Total synthesis of isoprekinamycin: structural evidence for enhanced diazonium ion character and growth inhibitory activity toward cancer cells

The structurally novel diazobenzo[a]fluorene antibiotic isoprekinamycin (IPK) has been synthesized for the first time employing a Suzuki coupling of a brominated AB ring synthon with a boronate ester representing the D ring, followed by anionic cyclization and appropriate functional group manipulations. The first indication that the diazobenzo[a]fluorene system exhibits in vitro anticancer activity is provided and X-ray crystallographic evidence for enhancement of diazonium ion character as a consequence of intramolecular H-bonding is described.     

β-delayed Proton Decay of 89Ru

A #-delayed proton activity with a half-life of 1.2 - 0.2 s was assigned to ⁸⁹Ru on the basis of a p-%(X) coincidence measurement in the reaction of ⁵⁸Ni (³⁶Ar, 2p3n ) using a He-jet tape transport system. The measured delayed-proton spectrum of ⁸⁹Ru and relative proton branching ratios to the low-lying states in ⁸⁸Mo were compared with statistical model calculations.     

Interfacial roughness and angle dependence of giant magnetoresistance in magnetic superlattices

Using the two-point conductivity formula, we numerically evaluate the giant magnetoresistance (GMR) in magnetic superlattices with currents in the plane of the layers (CIP), from which the effect of the interfacial roughness and magnetization configuration on the GMR is studied. With increasing interfacial roughness, the maximal GMR ratio is found to first increase and then decrease, exhibiting a peak at an optimum strength of interfacial roughness. For systems composed of relatively thick layers, the GMR is approximately proportional to ,where is the angle between the magnetizations in two successive ferromagnetic layers, but noticeable departures from this dependence are found when the layers become sufficiently thin. Received 21 September 1998 and Received in final form 22 December 1998     

Hydrothermal synthesis and photoluminescent properties of stacked indium sulfide superstructures

Unusual hierarchical stacked superstructures of cubic beta-In2S3 were fabricated via a facile hydrothermal process in the presence of a surfactant cetyltrimethylammonium bromide CTAB; the 3D superstructures were developed by helical propagation of surface steps from microflakes of 10-20 nm thickness.     

Three-stage multilayer formation kinetics during adsorption of an anionic fluorinated surfactant onto germanium. 1. Concentration effect

The adsorption of tetraethylammonium perfluorooctylsulfonate (TEA-FOS) from aqueous solution onto hydroxylated germanium is studied using in situ polarized attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). The adsorption is monitored at a series of bulk solution concentrations spanning from well below to above the critical micelle concentration (CMC; 1.0 mM). The kinetics of adsorption is followed by monitoring the intensity of the fluorocarbon bands. The orientation of the fluorocarbon director with respect to the germanium surface is determined by circular dichroism measurements of CF2 stretching bands. At bulk concentrations ranging from 10% of the CMC to at least 500% of the CMC, the adsorption occurs in an unusual sequence of three stages. Initially, rapid adsorption occurs within 200 min, leading to coverage of a monolayer or less. A long period of slow adsorption follows, during which we hypothesize that surfactant molecules form clusters, some of which serve as nuclei for multilayer growth. This stage concludes suddenly with an acceleration in the rate of adsorption, which eventually leads to multilayer formation. Because this is an anionic surfactant adsorbing onto a negatively charged surface at pH 6, the tetraethylammonium ions must mediate the interactions between the surfactant headgroups and the surface. The dichroism measurements show that TEA-FOS is initially oriented randomly or somewhat parallel to the surface, but over time adopts an orientation somewhat normal to the surface. This behavior is consistent with initial adsorption at isolated sites, followed by aggregation into isotropic admicelles, and finally growth into flattened admicelles. The sudden onset of accelerated adsorption can be explained either by autoaccelerating adsorption or nucleation and growth of a hydrophobic multilayer structure.     

