Synthesis and structural characterization of silanethiolato complexes having tert-butyldimethylsilyl and trimethylsilyl groups

Treatment of cyclotrisilathiane (Me2SiS)3 with 3 equiv. of RLi (R = Me, But) in hexane-Et2O afforded the lithium silanethiolates LiSSiMe2R, and the tmeda adduct [(tmeda)LiSSiMe2But]2 1 (tmeda =N,N,N',N'-tetramethylethylenediamine) was isolated in the case of R = But. Reaction of Fe(CH3CN)2(CF3SO3)2, CoCl2, and [Cu(CH3CN)4](PF6) with 1 gave rise to the silanethiolato complexes M(SSiMe2But)2(tmeda)(M = Fe 2, Co 3), and [Cu(SSiMe2But)]4 4, respectively. Complexes (C5H5)2Ti(SSiMe2R)2(R = Me 5, But 6) and Ni(SSiMe2R)2(dppe)[R = Me 7, But 8; dppe = 1,2-bis(diphenylphosphino)ethane] were prepared from treatments of (C5H5)2TiCl2 and NiCl2(dppe) with the corresponding lithium silanethiolates. Complex 7 readily reacted with (C5H5)TiCl3 to produce the Ti-Ni heterobimetallic compound (C5H5)TiCl(mu-S)2Ni(dppe) 9, in which silicon-sulfur bond cleavage took place. Characterization of all compounds through spectroscopic techniques and elemental analyses are also described. X-Ray structural data for compounds 1 and 3-9 are reported.     

Five- and Six-Coordinate 2-Methyl-2-propanethiolato Complexes of Zirconium(IV): Synthesis and Structures of [Li(DME)(3)][Zr(SCMe(3))(5)] and [(THF)Li](2)Zr(SCMe(3))(6)

Five-coordinate and six-coordinate 2-methyl-2-propanethiolato complexes of zirconium, [Li(DME)(3)][Zr(SCMe(3))(5)] (1) and [(THF)Li](2)Zr(SCMe(3))(6) (2), were obtained from the ZrCl(4)/LiSCMe(3) reaction system. The control of the Zr coordination number, by the ether ligands, THF or DME, bound to Li, is demonstrated by the conversion of 2 into 1 upon dissolution in DME. 1 and 2 were crystallographically characterized. The structures are extensively disordered. Crystal data follow: 1, hexagonal P6(3)/m, a = b = 12.496(3) ?, c = 17.561(9) ?, Z = 2, V = 2375(1) ?(3), R = 5.0%, R(w) = 6.8%; 2, trigonal R32, a = b = 11.813(3) ?, c = 28.37(1) ?, Z = 3, V = 3428(1) ?(3), R = 5.2%, R(w) = 6.4%.     

High-performance fluorescent particles prepared via miniemulsion polymerization

Highly fluorescent polymer particles were prepared with Eu beta-diketonates complex as a fluorophore by miniemulsion polymerization technique. Eu beta-diketonates complex has a long decay time, a large Stokes shift, and very narrow emission bands in comparison with other organic fluorescent compounds. Aqueous miniemulsion was prepared by mixing monomer, crosslinker, hydrophobe, and Eu beta-diketonates complex and then putting the mixture into an aqueous solution of surfactant, followed by ultrasonication. An aqueous solution of initiator was added to the miniemulsion to obtain fluorescent polymer particles, which were monodispersed without aggregation. Particle size was decreased to deca-nano scale by increasing the amount of surfactant. Fluorescent intensity was increased by using Eu beta-complex coordinated with additional ligand. Further fluorescence quantum yields and fluorescent properties in the presence of DNA were investigated to the confirm superiority of Eu beta-diketonates complexes in polymer particles.     

Synthesis and structures of niobium(V) complexes stabilized by linear-linked aryloxide trimers

The preparation and characterization of a series of niobium(V) complexes that incorporate the linear-linked aryloxide trimers 2,6-bis(4,6-dimethylsalicyl)-4-tert-butylphenol [H3(Me-L)] and 2,6-bis(4-methyl-6-tert-butylsalicyl)-4-tert-butylphenol [H3(tBu-L)] are described. The chloride complex [Nb(Me-L)Cl2]2 (1) was prepared in high yield by reaction of NbCl5 with H3(Me-L) in toluene. In contrast, the analogous reaction with H3(tBu-L) gave a mixture of [Nb(tBu-L)Cl2]2 (2) and [Nb(de-tBu-L)Cl2]2 (3a). During the formation of 3a, one of tert-butyl groups at the ortho position in the tBu-L ligand was lost. When the NbCl5/H3(tBu-L) reaction was carried out in acetonitrile, Nb[H(tBu-L)]Cl3(NCMe) (4) was obtained. Heating a solution of 4 in toluene generated 2 and 3a. The isolated complex 4 underwent ligand redistribution in acetonitrile to produce Nb[H(tBu-L)]2Cl(NCMe) (5). Treatment of NbCl5 with Li3(tBu-L) in toluene afforded 2. The chloride ligands in 1 and 2 smoothly reacted with 4 equiv of MeMgI and LiStBu, resulting in [Nb(R-L)Me2]2 [R = Me (6), tBu (7)] and Nb(Me-L)(StBu)2 (8), respectively. A number of the above complexes have been characterized by X-ray crystallography. In the structures of 1, 2, and 6, the R-L ligand is bound to the metal center with a U-coordination mode, while an alternative S-conformation is adopted for 3a and 8. Complexes 4 and 5 contain a bidentate H(tBu-L) diphenoxide-monophenol ligand.     

