Mono- and dihydryl-pentafluorosulfur-F-alkanes [1]

The systematic preparation of partially fluorinated pentafluorosulfur alkanes containing no additional halogens is reported. Thus, the indirect addition of “HF” (via KF/formamide) to SF₅CH=CF₂, SF₅CFCF₂, and SF₅C(CF₃)CF₂ produces SF₅CH(in2)CF₃, SF₅CHFCF₃, and SF₅C(CF₃)₂H respectively. The monohydryl-pentafluorosulfur-F- alkanes react readily with S₂O₆F₂ to form the corresponding fluorosulfates by oxidative displacement of hydrogen, while the dihydryl derivative undergoes cleavage to produce F-acetyl fluoride. Efforts to convert some of the new materials to the important but unknown pentafluorosulfur “ketone,” SF₅C(O)CF₃, were unsuccessful.     

Nanoparticle-cored dendrimers: synthesis and characterization

The synthesis and characterization of a group of new dendrimers-namely, nanoparticle-cored dendrimers (NCDs)-are described. These materials were obtained by the reduction of hydrogen tetrachloroaurate phase-transferred into toluene in the presence of Fréchet-type polyaryl ether dendritic disulfide wedges of generation 1-5. These materials, possessing nanometer-sized gold clusters at the core and dendritic wedges radially connected to the core by Au-S bonds, were analyzed by TEM and TGA, and by UV, IR, and NMR spectroscopies. The number of branching units connected to the core decreased with the generation of the dendritic wedge, and this number changed from 2.18/nm(2) for Au-G-2 to 0.27/nm(2) for Au-G-5. This result suggests that, in the higher-generation NCDs, a large fraction of the surface area of the metal cluster is not passivated and is therefore available for catalytic activity.     

The anionic alkylation of easily reducible arenes. A photochemical route to nucleophilic aromatic substitution of anthracene by organolithiums

High yield nucleophilic addition ensues upon mixing tetrahydrofuran solutions of benzyllithium or cyclooctadienyllithium and anthracene at low temperatures At least part of this addition proceeds by a single electron transfer pathway. Photolysis of the resulting adducts leads to the elimination of lithium hydride, giving net nucleophilic substitution in approximately 50% yield. The analogous reaction fails with naphthalene, where photolysis of the organolithium/ arene mixture leads to dimeric products derived from the organolithium.     

MO Study of flavin–protein interactions in flavodoxin catalysis

MINDO /3 calculations have been performed on the Clostridium MP flavodoxin active site (a complex of the redox active coenzyme flavin mononucleotide sandwiched between the side chains of methionine and tryptophan) at various redox levels using coordinates derived from x-ray diffraction studies of the holoenzyme. Frontier orbital indices were calculated and indicate that reduction of the flavin is accompanied by induced polar states in the amino acid side chains. This stabilization of charge by the amino acid side chains could account for the reaction rate enhancement of flavin reduction catalyzed by flavodoxin. Frontier orbitals for free flavin, for the flavodoxin bound flavin without the amino acid side chains, and for the oxidized Desulfovibrio vulgaris flavodoxin active site were computed for comparison.     

Pyrimidines. XIII. Novel pyrimidine to pyrimidine transformation reactions

Novel pyrimidine to pyrimidine transformation reactions are described. 1,3-Dimethyl-(or diethyl)-uracil(1) are converted into isocytosine, 2-thiouracil or uracil derivatives by treatment with guanidine, thiourea or urea, respectively. The latter two cases require base catalysis. The effects of some substituents at C-5 and C-6 of 1,3-dialkylated uracils (1a → 1e) on this transformation were examined and a plausible mechanism is offered for their reaction. The utility of this reaction is exemplified by the facile two-step conversion of pseudouridine into the anlileukemic agent, pseudoisocytidine, in good overall yield.     

Thermal degradation studies of alkyl-imidazolium salts and their application in nanocomposites

Increasing the thermal stability of organically-modified layered silicates is one of the key points in the successful technical application of polymer-layered silicate nanocomposites on the industrial scale. To circumvent the detrimental effect of the lower thermal stability of alkyl ammonium-treated montmorillonite, a series of alkyl-imidazolium molten salts were prepared and characterized by elemental analysis, thermogravimetry (TGA) and thermal desorption mass spectroscopy (TDMS). The effect of counter ion, alkyl chain length and structural isomerism on the thermal stability of the imidazolium salts was investigated. Alkyl-imidazolium-treated montmorillonite clays were prepared by ion exchange of the imidazolium salts with Na-montmorillonite. These organically-modified clays were characterized by X-ray diffraction (XRD), TDMS and thermogravimetry coupled with Fourier transform infrared spectroscopy (TGA-FTIR), and compared to the conventional quaternary alkyl ammonium montmorillonite. Results indicate that the counter ion has an effect on the thermal stability of the imidazolium salts, and that imidazolium salts with PF₆⁻, N(SO₂CF₃)₂⁻ and BF₄⁻ anions are thermally more stable than the halide salts. A relationship was observed between the chain length of the alkyl group and the thermo-oxidative stability; as the chain length increased from propyl, butyl, decyl, hexadecyl, octadecyl to eicosyl, the stability decreased. The results also show that the imidazolium-treated montmorillonite has greater thermal stability compared to the imidazolium halide. Analysis of the decomposition products by FTIR provides an insight about the decomposition products which are water, carbon dioxide and hydrocarbons.     

Electrospray ionization quadrupole time-of-flight mass spectrometry and quadrupole mass spectrometry for genotyping single nucleotide substitutions in intact polymerase chain reaction products in K-ras and p53

Single nucleotide polymorphisms (SNPs) and mutations were genotyped for both homozygous and heterozygous PCR products of p53, a tumor suppressor gene, and K-ras, an oncogene, using electrospray ionization (ESI) quadrupole time-of-flight (Q-TOF) mass spectrometry (MS) and ESI-quadrupole MS analysis. Mass accuracy was adequate for both instruments to detect genetic changes in homozygous PCR products, including the most difficult to distinguish (adenine [A] --> thymine [T] transversion). However, for the detection of A --> T shifts (9.0 Da difference) in heterozygous PCR products, the increased resolution of ESI-Q-TOFMS proved essential. Although, greater mass differences in heterozygotes (e.g. cytosine [C] <--> T or guanine [G] <--> A) can be discriminated using ESI-quadrupole MS analysis.