Low molar mass polybutadiene made crosslinkable by the introduction of styrenic moieties via urethane linkage: synthesis, kinetic and crosslinking studies

The introduction of styrenic moieties was chosen for the radical crosslinking of polybutadiene bearing hydroxy functions. The modifications were carried out with 3-isopropenyl-α,α-dimethylbenzyl isocyanate (TMI) with or without catalyst (DBTL). A 2nd order kinetic fits our experimental results up to high conversion. Arrhenius parameters were calculated. Thermally catalyzed crosslinking was studied. The reaction was followed by measuring swelling (Q) in toluene as well as mechanical parameters (storage modulus E^′ at the rubbery plateau and tanδ). The influence of temperature, the nature and concentration of initiators, the number of styrenic groups per chain (n=1.2, 2, 2.4) were investigated. In the range of our experimental conditions, a “reaction master curve” was established to predict the evolution of E^′ and Q as a function of time, for any temperature, initiator concentration and value of n.     

Lanthanide bis(trifluoromethanesulfonyl)amides, synthesis, characterization and catalytic activity

The synthesis of lanthanum, neodymium and ytterbium bis(trifluoromethanesulfonyl)amides, named triflimidates, from acetates, carbonates and oxides is investigated. When the synthesis is performed in water, all the salts contain one molecule of water and the lanthanum and neodymium salts synthesized from the acetates also contain one molecule of acetic acid. After removal of the water and acetic acid in refluxing ethanol, the salts are obtained anhydrous but associated for lanthanum and neodymium, whereas the ytterbium salt is monomeric and volatile. When the synthesis is performed directly in ethanol, the neodymium salt contains two molecules of coordinated ethanol.In non-hazardous solvents, these triflimidates are better catalysts than the analogous triflates toward either Friedel-Crafts acylations, or Fries transpositions or Baeyer-Villiger oxidations. Unexpectedly, the cerium(IV) triflimidate catalyzes the oxidation of aromatic ketones to give the corresponding acids.     

In situ formation of palladium(0) from a P,C-palladacycle

In DMF at 80 °C, a Pd⁰ complex is generated in situ from the dimeric P,C-palladacycle (1) in the absence of any reducing agents, presumably via a reductive elimination. The Pd⁰ complex formed in an endergonic equilibrium has been trapped and stabilized by an additional P(o-Tol)₃ and has been detected in cyclic voltammetry by its oxidation peak. Its formation is favored by acetate anions (often used as base in Heck reactions) via the formation of a monomeric anionic P,C-palladacycle ligated by acetate ions. As postulated, P,C-palladacycles are a reservoir of monophosphine-Pd⁰ complexes active in oxidative additions with aryl halides.     

Physical stability vs. chemical lability in microporous metal coordination polymers: a comparison of [Cu(OH)(INA)]n and [Cu(INA)2]n: INA = 1,4-(NC5H4CO2)

Two microporous copper isonicotinate polymers [Cu(OH)(INA)] and [Cu(INA)2] have been formed hydrothermally in good yield and purity; each have 1D channels of ca. 4 x 6 A dimension, but with quite different hydrophilicities; both frameworks retain structural integrity to above 200 degrees C, however whilst [Cu(OH)(INA)] is also chemically stable, [Cu(INA)2] is highly labile and readily transforms to the molecular complex [Cu(INA)2(H2O)4] in water at room temperature.     

Physico-chemical measurements of CL-20 for environmental applications. Comparison with RDX and HMX

CL-20 is a polycyclic energetic nitramine, which may soon replace the monocyclic nitramines RDX and HMX, because of its superior explosive performance. Therefore, to predict its environmental fate, analytical and physico-chemical data must be made available. An HPLC technique was thus developed to measure CL-20 in soil samples based on the US Environmental Protection Agency method 8330. We found that the soil water content and aging (21 days) had no effect on the recoveries (>92%) of CL-20, provided that the extracts were kept acidic (pH 3). The aqueous solubility of CL-20 was poor (3.6 mg l(-1) at 25 degrees C) and increased with temperature to reach 18.5 mg l(-1) at 60 degrees C. The octanol-water partition coefficient of CL-20 (log KOW = 1.92) was higher than that of RDX (log KOW = 0.90) and HMX (log KOW = 0.16), indicating its higher affinity to organic matter. Finally, CL-20 was found to decompose in non-acidified water upon contact with glass containers to give NO2- (2 equiv.), N2O (2 equiv.), and HCOO- (2 equiv.). The experimental findings suggest that CL-20 should be less persistent in the environment than RDX and HMX.     

Improved confidence set estimators of a multivariate normal mean and generalizations

Summary LetX be the observed vector of thep-variate (p≧3) normal distribution with mean θ and covariance matrix equal to the identity matrix. Denotey ₊=max{0,y} for any real numbery. We consider the confidence set estimator of θ of the formC _δa,φ={θ:|θ−δ^a,φ(X)}≦c}, whereδ ^a,φ=[1−aφ({X})/{X}²]₊X is the positive part of the Baranchik (1970,Ann. Math. Statist.,41, 642–645) estimator. We provide conditions on ϕ(•) anda which guarantee thatC _δa.φ has higher coverage probability than the usual one, {θ:|θ−X|≦c}. This dominance result will be shown to hold for spherically symmetric distributions, which include the normal distribution,t-distribution and double exponential distribution. The latter result generalizes that of Hwang and Chen (1983,Technical Report, Dept. of Math., Cornell University).     

Metal Ions Binding to Natural Organic Matter Extracted from Wheat Bran: Application of the Surface Complexation Model

Ions binding to solid organic matter was investigated in this study. A simple surface complexation model, the diffuse double-layer model, was used to describe Pb(II), Cd(II), Zn(II), and Ni(II) binding to a lignocellulosic substrate extracted from wheat bran. The lignocellulosic substrate was represented by two acid sites: a low-pH ("carboxylic") site and a high-pH ("phenolic") site, the phenolic-type sites contributing significantly to the binding behavior, even at relatively low pH. By using the previously determined concentrations of sites and acidity constants, the surface complexation model was applied to Pb, Cd, Zn, and Ni binding as a function of pH in a 0.1 M NaNO(3) medium. The model fits were good over a wide range of pH (2相似文献   

Peptoid atropisomers

We report the isolation of N-aryl peptoid oligomers that adopt chiral folds, despite the absence of chiral centers. Peptoid monomers incorporating ortho-substituted N-aryl side chains are identified that exhibit axial chirality. We observe significant energy barriers to rotation about the stereogenic carbon-nitrogen bond, allowing chromatographic purification of stable atropisomeric forms. We study the atropisomerism of N-aryl peptoid oligomers by computational modeling, NMR, X-ray crystallography, dynamic HPLC, and circular dichroism. The results demonstrate a new approach to promote the conformational ordering of this important class of foldamer compounds.