweak sphalerons. This model requires the presence of certain nonholomorphic R-parity violating terms. For completeness we also present the most general R-parity violating Lagrangian with soft nonholomorphic terms and study their consequences for the charged-scalar mass matrix. New contributions to neutrino masses in this scenario are discussed.     

How neutrinos get mass and what other things may happen besides oscillations?

In this talk I address the theoretical issue of why new physics is required to obtain a nonzero neutrino mass. I then discuss what other things may happen besides neutrino oscillations. In particular I consider a possible new scenario of leptogenesis in R-parity nonconserving supersymmetry.     

Coupe du roi bisection of proteins. Spontaneous tetramerization of two peptides that span the sequence of the rabbit uteroglobin monomer

The study of dividing objects into isometric segments has yielded novel approaches to the synthesis of high-symmetry organic compounds. Reported herein is the first application of this concept to a protein, rabbit uteroglobin (UG). Bisection of UG into two identical homochiral segments led to the design of the heterodimeric 70mer peptide alpha(1,2)-S-S-alpha(3,4) that spans the sequence of the native UG monomer. The ability of this compound to form a globular 140mer tetramer consisting of two noncovalently bound heterodimers was assessed by ultracentrifugation at sedimentation equilibrium and by fluorescent spectroscopy. On the other hand, the monomeric peptides alpha(1,2)-SH and alpha(3,4)-SH were shown to selectively form the alpha(1,2)-S-S-alpha(3,4) heterodimer via spontaneous air oxidation in phosphate buffer at neutral pH.     

Peptide dendrimers based on polyproline helices

We present a new family of peptide dendrimers based on polyproline helices and cis-4-amino-L-proline as a branching unit. Dendrimers were synthesized by a convergent solid-phase peptide synthesis approach. The conformational transition between polyproline type I helix and polyproline type II helix was observed by circular dichroism in branched polyproline building blocks with more than 14 proline residues and in the resulting dendrimers. Both linear and dendritic polyprolines were found to be actively internalized by rat kidney cells. Preliminary results show that the antibiotic ciprofloxacin form complexes with branched polyproline chains in 99.5% propanol.     

Regioselectivity of ring closure of 2-thia- and 2-sulfonyl-5-methyl-5-hexenyl radicals

Ring closure of the alpha-substituted radicals 4 (X = S, SO(2)) is observed to be irreversible and to lead to significant amounts of the product of 6-endo cyclization. Indeed, reduction of the sulfonyl-based radical 4 (X = SO(2)), in which regioselectivity is believed to be controlled by a combination of both steric and FMO interactions, is found to provide an excellent route to the cyclic sulfone 7 (X = SO(2)) in high yield. [reaction: see text]     

Indirect evidence of direct electron communication between the active site of galactose oxidase and a graphite electrode

Bi-enzymatic biosensor based on galactose oxidase (GalOD) and horseradish peroxidase (HRP) using ferrocene as an efficient mediator was constructed. When a dependence of a working potential on the sensor performance was examined, an unusual behaviour was observed. With increasing of an applied working potential a lower concentration of substrate to attain full linear range was needed. A fully linear dependence from the first substrate addition was observed at and above the working potential of 150 mV. This activation of the biosensor response by an applied working potential very well corresponds with a formal potential of GalOD (156 mV). When a membrane prevented GalOD access to the electrode surface was applied, no activation effect of a working potential on the sensor performance was observed. Thus, it can be assumed that direct electron communication between GalOD and the electrode occurred.