Synthesis and properties of silacyclobutylsilazanes

Ammonolysis of silacyclobutanes {ie305-01} (R=Cl, CH₃) gives silacyelobutane di- and polysilazanes. Reaction of the disilazane {ie305-02} with 1-chloro-1-methyl-1-silacyelobutane at 20–80° gives a trisilyl-substituted amine {ie305-03}. Trisilyl-substituted amines with one silacyclobutyl group, are obtained by reacting silacyclobutanes {ie305-04} (R=CH₃, C₆H₅). with sodium or potassium silylamides prepared from hexamethyldisilazane. It is shown that it is possible to obtain silylamides by reacting disilazanes directly with potassium metal at 90–100°.     

Polymers Containing Lactone Groups

Polymers containing intact lactone groups are a new class of macromolecules with reactive groups, which are relatively easy to obtain by polymerization, polycondensation and polyaddition, as well as by reactions on existing macromolecules. Polymers with β-lactone Groups in particular can enter into numerous addition reactions, which can be used, for example, to obtain macromolecules containing hydroxy acid or amino acid groupings. The reactions proceed under mild conditions, and can even be carried out in aqueous media, frequently giving water-soluble polymers. The polymers can be cross-linked at low temperatures, even from the aqueous phase, by the addition of bifunctional or oligofunctional reagents. Polymers containing β-lactone groups can also be used as a basis for graft co-polymers; polyester or polyether branches can be grafted on, depending on whether monomeric lactones or monomeric epoxides are used.     

Aggregation des menschlichen Serumalbumins unter den Bedingungen der W ärmedenaturierung

Ohne Zusammenfassung     

Controlled vesicle self-assembly in microfluidic channels with hydrodynamic focusing

Traditional liposome preparation methods are based on mixing of bulk phases, leading to inhomogeneous chemical and/or mechanical conditions during formation; hence liposomes are often polydisperse in size and lamellarity. Here we show the formation of liposomes that encapsulate reagents in a continuous two-phase flow microfluidic network with precision control of size from 100 to 300 nm by manipulation of liquid flow rates. We demonstrate that by creating a solvent-aqueous interfacial region in a microfluidic format that is homogeneous and controllable on the length scale of a liposome, we can facilitate the fine control of liposome size and polydispersity.     

Unusual Thermolysis of Diisobutyl Polysulfides

Russian Journal of Organic Chemistry -     

Synthesis of 5-Alkyl(benzyl)idene-3-hydroxymethyl-2-thioxothiazolidin-4-ones

Russian Journal of General Chemistry -     

Synthesis and properties of residual graphite nitrate obtained by treatment of graphite nitrate with water

The possibility of obtaining residual graphite nitrate by water treatment of graphite nitrate and its subsequent drying was studied. The expansion coefficients were determined in the temperature range 500–900°C with a step of 100°C for the samples obtained.     

Combined charge and spin density experimental study of the yttrium(III) semiquinonato complex Y(HBPz3)2(DTBSQ) and DFT calculations

High-resolution X-ray diffraction and polarized neutron diffraction experiments have been performed on the Y-semiquinonate complex, Y(HBPz3)2(DTBSQ), in order to determine the charge and spin densities in the paramagnetic ground state, S = (1/2). The aim of these combined studies is to bring new insights to the antiferromagnetic coupling mechanism between the semiquinonate radical and the rare earth ion in the isomorphous Gd(HBPz3)2(DTBSQ) complex. The experimental charge density at 106 K yields detailed information about the bonding between the Y3+ ion and the semiquinonate ligand; the topological charge of the yttrium atom indicates a transfer of about 1.5 electrons from the radical toward the Y3+ ion in the complex, in agreement with DFT calculations. The electron density deformation map reveals well-resolved oxygen lone pairs with one lobe polarized toward the yttrium atom. The determination of the induced spin density at 1.9 K under an applied magnetic field of 9.5 T permits the visualization of the delocalized magnetic orbital of the radical throughout the entire molecule. The spin is mainly distributed on the oxygen atoms [O1 (0.12(1) mu B), O2(0.11(1) mu B)] and the carbon atoms [C21 (0.24(1) mu B), C22(0.20(1) mu B), C24(0.16(1) mu B), C25(0.12(1) mu B)] of the carbonyl ring. A significant spin delocalization on the yttrium site of 0.08(2) mu B is observed, proving that a direct overlap with the radical magnetic orbital can occur at the rare earth site and lead to antiferromagnetic coupling. The DFT calculations are in good quantitative agreement with the experimental charge density results, but they underestimate the spin delocalization of the oxygen toward the yttrium and the carbon atoms of the carbonyl ring.