Dehydrogenative Annulation of Silylated 1H-Indoles with Alkynes via Silyl Migration.

We investigated the dehydrogenative annulation of silylated 1H-indole derivatives with alkynes to synthesize a silole-fused indole. The addition of the in situ generated silylium ion to alkynes was followed by the sila-Friedel-Crafts reaction via silyl migration, realizing regioselective dehydrogenative annulation controlled by the steric bulkiness of a base. The optical properties of the obtained siloloindoles indicated fluorescence of which the intensity depends on the location of the fused silole.

The Steric Effect in Preparations of Vanadium(II)/(III) Dinitrogen Complexes of Triamidoamine Ligands Bearing Bulky Substituents.

The reactions of newly designed lithiated triamidoamines Li3LR (R = iPr, Pen, and Cy2) with VCl3(THF)3 under N2 yielded dinitrogen-divanadium complexes with a µ-N2 between vanadium atoms [{V(LR)}2(µ-N2)] (R = iPr (1) and Pen (2)) for the former two, while not dinitrogen-divanadium complexes but a mononuclear vanadium complex with a vacant site, [V(LCy2)] (R = Cy2 (3)), were obtained for the third ligand. The V-NN2 and N-N distances were 1.7655(18) and 1.219(4) Å for 1 and 1.7935(14) and 1.226(3) Å for 2, respectively. The ν(14N-14N) stretching vibrations of 1 and 2, as measured using resonance Raman spectroscopy, were detected at 1436 and 1412 cm-1, respectively. Complex 3 reacted with potassium metal in the presence of 18-crown-6-ether under N2 to give a hetero-dinuclear vanadium complex with µ-N2 between vanadium and potassium, [VK(LCy2)(µ-N2)(18-crown-6)] (4). The N-N distance and ν(14N-14N) stretching for 4 were 1.152(3) Å and 1818 cm-1, respectively, suggesting that 4 is more activated than complexes 1 and 2. The complexes 1, 2, 3, and 4 reacted with HOTf and K[C10H8] to give NH3 and N2H4. The yields of NH3 and N2H4 (per V atom) were 47 and 11% for 1, 38 and 16% for 2, 77 and 7% for 3, and 80 and 5% for 4, respectively, and 3 and 4, which have a ligand LCy2, showed higher reactivity than 1 and 2.

Synthesis of 1-Silabenzo[d,e]isochromanes via Electrophilic Aromatic Substitution of Aldehydes Activated by Silylium Ion.

A strong Lewis acid silylium ion was utilized for dehydrogenative annulation between dialkyl(1-naphthyl)silanes 1 and aldehydes 2. Silane 1a was reacted with [Ph3C][B(C6F5)4] in the presence of 2,6-di-tert-butyl-4-methylpyridine and aldehydes 2 to afford the annulation product, 1-silabenzo[d,e]isochromanes 3, in moderate isolated yields. The annulation occurred only at the 8-position on the 1-naphthyl group. The silylium ion-promoted hydrosilylation proceeded competitively to afford silyl ethers 4 via the same intermediates, silylcarboxonium ions, in the dehydrogenative annulation. The ratio of 3 and 4 was affected by solvents and the electronic properties of aromatic aldehydes; for example, the use of less polar solvents and that of benzaldehydes with an electron-withdrawing group at the para-position predominantly yielded 3. This annulation reaction was applicable to aldehydes bearing a heteroaromatic group and aliphatic alkyl groups. Judging from these results, both the formation of silylcarboxonium ions by in situ-generated silylium ions and the electrophilic aromatic substitution are important for this annulation reaction.

Effect of Counteranions in Electrocatalytic Hydrogen Generation Promoted by Bis(phosphinopyridyl) Ni(II) Complexes.

