Divinyl Sulfoxide: XI. Selective Addition of Carbonodithioate Anions to Divinyl Sulfoxide in the Water-Benzene System

Selective monoaddition of carbonodithioate anions to divinyl sulfoxide gives rise to O-alkyl S-[2-(vinylsulfinyl)ethyl] carbonodithioates [ROC(S)SK, R = Et, Bu; 42–50°C, 6 h, NaHCO₃, aqueous benzene].     

Organoinorganic composites based on tetraethoxysilane and nitrogen polybases

Hybrid organoinorganic composites insoluble in water and organic solvents were prepared by the hydrolysis of tetraethoxysilane in the presence of poly-1-vinylpyrazole, poly-1-vinylimidazole, and poly-4-vinylpyridine. The composition of the composites was determined by the nature of the polymeric nitrogen base and hydrolysis conditions. The composites synthesized showed high sorption activity in the extraction of the [PdCl₄]^2?, [PtCl₆]^2?, and [AuCl₄]^? ions from hydrochloric acid solutions.     

Synthesis and antitumor activities of mitomycin C (1----3)-beta-D-glucan conjugate.

The conjugate of mitomycin C (MMC) with linear (1----3)-beta-D-glucan from Alcaligenes faecalis var. myxogenes IFO 13140 was synthesized and its antitumor activities investigated. The conjugate (MMC-carboxymethylated linear (1----3)-beta-D-glucan (CMPS)) was obtained by treatment of CMPS with MMC in the presence of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide. In vitro cytotoxicity of MMC-CMPS against L1210 leukemia cells was similar to that of MMC. In i.p.-i.p. system in vivo against P388 leukemia in mice, the maximum increase of MMC-CMPS conjugate in life span (ILSmax) was higher than that of MMC but the therapeutic index was reduced. However, the antitumor activity of MMC-CMPS conjugate against subcutaneously implanted sarcoma 180 solid tumor in mice by i.p. administration was similar to that of MMC at a dose of 1.5 mg eq MMC/kg/d x 7 and the reduction of the number of leukocytes caused by MMC was suppressed by attaching MMC to CMPS. In addition, on assay using serum of sarcoma 180 solid tumor-bearing mice with injection of MMC-CMPS conjugate, a drastic loss of tumor cells and an increase in polymorphonuclear leukocytes (PMN) were observed. This result suggested that MMC-CMPS conjugate induced tumor-regressing factor similar to CMPS.     

Dehydrogenation of 1-(diphenylphosphinoyl)-2-(N′-phenylhydrazino)ethane and N-butyl-N′-phenylhydrazine

Dehydrogenation of 1-(diphenylphosphinoyl)-2-hydrazino-substituted ethanes and N-butyl-N′-phenylhydrazine to the corresponding hydrazone derivatives is performed. Both reactions were established to involve predominantly, if not exclusively, an azo intermediate.     

Evaluation of parameters critical to observing proteins inside living Escherichia coli by in-cell NMR spectroscopy

Our recently developed in-cell NMR procedure now enables one to observe protein conformations inside living cells. Optimization of the technique demonstrates that distinguishing the signals produced by a single protein species depends critically on protein overexpression levels and the correlation time in the cytoplasm. Less relevant is the selective incorporation of (15)N. Poorly expressed proteins, insoluble proteins, and proteins that cannot tumble freely due to associations within the cell cannot yet be observed. We show in-cell NMR spectra of bacterial NmerA and human calmodulin and discuss limitations of the technique as well as prospects for future applications.     

Static micromixers based on large-scale industrial mixer geometry

Mixing liquids at the micro-scale is difficult because the low Reynolds numbers in microchannels and in microreactors prohibit the use of conventional mixing techniques based on mechanical actuators and induce turbulence. Static mixers can be used to solve this mixing problem. This paper presents micromixers with geometries very close to conventional large-scale static mixers used in the chemical and food-processing industry. Two kinds of geometries have been studied. The first type is composed of a series of stationary rigid elements that form intersecting channels to split, rearrange and combine component streams. The second type is composed of a series of short helix elements arranged in pairs, each pair comprised of a right-handed and left-handed element arranged alternately in a pipe. Micromixers of both types have been designed by CAD and manufactured with the integral microstereolithography process, a new microfabrication technique that allows the manufacturing of complex three-dimensional objects in polymers. The realized mixers have been tested experimentally. Numerical simulations of these micromixers using the computational fluid dynamics (CFD) program FLUENT are used to evaluate the mixing efficiency. With a low pressure drop and good mixing efficiency these truly three-dimensional micromixers can be used for mixing of reactants or liquids containing cells in many microTAS applications.     

Photolysis of hexamethyldisilane at 206 nm

The photolysis of Me₆Si₂ at 206 nm results in two main decomposition processes: simple Si---Si bond breaking with a quantum yield of Φ = 0.21 ± 0.03, and Me₃SiH elimination with the concomitant formation of Me₂SiCH₂ with Φ = 0.18 ± 0.01. There is also a minor decomposition channel with a very small quantum yield, Φ = (5.6 ± 0.2) × 10⁻³, which results in the formation of Me₄Si and Me₂Si. The main fate of the excited Me₆Si₂ molecule produced during photolysis is stabilization by collisional deactivation. The end products observed indicate that the reaction pathways followed by the main intermediates, Me₃Si and Me₂SiCH₂, are the same as those found in the photolysis of Me₄Si (Ahmed et al., J. Photochem. Photobiol. A: Chem. 86 (1995) 33).     

Acylation of n-phenyl-2-(indol-3-yl)succinimides

Treatment of N-phenyl-2-(1-R-indol-3-yl)succinimides with acetyl perchlorate leads to acylation of the benzene ring of the indole substituent.L. M. Litvinenko Institute of Physico-Organic and Carbon Chemistry, Ukrainian Academy of Sciences, Donetsk 340114. A. N. Kosygin State Textile Academy, Moscow 117918, GSP-1. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 85–88, January, 1997.     

Catalytic Properties of Acid Solutions and the Structure of Acid–Base Complexes with Strong Hydrogen Bonds

The catalytic action of acid solutions involves an equilibrium step in the formation of a reactive complex of reactant molecules with catalyst entities. The relative concentrations of these complexes are determined by using thermodynamic parameters (acidity functions and activities of catalyst components). Data on the structure of complexes with strong H-bonds can be obtained from the vibrational spectra of these species. These data are required for establishing the mechanisms of catalytic reactions and for predicting the catalytic properties of acid solutions containing these complexes.