Synthesis and structural characterisation of a cationic trinuclear organobismuth complex with an unprecedented coordination mode of hydrotris(2-mercaptoimidazolyl)borate ligands

A new coordination mode of hydrotris(2-mercaptoimidazolyl)borate ligands was found in the reaction of [Na(Tm(tBu))] with Me(2)BiCl to form a trinuclear organobismuth complex [(Me(2)Bi)(3)(Tm(tBu))(2)](+)[Me(2)BiCl(2)](-)(Tm(tBu)= hydrotris(2-mercapto-1-tert-butylimidazolyl)borate).     

Development of a novel analytical method for determination of chondroitin sulfate using an in-capillary enzyme reaction

A novel analytical method for determination of total amount of chondroitin sulfate (CS) based on its conversion to desulfated chondro-disaccharide via an enzyme-catalyzed reaction, was developed. Using the in-capillary enzyme reaction, the method was also applied to the successful construction of an on-line analytical system. Within this system, electrophoretic migration was used to mix zones containing the enzyme mixture (chondroitinase ABC, chondro-4-sulfatase, chondro-6-sulfatase and 2-o-sulfatase) and the substrate (CS). The reaction was then allowed to proceed in the presence of a weak electric field and, finally, the product (desulfated chondro-disaccharide) of enzyme reaction migrated to the detector under the influence of an applied electric field. A polyvinyl alcohol-coated capillary was used to reduce protein adsorption. Desulfated chondro-disaccharide was successfully migrated toward the anode in 10 mM Tris-acetate buffer (pH 7.0) under reversed polarity and detected at 232 nm. The established method was validated and demonstrated to be applicable in the determination of total amount of CS in a commercial ophthalmic solution. No interference from the formulation excipients was observed. Good linearity was obtained, with correlation coefficients above 0.999. Recoveries and precisions ranged from 100.0 to 100.5%, and from 0.2 to 0.6% of the relative standard deviation, respectively. Good agreement was obtained between the established method and traditional photometric method based on carbazole reaction. In this study, application of the method to disaccharide compositional analysis was also performed.     

Chiral norbornadienes as efficient ligands for the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to fumaric and maleic compounds

[reaction: see text] A rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to fumaric and maleic compounds has been developed. While phosphorus-based chiral ligands fail to induce high stereoselectivity, chiral norbornadiene ligands have proved to be uniquely effective to achieve high enantioselectivity in these 1,4-addition reactions.     

Novel stereoselective entry to 2'-beta-carbon-substituted 2'-deoxy-4'-thionucleosides from 4-thiofuranoid glycals

2'-Beta-methyl- and 2'-beta-hydroxymethyl-2'-deoxy-4'-thionucleosides have been synthesized through PhSeCl-mediated electrophilic glycosidation using 4-thiofuranoid glycals having carbon substituents at the C2-position as a glycosyl donor. Preparation of these glycals were carried out by means of the C2 lithiation of 1-chloro-4-thiofuranoid glycal with LTMP followed by the Birch reduction of the chlorine atom. [reaction: see text]     

High-energy quasi-phase-matched optical parametric oscillation in a 3-mm-thick periodically poled MgO:LiNbO3 device

We have demonstrated high-energy quasi-phase-matched optical parametric oscillation in a 3-mm-thick periodically poled 5-mol. % MgO-doped LiNbO3 device with a 32.1-microm grating period and a 30-mm length. With a large-spot-size pump laser of 2.2-mm diameter, we obtained a total output pulse energy of 22 mJ for both the signal (wavelength 1.82 microm) and the idler (2.56 microm) waves at an input pump energy of 46 mJ.     

Adsorption of thiolates to singly coordinated sites on Au111 evidenced by photoelectron diffraction

The adsorption structure of methylthiolate (CH3S) adsorbed on Au(111), a long-standing controversial issue, has been unambiguously determined by scanned-energy and scanned-angle S 2p photoelectron diffraction. The methylthiolate molecules are found to occupy atop sites with a S-Au distance of 2.42 +/- 0.03 A. The angular distribution of the S 2p photoelectrons due to forward scattering reveals that the S-C bond is inclined by approximately 50 degrees from the surface normal towards both the [211] and [121] (nearest-neighbor thiolate) directions.     

Terahertz conductivity and possible BLOCH gain in semiconductor superlattices

We have investigated terahertz emission due to dynamical electron transport in wide-miniband GaAs/Al(0.3)Ga0.7As superlattices. By noting that the time-domain THz emission spectroscopy inherently measures the step-response of the electron system to the bias electric field, the obtained THz spectra were compared with the high-frequency conductivities predicted for miniband transport. Excellent agreement between theory and experiment strongly supports that the THz gain due to Bloch oscillating electrons persists at least up to 1.7 THz. It was also found that Zener tunneling into the second miniband sets the high-frequency limit to the THz gain for the samples studied here.     

Preferential inactivation of paediatric solid tumour cells by sequential exposure to Merocyanine 540-mediated photodynamic therapy and Edelfosine: implications for the ex vivo purging of autologous haematopoietic stem cell grafts

Paediatric solid tumours exhibit steep dose-response curves to alkylating agents and are therefore considered candidates for high-dose chemotherapy and autologous stem cell support. There is growing evidence that autologous stem cell grafts from patients with solid tumours are frequently contaminated with live tumour cells. The objective of this study was to perform, in a preclinical purging model, an initial assessment of the safety and efficacy of a two-step purging procedure that combined Merocyanine 540-mediated photodynamic therapy (MC540-PDT) with a brief exposure to the alkyl-lysophospholipid, Edelfosine. Human and murine bone marrow cells and Neuro-2a murine neuroblastoma, SK-N-SH human neuroblastoma, SK-ES-1 and U-2 OS human osteosarcoma, G-401 and SK-NEP-1 human Wilms' tumour, and A-204 human rhabdomyosarcoma cells were exposed to a fixed dose of MC540-PDT followed by a brief incubation with graded concentrations of Edelfosine. Survival was subsequently assessed by in vitro clonal assay or, in the case of CD34-positive haematopoietic stem cells, by an immunohistochemical method. Combination purging with MC540-PDT and Edelfosine depleted all tumour cells by >4 log while preserving at least 15% of murine granulocyte/macrophage progenitors (CFU-GM), 34% of human CFU-GM, and 31% of human CD34-positive cells. The data suggest that combination purging with MC540-PDT and Edelfosine may be useful for the ex vivo purging of autologous stem cell grafts from patients with paediatric solid tumours.