Thiocarbonyl-imide aus der Umsetzung von 2,2,4,4-Tetramethyl-3-thioxocyclobutanon mit Aryl-aziden

Thiocarbonyl Imides from the Reaction of 2,2,4,4-Tetramethyl-3-thioxocylobutanone and Aryl Azides Reaction of 2,2,4,4-tetramethyl-3-thioxocylobutanone ( 6 ) and 4-methoxyphenyl, phenyl, and 4-nitrophenyl azide ( 7a–c , respectively), at 80°, leads to the 11-aryl-5,10-dithia-11-azadispiro[3.1.3.2]undecane-2,8-diones 8a–c (Scheme 3), respectively, in 67–83% yield. The structure of 8b has been established by X-ray crystallography. The formation of the products may be explained via an intermediate thiocarbonyl imide of type D (Scheme 4), generated by the 1,3-dipolar cycloaddition of the aryl azide with the C? S bond of 6 and elimination of N₂.     

Amphiphilic poly(phenyleneethynylene)s can mimic antimicrobial peptide membrane disordering effect by membrane insertion

Antimicrobial peptides (AMPs) are a class of peptides that are innate to various organisms and function as a defense agent against harmful microorganisms by means of membrane disordering. Characteristic chemical and structural properties of AMPs allow selective interaction and subsequent disruption of invaders' cell membranes. Polymers based on m-phenylene ethynylenes (mPE) were designed and synthesized to mimic the amphiphilic, cationic, and rigid structure of AMPs and were found to be good mimics of AMPs in terms of their high potency toward microbes and low hemolytic activities. Using a Langmuir monolayer insertion assay, two mPEs are found to readily insert into anionic model bacterial membranes but to differ in the degree of selectivity between bacterial and mammalian erythrocyte model membranes. Comparison of grazing incidence X-ray diffraction (GIXD) data before and after the insertion of mPE clearly indicates that the insertion of mPE disrupts lipid packing, altering the tilt of the lipid tail. X-ray reflectivity (XR) measurements of the lipid/mPE system demonstrate that mPE molecules insert through the headgroup region and partially into the tail group region, thus accounting for the observed disordering of tail packing. This study demonstrates that mPEs can mimic AMP's membrane disordering.     

Internal structure of dendrimers in the melt under shear: a molecular dynamics study

The molecular structure of fluids composed of dendrimers of different generations is studied using nonequilibrium molecular dynamics (NEMD). NEMD results for dendrimer melts undergoing planar Couette flow are reported and analyzed with particular attention paid to the shear-induced changes in the internal structure of dendrimers. The radii of gyration, pair distribution functions and the fractal dimensionality of the dendrimers are determined at different strain rates. The location of the terminal groups is analyzed and found to be uniformly distributed throughout the space occupied by the molecules. The fractal dimension as a function of strain rate displays crossover behavior analogous to the Newtonian/non-Newtonian transition of shear viscosity.     

‘Three-Component Reaction’ with aromatic thioketones,phenyl azide,and dimethyl fumarate

The reaction of thiobenzophenone (= diphenylmethanethione; 8a ) or 9H-fluorene-9-thione ( 8b ) and methyl fumarate ( 9 ) in excess PhN₃ at 80° yields a mixture of diastereoisomeric thiiranes 10 and 11 (Scheme 1). A mechanism involving the initial formation of 1-phenyl-4, 5-dihydro-1H-1, 2, 3-triazole-4, 5-dicarboxylate 12 by 1, 3-dipolar cycloaddition of PhN₃ and 9 is proposed in Scheme 2. The diazo compound 13 , which is in equilibrium with 12 , undergoes a further 1, 3-dipolar cycloaddition with thioketones 8 to give 2, 5-dihydro-1, 3, 4-thiadiazoles 14 . Elimination of N₂ yields the thiocarbonyl ylide 15 which cyclizes to the corresponding thiirane. Desulfurization of the thiiranes 10 and 11 with hexamethylphosphorous triamide leads to the olefinic compounds 16 (Scheme 3). The crystal structures of 10a , 11a , and 16b were determined.     

A massively parallel multireference configuration interaction program: The parallel COLUMBUS program

A massively parallel version of the configuration interaction (CI) section of the COLUMBUS multireference singles and doubles CI (MRCISD) program system is described. In an extension of our previous parallelization work, which was based on message passing, the global array (GA) toolkit has now been used. For each process, these tools permit asynchronous and efficient access to logical blocks of 1- and 2-dimensional (2-D) arrays physically distributed over the memory of all processors. The GAs are available on most of the major parallel computer systems enabling very convenient portability of our parallel program code. To demonstrate the features of the parallel COLUMBUS CI code, benchmark calculations on selected MRCI and SRCI test cases are reported for the CRAY T3D, Intel Paragon, and IBM SP2. Excellent scaling with the number of processors up to 256 processors (CRAY T3D) was observed. The CI section of a 19 million configuration MRCISD calculation was carried out within 20 min wall clock time on 256 processors of a CRAY T3D. Computations with 38 million configurations were performed recently; calculations up to about 100 million configurations seem possible within the near future. © 1997 by John Wiley & Sons, Inc.     

Contribution to the study of elastic properties of KGd(WO4)2:Er3+ single crystals by Brillouin spectroscopy

In this paper we present the study of the acoustic phonons propagating in Er³⁺‐doped KGd(WO₄)₂ single crystals by Brillouin spectroscopy. For the investigated crystals the velocities of the longitudinal and transverse acoustic phonons [100], [010], [001], [101] and [110] have been determined. Moreover, the values of the elastic constants: C₂₂, C₄₄ and C₆₆ of Er³⁺‐doped KGd(WO₄)₂ single crystals have been estimated. It was revealed that the presence of the Er³⁺‐ions in KGd(WO₄)₂ crystals, for the used doping concentration 1 at% does not influence their elastic properties. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Observation of the boundary layer on the top of ice growing from melt

The boundary layer appearing near the ice front during directional freezing of water was investigated by the Mach-Zehnder interferometer. Temperature profiles in the cell during experiments were displayed. Properties of this layer were measured in dependence on growth rate and properties of water. The gas bubbles capturing and building of air channels in the ice were also observed. Nature of the observed transition layer is briefly discussed.     

Stereospecific synthesis of P-epimeric (Rp1, Rp2)-bis-[O-l-menthylphenylphosphonothionyl] diselenide. A new variant of the stereoselective Staudinger reaction

An efficient procedure is described that leads to pure (S_P)- O -l-menthylphenylthiophosphinate. The absolute configuration of this diastereomer was assigned by chemical correlation and confirmed by X-ray crystallography. The reaction of the isomer with phenyl azide, leading to amidate, is a new variant of the stereoselective Staudinger reaction. Addition of elemental selenium to the (S_P)-thiophosphinate led to diastereomeric O-l-menthylphenylselenophosphonothioic acid, which was finally oxidized to the diastereomeric (R_P1,R_P2)-bis-[O-l-menthylphenylphosphonothionyl] diselenide. The diselenide structure was unambiguously confirmed by ³¹P NMR spectroscopy.