Janus particles with a functional gold surface for control of surface plasmon resonance

We report in this study the presence of Janus particles, which are candidates for use with electronic color papers. We used negatively charged polystyrene particles (370 nm) as the core particles, and gold was then sputtered onto their packed monolayer under several conditions. The sputtered particles were next redispersed into the aqueous medium by gentle sonication. Gold nanoparticles localized on one side of the cores could also serve as seeds for subsequent shell growth by electroless gold plating. Through these treatments, a series of well-dispersed Janus particles were obtained with gold nanostructures of different size and shape only on one side. Their dispersions showed different colors originating from the surface plasmon resonance absorption of gold nanoparticles localized on the hemisphere. The particles obtained by this approach have potential applications such as in sensors and electronic color paper.     

Prodrugs of 2',3'-dideoxyinosine (DDI): improved oral bioavailability via hydrophobic esters.

Five ester prodrugs of 2'3'-dideoxyinosine (DDI) were synthesized for the purpose of improving oral bioavailability. The prodrugs, acetate (C2-DDI), octanoate (C8-DDI), stearate (C18-DDI), benzoate (Bz-DDI), and hemisuccinate (Suc-DDI) were proved to quantitatively regenerate their parent drug by enzymatic hydrolysis. Though the chemical stability of the prodrugs under acidic conditions was not improved, their solubility in water was significantly decreased by esterification, except for Suc-DDI. Bioavailability was evaluated by oral administration to rats. Two hydrophobic prodrugs (C8-DDI and Bz-DDI) showed higher absolute bioavailability (23.5% and 31.0%, respectively) than did DDI (15.2%), though that of C2-DDI (11.5%) and Suc-DDI (4.5%) was poor.     

Immobilization of yeast and the function of immobilized yeast.

Hansenula anomala, which catalyzes an asymmetric reduction, was immobilized in bulk or spherical crosslinked polymers. The catalytic activity of the yeast for enantio-selective reduction of 3,8-dioxo-4-methoxycarbonyl-9-methyl-delta 4(10)-octalin (lab) was severely affected by the immobilization conditions, such as the crosslink density, and by hydrophobicity of polymers and other components used for immobilization, oxygen concentration in the medium, etc. In some immobilized systems, the ratio of resulting enantiomers was inverted from that in a free yeast system.     

Enantiomeric separation of dansylamino acids by capillary zone electrophoresis based on complexation with cyclodextrins

Summary The enantiomeric separation ability of unmodified and methylated cyclodextrins (CDs) during capillary zone electrophoresis (CZE) was investigated using twelve dansylamino acids. Unmodified - and -CDs exhibited high enantioselectivities. -CD could scarcely separate the enantiomers before and after dimethylation, but obtained enantioselectivity after trimethylation. On the other hand, dimethylation of -CD removed much of its high enantioselectivity. Moreover, the chemical modifications produced a reverse in the migration order of the enantiomers. The inclusion of dansyl-DL-phenylalanine with CDs was evaluated using 600 MHz ¹H NMR spectroscopy.     

Template functions of particle monolayers on hydrophobic solid substrates

The template function of cationic particle monolayers bearing quaternary ammonium groups on their surfaces towards anionic colloids was investigated in this paper. Monodispersed cationic polymer particles having quaternary ammonium groups were self-organized on octadecylated glass plates through hydrophobic interaction. The morphology of the resulting particle monolayers was changed by tuning hydrophilic–hydrophobic balance of particles to fabricate aggregated type and dispersed type of particle monolayers. Gold and silver colloids were selectively deposited onto the particle monolayers through electrostatic interaction. The deposited gold and silver colloids on particle monolayers showed plasmon absorbance. Fluorescent silica colloids were also selectively deposited on particle monolayers to permit fluorescence labeling of the particle monolayers. Cationic particle monolayers fabricated on hydrophobic solid octadecylated were found to effectively work as templates for the deposition of above mentioned inorganic colloids.