Amphiphilic Polyoxometalates for the Controlled Synthesis of Hybrid Polystyrene Particles with Surface Reactivity

Amphiphilic organo‐polyoxometalates (POMs) used in the radical emulsion polymerization of styrene allowed the preparation in aqueous medium of stable 50–100 nm polystyrene–POM composite latexes. Thanks to the presence of a trithiocarbonate group in the POM amphiphile, POMs could be covalently linked to the polymer particle surface. The chemical and catalytic integrity of the POMs was confirmed, and the POM‐mediated surface photoactivity of the latexes was demonstrated by the spatially controlled nucleation of silver nanoparticles at the periphery of the composites.     

Enantiospecific C?H Activation Using Ruthenium Nanocatalysts

The activation of C H bonds has revolutionized modern synthetic chemistry. However, no general strategy for enantiospecific C H activation has been developed to date. We herein report an enantiospecific C H activation reaction followed by deuterium incorporation at stereogenic centers. Mechanistic studies suggest that the selectivity for the α‐position of the directing heteroatom results from a four‐membered dimetallacycle as the key intermediate. This work paves the way to novel molecular chemistry on nanoparticles.     

HPLC�CDAD Analysis of Hydrochlorothiazide and Irbesartan in Hypertensive Patients on Fixed-Dose Combination Therapy

Hydrochlorothiazide (HCTZ) and the angiotensin II type 1 receptor antagonist (ARB) irbesartan (IRBE) are well-known antihypertensive drugs, frequently administered as a low-dose combination in a single pill. In this work, a simple, sensitive, and selective high-performance liquid chromatographic (HPLC) method with diode-array detection was developed for simultaneous determination of HCTZ and IRBE levels in the plasma of hypertensive patients given a fixed combination of 12.5 mg HCTZ and 300 mg IRBE. Compounds were extracted from acidified plasma samples with 3 mL ethyl acetate, and eluted at 6 and 19 min from a C₄ column by elution with an acetonitrile?Cphosphate buffer (pH 3.6) mobile-phase gradient at a flow rate of 1 mL min^?1. The assay was linear over the ranges 2.5?C500 and 20?C4,000 ng mL^?1 for HCTZ and IRBE, respectively. Overall intra-assay and inter-assay variation were within acceptance limits. Limits of quantification were 2.5 and 20 ng mL^?1 for HCTZ and IRBE, respectively. Plasma samples remained stable for 12 h at room temperature, through three thaw?Cfreeze cycles, and for 2 and 7 months at ?20 °C. In hypertensive patients, residual concentrations were 22.3 ± 6.0 and 241.8 ± 39.0 ng mL^?1 for HCTZ and IRBE, respectively. There was no interference from other co-administered drugs. Despite the different physicochemical properties of HCTZ and IRBE, our method enables accurate measurement of both drugs for assessment of compliance by patients treated by fixed-dose combination therapy with HCTZ?CIRBE.     

Surface modification of poly(butylene terephthalate) nonwoven by photochemistry and biofunctionalization with peptides for blood filtration

The surface of meltblown poly(butylene terephthalate) (PBT) nonwoven was modified by photochemistry using the photolinker O‐succinimidyl 4‐azido‐2,3,5,6‐tetrafluorobenzoate for the introduction of activated ester functions and then coupling of molecular probes or biomolecules. Approximately 4000 pmol of (L )‐4,5‐[³H]‐lysine was fixed per PBT sample (1.13 cm²) and measured by liquid scintillation counting. The method consisted in a two‐step process: (a) coating of the clip (0.05 mg/sample) on the fibrous surface of the PBT followed by UV irradiation (30 min, 254 nm) and (b) coupling of amine‐terminated molecules (10^?3 M in phosphate buffer–CH₃CN [1/1, v/v], 20 h). Moreover, about 2000 pmol of ³H‐lysine can be immobilized on the PBT surface after UV irradiation (without clip) by aminolysis reactions with the created oxygenated functions. The derivatizations (via the clip and UV irradiation only) were stable after long‐term heating at 100 °C in water or under steam‐sterilization conditions. They induce neither modifications of the nonwoven morphology nor cytotoxicity. This method was applied for the grafting of peptides Gly‐Arg‐Gly‐Asp‐Ser and Gly‐Gly‐Gly‐Gly‐Gly to perform blood filtration experiments and to retain the leukocytes. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Random Walk on Surfaces with Hyperbolic Cusps

We consider the operator associated with a random walk on finite volume surfaces with hyperbolic cusps. We study the spectral gap (upper and lower bound) associated with this operator and deduce some rate of convergence of the iterated kernel towards its stationary distribution.