We previously reported the preparation and characterization of a Ni(II) complex capable of electrocatalytic hydrogen generation. The complex [Ni(LNH2)2Cl]Cl (1) includes a 6-((diphenylphosphino)methyl)pyridin-2-amine ligand (LNH2), which has an amino group as a base that acts as a proton transfer site by virtue of its location near the metal center. In order to study the effect of counteranions in hydrogen generation, two additional NiII(LNH2) complexes with weakly coordinating/noncoordinating counteranions, [Ni(LNH2)2](OTs)2 (OTs- = p-toluenesulfonate) (2) and [Ni(LNH2)2](BF4)2 (3), were synthesized. Their X-ray crystal structures reveal that the Ni(II) ion is coordinated with two bidentate LNH2 ligands in both complexes. Complex 2 contains both trans and cis isomers in the unit cell. The former is in an axially elongated square-pyramidal geometry (τ5 = 0.17), and the latter is in a nearly square planar geometry (τ4 = 0.11) with two weakly interacting OTs- anions at the axial sites. Complex 3 has only the cis isomer in the solid state, which is in a nearly square planar geometry (τ4 = 0.10). These complexes are slightly different from 1, which has a distorted-square-pyramidal geometry (τ5 = 0.25) with a coordinated chloride anion. UV-vis spectra of 2 and 3 in MeCN show a spectral pattern characteristic of a square-planar Ni(II) complex. These spectra are slightly different from the unique spectrum of 1, which is typical of an axially coordinating Ni(II) species as a result of having a Cl- anion at the apical position. Electrocatalytic hydrogen generation promoted by these three Ni(II) complexes (1.0 mmol) demonstrates an increase in the catalytic current induced by stepwise addition of HOAc (pKa = 22.3 in MeCN) as a proton source. The complexes demonstrate turnover frequencies (TOF) of 3800 s-1 for 1, 5400 s-1 for 2, and 8800 s-1 for 3 in MeCN (3 mL) containing 0.1 M [n-Bu4N](ClO4) in the presence of HOAc (145 equiv) at overpotentials of ca. 530, 490, and 430 mV, respectively.

Dual-Energy Computed Tomography in Patients With Small Hepatocellular Carcinoma: Utility of Noise-Reduced Monoenergetic Images for the Evaluation of Washout and Image Quality in the Equilibrium Phase.

PURPOSE: This study aimed to evaluate the utility of virtual monoenergetic images for detecting washout of small (≤2 cm) hepatocellular carcinoma (HCC) in the equilibrium phase. METHODS: We performed 120-kVp-equivalent linear-blended (M120) and monoenergetic reconstructions from 40 to 90 keV by standard (40, 50, 60, 70, 80, 90) and novel noise-reduced (nMERA: 40+, 50+, 60+, 70+, 80+, 90+) monoenergetic reconstruction algorithms. Image quality and tumor visibility of delayed washout of HCCs in the equilibrium phase were compared between standard monoenergetic reconstruction algorithm and nMERA by objective and subjective analyses. RESULTS: Contrast-to-noise ratio of the tumor at 40+ was the highest, whereas the score of tumor visibility peaked at 50+. The score of overall image quality at 40+ was significantly lower than those on all other image series, and the image quality among other image series were not significantly different. CONCLUSIONS: Virtual monoenergetic image reconstructed with nMERA 50+ was most appropriate to detect washout of small HCCs.

Black-hole universe: time evolution.

Time evolution of a black hole lattice toy model universe is simulated. The vacuum Einstein equations in a cubic box with a black hole at the origin are numerically solved with periodic boundary conditions on all pairs of faces opposite to each other. Defining effective scale factors by using the area of a surface and the length of an edge of the cubic box, we compare them with that in the Einstein-de Sitter universe. It is found that the behavior of the effective scale factors is well approximated by that in the Einstein-de Sitter universe. In our model, if the box size is sufficiently larger than the horizon radius, local inhomogeneities do not significantly affect the global expansion law of the Universe even though the inhomogeneity is extremely nonlinear.

First isolation of Desulfovibrio from the human vaginal flora.

