The synthesis of N-substituted ketimines from oxazirdines

N-Unsubstituted diaryl, alkyl aryl and dialkyl ketimines are prepared in good yield at ambient temperature by the reaction of KOBu^t on oxaziridines having an α-hydrogen atom on the N-alkyl substituent; the mechanism and stereochemistry of the reaction are discussed.     

Stereoselective reductase-catalysed deoxygenation of sulfoxides in aerobic and anaerobic bacteria

Direct and indirect evidence, of unexpected stereoselective reductase-catalysed deoxygenations of sulfoxides, was found. The deoxygenations proceeded simultaneously, with the expected dioxygenase-catalysed asymmetric sulfoxidation of sulfides, during some biotransformations with the aerobic bacterium Pseudomonas putida UV4. Stereoselective reductase-catalysed asymmetric deoxygenation of racemic alkylaryl, dialkyl and phenolic sulfoxides was observed, without evidence of the reverse sulfoxidation reaction, using anaerobic bacterial strains. A purified dimethyl sulfoxide reductase, obtained from the intact cells of the anaerobic bacterium Citrobacter braakii DMSO 11, yielded, from the corresponding racemates, enantiopure alkylaryl sulfoxide and thiosulfinate samples.     

Über die Eigenschaften hydratisierten Chromoxydes. Teil V

Ohne ZusammenfassungÜbersetzt von Dr. K. Jäckel, Marburg/L.Wir danken Herrn Prof. N. R. Dhar D.Sc. (London und Paris), F.R.I.C., F.N.I., I.E.S. (Eetd) Direktor Shila Dhar Institut für Bodenkunde und Vorstand der Chemischen Abteilung, Universität Allahabad, für sein lebhaftes Interesse und seine Ratschläge für die Arbeit.     

Hydrodynamics of a bounded vertical film with nonlinear surface properties

The drainage of a thin liquid film with an insoluble monolayer down a vertical wall is studied. Lubrication theory is used to develop a model where the film is pinned at the top with a given thickness and the film drains into a bath at the bottom. A nonlinear equation of state is used for the surface tension and the surface viscosity is a nonlinear function of the surfactant concentration; these are appropriate for some aqueous systems. The three partial differential equations are solved via discretization in space and then the resulting differential algebraic system is solved. Results are described for a wide range of parameters, and the conditions under which the free surface is immobilized are discussed.     

Carbon-13 and nitrogen-15 nuclear magnetic resonance of physostigmine (eserine)

The ¹⁵N and ¹³C nmr spectra of physostigmine are discussed along with complete assignment of the signals. This alkaloid ¹⁵ N nmr spectrum is notable because it contains nitrogens in three different environments.     

New paper chromatographic separation of microquantities of opium alkaloids

Summary A paper Chromatographic technique on salt-buffered papers for separating the alkaloids of opium has been devised. The method has been used for determining the origin of opium samples by studying the pattern of theR _f values of the alkaloids present and the effect on it produced by the presence of various adulterants.

---

Zusammenfassung Die chromatographische Trennung der Opiumalkaloide auf gepuffertem Papier wurde beschrieben. Das Verfahren wurde zur Herkunftsbestimmung von Opiumproben auf Grund desR _f -Musters der anwesenden Alkaloide benützt. Der Einfluß verschiedener Fälschungszusätze wurde untersucht.

---

Résumé Mise au point d'une technique de Chromatographie sur papier pour la séparation des alcaloïdes de l'opium, oú les papiers sont imprégnés des sels tampons. Utilisation de la méthode pour déterminer l'origine des échantillons d'opium en étudiant les valeurs duR _f des alcaloïdes présents et l'effet produits sur celles-ci par la présence d'adultérants divers.

     

Synthesis and formulation of self-immolative PEG-aryl azide block copolymers and click-to-release reactivity with trans-cyclooctene

Self-immolative aryl azides can react with trans-cyclooctenes (TCO), triphenylphosphines or hydrogen sulfide (H₂S) to activate prodrugs, imaging probes and drug delivery systems. To date, the synthesis of polymers containing these aryl azide self-immolative linkers and their reactivity with a strained alkene (i.e., in a bioorthogonal reaction) has not been explored. Also, due to the instability of aryl azides towards light and high temperatures, the polymerization methods compatible with aryl azides are limited. Through systematic investigation of the reversible addition-fragmentation chain transfer (RAFT) and atom transfer radical polymerization (ATRP) methods, a self-immolative PEG-aryl azide block copolymer (PEG₄₅-b-ABOC₂₈ 2 ) and a non-responsive 4-fluoroaryl block copolymer (PEG₄₅-b-FBOC₂₄ 3 ) was prepared. ATRP provided the desired polymers in a highly controlled manner, whereas the RAFT conditions led to higher levels of aryl azide polymer degradation. The ATRP derived polymers 2 and 3 were formulated into nanoparticles of approximately 200 nm diameter, and particle triggering was demonstrated by the [3+2]-cycloaddition reaction of TCO with PEG₄₅-b-ABOC₂₈ 2 in solution (pure polymer) and as a formulated nanoparticle. Preliminary in vitro cell viability studies suggested that the stimuli-responsive aryl azide polymers/nanoparticles are not cytotoxic up to 200 μg/ml concentrations.