Cathode-catalyzed transesterification of alkylphosphonates

The cathodic electrolysis of aliphatic alcohols and alkylphosphonates in acetonitrile with 0.5 N Et₄NClO₄ as the base electrolyte leads to mono- and ditransesterified phosphonates. The yield and ratio of these products is a function of the nature of the starting reagents and amount of current passed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 200–204, January, 1991.     

Investigations on surface diffusion in sparingly soluble monolayers at the gas/liquid interface using radiotracer technique

Summary A method is proposed for calculating surface selfdiffusion coefficients in sparingly soluble monolayers at fluid interfaces based on radiotracer measurements and allowing for counter geometry. On this basis an analysis of experimental results is possible without having to allow for processes competing with surface self-diffusion. Monolayers of various long-chainn-alcohols andn-alkane-carboxylic acids were studied in the area range between 0.23 nm²/molecule and 2.0 nm²/molecule. Surface self-diffusion coefficientsD _s were determinded only up to areas of 0.75 nm2/molecule since, in case of greater areas, the analysis of surface concentration becomes inexact due to the increasing influence of density convection. For the systems studied,D _s values lie in the order of 10^–5 cm²/s. In all compounds studied, the values ofD _s increase with area per molecule. In addition, dependence on the type of hydrophilic group and alkyl-chain length of monolayer molecules was proved. The results are discussed by means of various model concepts.

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Zusammenfassung Ein Verfahren zur Berechnung der Oberflächenselbstdiffusionskoeffizienten in schwerlöslichere Monoschichten an fluiden Phasengrenzen auf der Grundlage von Radiotracermessungen und unter Berücksichtigung der Zählrohrgeometrie wird vorgeschlagen. Auf dieser Basis ist eine Auswertung der Experimentalergebnisse möglich, ohne daß zur Oberflächenselbstdiffusion in Konkurrenz stehende Transportvorgänge berücksichtigt werden müssen. Untersucht wurden Monoschichten verschiedener längerkettigern-Alkanole undn-Alkancarbonsäuren im Flächenbereich zwischen 0,23 nm²/Molekül und 2 nm²/Molekül. OberflächenselbstdiffusionskoeffizientenD _s wurden nur bis zu Flächenwerten von 0,75 nm²/Molekül bestimmt, weil bei höheren Flächen die Auswertung der Oberflächenkonzentrationsänderungen wegen des zunehmenden Einflusses von Dichtekonvektion ungenau wird. DieD _s -Werte liegen für die untersuchten Systeme in der Größenordnung 10^–5 cm2/s. Bei allen untersuchten Verbindungen nehmen die Werte von D_s mit steigender Fläche pro Molekül zu. Außerdem wurde die Abhängigkeit von der Art der hydrophilen Gruppe und der Alkylkettenlänge der Monoschichtmoleküle nachgewiesen. Die Ergebnisse wurden anhand verschiedener Modellvorstellungen diskutiert.

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With 8 figures and 1 table     

Synthesis and microbial transformation of β-amino nitriles

Rhodococcus equi A4, Rhodococcus erythropolis NCIMB 11540 and Rhodococcus sp. R312 were investigated towards their ability to produce β-amino amides and acids from β-amino nitriles. The microorganisms show comparable trends: five-membered alicyclic 2-amino nitriles were transformed significantly faster than the six-membered compounds and the products of trans-2-amino nitriles (amides and acids) were formed considerably faster than the cis-counterparts (amides). The trans-five membered nitriles gave the amides (1b, 5b) in excellent enantiomeric excess (94-99%), the biotransformation of trans-six membered substrates resulted in the formation of the acid (3c, 7c) in excellent ee (87-99%). The ee's of the cis-compounds were throughout lower. Fifteen new substances were synthesized and characterized in the course of this work.     

Oligodeoxynucleotide analogues containing 3′-deoxy-3′-C-threo-hydroxymethylthymidine: Synthesis, hybridization properties and enzymatic stability

Novel Oligodeoxynucleotide analogues containing 3′-C-threo-methylene phosphodiester internucleoside linkages were synthesized on automated DNA-synthesizers using the phosphoramidite approach. The sugar modified phosphoramidite building block 5 was obtained by phosphitylation of 1-(2,3-dideoxy-5-O-(4,4′-dimethoxytrityl)-3-C-hydroxymethyl-β-D-threo-pentofuranosyl)thymine (4) which was synthesized in only three steps from 5′-O-(4,4′-dimethoxytrityl)thymidine (1). The hybridization properties and enzymatic stability of the oligonucleotide analogues were studied by UV experiments. 17-Mers having one or three modifications in the middle or two modifications in each end hybridized to DNA with moderate lowered affinity compared to unmodified 17-mers (ΔT_m 1–3°C per modification). Furthermore, the end-modified and all-modified oligonucleotides were stable towards snake venom phosphodiesterase.     

The particle structure ofv-dimensional Ising models at low temperatures

In this work we study thev-dimensional Ising model at low temperatures and establish the existence of an upper gap in the energy-momentum spectrum of the two-point function forv3. Forv=2, it is known that this gap is absent.Supported in part by Conselho Nacional de Pesquisas (CNPq-Brazil), Universidade Federal de Minas Gerais (Brazil) and the National Science Foundation under Grant PHY76-17191