Four Desulfovibrio species, including 2 subtypes of 1 species, namely, Desulfovibrio piger, Desulfovibrio desulfuricans MB subtype and Essex 6 subtype, Desulfovibrio fairfieldensis, and Desulfovibrio vulgaris, have been isolated from the human oral and intestinal flora, but not previously from the vaginal flora. They are opportunistic pathogens and have been considered as possible environmental and etiologic agents involved in ulcerative colitis and chronic periodontitis. We isolated Desulfovibrio intestinalis from vaginal specimens of four Japanese women; a species which has not been previously isolated from humans. The vaginal isolates were highly resistant to cefoxitin, piperacillin, and piperacillin-tazobactam but were susceptible to the other antimicrobial agents tested. Our findings suggested that vaginal Desulfovibrio species may be involved in gynecological or obstetric pathology, and provides additional information of the medical relevance on human Desulfovibrio species.

Susceptibilities of 23 Desulfovibrio isolates from humans.

Antimicrobial susceptibilities of 23 strains of Desulfovibrio spp. were tested by Etest. Generally, Desulfovibrio spp. were highly susceptible to sulbactam-ampicillin, meropenem, clindamycin, metronidazole, and chloramphenicol: MIC(90)s of 6, 4, 0.19, 0.25, and 8 microg/ml, respectively. In addition, these strains generally showed high MICs to piperacillin and piperacillin-tazobactam. Desulfovibrio fairfieldensis (eight strains) was the species least susceptible to most agents, especially beta-lactams, and was the only species resistant to fluoroquinolones. Desulfovibrio desulfuricans strain Essex 6 isolates were less susceptible to beta-lactams than D. desulfuricans strain MB isolates.

In vitro activity of tomopenem (CS-023/RO4908463) against anaerobic bacteria.

The antianaerobic activity of tomopenem, a new longer-half-life parenteral carbapenem, was compared with other carbapenems. Tomopenem showed broad activity against 63 reference species. The activity of tomopenem against 293 clinical isolates was potent (MIC(90), 0.06 to 4 microg/ml) and comparable to those of meropenem and doripenem and more potent than that of panipenem.

In vitro antianaerobic activity of DX-619, a new des-fluoro(6) quinolone.

The in vitro activity of DX-619, a new des-F(6) quinolone, against anaerobic bacteria was evaluated. DX-619 showed potent activity against Bacteroides, Prevotella, Fusobacterium, Micromonas, Actinomyces, and Clostridium spp., with MIC(50)s/MIC(90)s of

[Application of "Microring AN" to "Level 1": presumptive identification of anaerobic gram-negative bacilli].

Commonly isolated anaerobic gram-negative rods (4 genus 64 strains), some other important gram-negative anaerobic species (9 genus 45 strains), and cigar-shaped clostridia (11 strains) were studied on their susceptibility patterns to 6 agents on "Microring AN". Some modifications were made in the methods and interpretation of results. Susceptibility patterns to erythromycin, rifampicin, colistin, benzylpenicillin, kanamycin, and vancomycin were following (sensitive [S], intermediate [I], resistant [R], variable [V]): for Bacteroides fragilis group, V, S, R, R, R, R, respectively; for non-pigmented Prevotella, V, S, V, V, R, R, respectively; for pigmented Prevotella, S, S, SR, V, V, R, respectively: for Fusobacterium nucleatum/necrophorum, R(S), S(I), S(IR), S(R), S, R, respectively; and for F. varium, R, R, S/I, R(S), S, R, respectively. Some results were different from that in the data table in the instruction of "Microring AN", because of differences of methodology and changes of susceptibility of those species during years. As to the other groups, that are not included in the data table in the instruction, results were following: for Bilophila wadsworthia, R, R, S, R, S, R, respectively; Desulfovibrio, V, R(S), R, R, S, R, respectively; for cigar-shaped clostridia, V, S(R), R, R, S(R), S, respectively. "Microring AN" was useful for presumptive identification in genus, species, or group level, though morphological observation and some additional simple tests such as bile-sensitivity and catalase were essential.