A new family of Ru(II) polypyridyl complexes containing open-chain crown ether for Mg2+ and Ca2+ probing

Six polypyridyl bridging ligands BL(1-6) containing open-chain crown ether, where BL(1-3) formed by the condensation of 4,5-diazafluoren-9-hydrazine with 1,7-bis-(4-formylphenyl)-1,4,7-trioxaheptane, 1,10-bis-(4-formylphenyl)-1,4,7,10-tetraoxadecane, and 1,13-bis-(4-formylphenyl)-1,4,7,10,13-pentaoxatridecane, respectively, BL(4-6) formed by the reaction of 9-(4-hydroxy)phenylimino-4,5-diazafluorene with diethylene glycol di-p-tosylate, triethylene glycol di-p-tosylate, and tetraethylene glycol di-p-tosylate, respectively, have been synthesized. Reaction of Ru(bpy)(2)Cl(2).2H(2)O with BL(1-6), respectively, afforded six bimetallic complexes [(bpy)(2)RuBL(1-6)Ru(bpy)(2)](4+) as PF(6)(-) salts. Cyclic voltammetry of these complexes is consistent with one Ru(II)-centered oxidation around 1.32V and three ligand-centered reductions. These complexes show metal-to-ligand charge transfer absorption at 413-444 nm and emission at 570 nm. Binding behavior of complexes with alkali and alkaline-earth metal ions are investigated by UV-vis absorption, fluorescence, and cyclic voltammetry. Addition of alkali and alkaline-earth metal ions to the solution of [(bpy)(2)RuBL(1-6)Ru(bpy)(2)](PF(6))(4) all result in a progressive quenching of fluorescence, a hyperchromic effect of UV-vis absorption, and a progressive cathodal shift of Ru(II)-centered E(1/2). Ru-BL(2) and Ru-BL(5) show the highest binding ability toward Mg(2+) among the five cations examined while Ru-BL(3) and Ru-BL(6) exhibit good selective recognition ability to Ca(2+).     

Solvothermal synthesis and characterization of two 2-D layered germanium thioantimonates with transition-metal complexes

Two germanium thioantimonates [Co(dien)(2)](2)GeSb(4)S(10) (1, dien = diethylenetriamine) and [Mn(en)(3)]GeSb(2)S(6) (2, en = ethylenediamine) have been solvothermally synthesized and characterized by IR, UV/Vis, fluorescence spectroscopy, elemental analysis, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. 1 contains heterometallic pseudosemicube [GeSb(2)S(7)] clusters and chain-like Sb(4)S(10) tetramers, which are interconnected to form a unique double layer of [GeSb(4)S(10)](4-) with 10-MR helical channels. 2 features a sheet layer of [GeSb(2)S(6)](2-) with ellipse-like 12-MR, where one [GeS(4)] tetrahedra, one [SbS(3)] trigonal-pyramid and one Ψ-[SbS(4)] trigonal bipyramid are combined to form another heterometallic [GeSb(2)S(8)] cluster as a building unit. 1 and 2 exhibit absorption edges at 2.36 eV and 2.10 eV, respectively. 2 exhibits a fluorescence emission at room temperature.     

Preparation and characterization of thermosensitive pluronic F127-b-poly(ɛ-caprolactone) mixed micelles

The mixed micelles composed of pluronic F127-b-poly(?-caprolactone) (F127-CL) and bovine serum albumin (BSA) or polylactic acid (PLA) were fabricated for application as promising drug carriers. F127-CL copolymers were characterized by (1)H NMR, FT-IR, GPC, DSC, XRD and POM. They can self-assemble into micelles in water by solvent evaporation method. The thermo-responsivities of the pure and mixed micelles were investigated. The drug release behaviors were investigated in phosphate-buffered solution (PBS) and acetate buffer solution (ABS), respectively, at 37°C. The hemolysis and coagulation assay and the tumor cell growth inhibition assays were further evaluated. The morphologies of pure micelles underwent from the coexistence of the rods and spheres to the spheres with increasing the lengths of CL. The micelle behaviors were influenced with the addition of BSA and PLA. Both pure and mixed micelles of F127-CL with CL length of 200 show thermo-responsivities from 25 to 45°C, while form larger aggregations at high temperature. The hemolysis and coagulation assays showed that the micelles possess good blood compatibility. The cytotoxicity results showed that the copolymer was a safe carrier and the encapsulated doxorubicind.HCl remained its potent anti-tumor effect. The in vitro release profiles displayed a sustained release of DOX.HCl from the micelles. The block copolymers can be great potential as a nanocontainer in drug delivery systems.