New sources of “active” halogen bis(dialkylamide)hydrogen dibromobromates, efficient reagents for destruction of ecotoxicants

Bis(dialkylamide)hydrogen dibromobromates were synthesized and their reactivity was investigated in decomposition of diethylphosphonic, diethylphosphoric, and 4-toluenesulfonic acids 4-nitrophenyl esters. The nucleophilic reactivity of a typical α-nucleophile, hypobromite ion, is independent of the source of the active bromine. The cetyltrimethylammonium dibromobromate is a unique reagent for destruction of ecotoxicants. In weakly alkaline media the half-life of 4-nitrophenyl diethylphosphonate did not exceed 6 s at [BrO^?] 0.02 mol l^?1, and the apparent reaction rate compared to water increased ～40-fold. The main factor governing the micellar effects of surfactants is concentrating the substrate in the micellar pseudophase.     

Globally anisotropic high porosity silica aerogels

We discuss two methods by which high porosity silica aerogels can be engineered to exhibit global anisotropy. First, anisotropy can be introduced with axial strain (i.e. axial compression). In addition, intrinsic anisotropy can result during growth and drying stages and, suitably controlled, it can be correlated with preferential radial shrinkage in cylindrical samples. We have performed small angle X-ray scattering (SAXS) to characterize these two types of anisotropy. We show that global anisotropy originating from either strain or shrinkage leads to optical birefringence and that optical cross-polarization studies are a useful characterization of the uniformity of the imposed global anisotropy.     

Indentation responses of piezoelectric films

Frictionless indentation responses of transversely isotropic piezoelectric film/rigid substrate systems under circular cylindrical indenter (i.e., punch), conical indenter (i.e., cone), and spherical indenter (i.e., sphere) are investigated. Both insulating and conducting indenters are considered. The technique of Hankel transformation is employed to derive the corresponding dual integral equations for the mixed boundary value indentation problems. For the two limiting cases of infinitely thick and infinitely thin piezoelectric films, closed-form solutions are obtained. For piezoelectric films of finite thickness, a numerical method is constructed to solve the dual integral equations and semi-empirical models having only two unknown parameters are proposed for the responses of indentation force, electric charge and electric potential, and contact radius. With the two parameters inferred from the numerical results, the semi-empirical formulae are found to provide good estimates of the indentation responses for the two limiting cases of infinitely thick and thin piezoelectric films, as well as those in between. The inferred parameters in the proposed semi-empirical formulae for normalized indentation force and electric charge are checked against four different piezoelectric materials and are found to be insensitive to the selection of piezoelectric materials. It is believed that the proposed semi-empirical indentation formulae are useful in developing experimental indentation techniques to extract the material properties of piezoelectric films.     

Synthesis and characterization of novel polyimides with 2,2‐bis[4(4‐aminophenoxy)phenyl]phthalein‐3′,5′‐bis(trifluoromethyl)anilide

2,2‐Bis[4(4‐aminophenoxy)phenyl]phthalein‐3′,5′‐bis(trifluoromethyl)anilide (6FADAP), containing fluorine and phthalimide moieties, was synthesized via the Williamson ether condensation reaction from 1‐chloro‐4‐nitrobenzene and phenolphthalein‐3′,5′‐bis(trifluoromethyl)anilide, which was followed by hydrogenation. Monomers such as 2,2‐bis[4(4‐aminophenoxy)phenyl]phthalein‐anilide containing phthalimide groups and 2,2‐bis[4(4‐aminophenoxy)phenyl]phthalein containing only phthalein moieties were also synthesized for comparison. The monomers were first characterized by Fourier transform infrared (FTIR), ¹H NMR, ¹⁹F NMR, elemental analysis, and titration and were then used to prepare polyimides with 2,2‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride. The polyimides were designed to have molecular weights of 20,000 g/mol via off‐stoichiometry and were characterized by FTIR, NMR, gel permeation chromatography (GPC), differential scanning calorimetry, and thermogravimetric analysis. Their solubility, water absorption, dielectric constant, and refractive index were also evaluated. The polyimides prepared with 6FADAP, containing fluorine and phthalimide moieties, had excellent solubility in N‐methylpyrrolidinone, N,N‐dimethylacetamide, tetrahydrofuran, CHCl₃, tetrachloroethane, and acetone, and GPC analysis showed a molecular weight of 18,700 g/mol. The polyimides also exhibited a high glass‐transition temperature (290 °C), good thermal stability (～500 °C in air), low water absorption (1.9 wt %), a low dielectric constant (2.81), a low refractive index, and low birefringence (0.0041). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3361–3374, 2003     

Vinyl‐type polymerization of norbornene by nickel(II) bisbenzimidazole catalysts

Novel nickel(II) bisbenzimidazole complexes were prepared via a three‐step synthetic procedure consisting of aniline/diacid condensation, ligand N‐alkylation, and metal complexation. The complexes were characterized by X‐ray crystallography and found to possess a pseudotetrahedral geometry. Upon activation with methylaluminoxane, these nickel bisbenzimidazoles did not polymerize simple olefins (e.g., ethylene, propylene, and 1‐butene) but were found to carry out the rapid and efficient polymerization of norbornene. The polynorbornene products were characterized by gel permeation chromatography/light scattering, ¹³C NMR, and IR, and their Mark–Houwink and dn/dc parameters were determined. The molecular weights of the polynorbornenes were very high (weight‐average molecular weight = 587,000–797,000 g/mol). ¹³C NMR suggested that the polymerization occurred via vinyl addition (i.e., a 2,3‐linked polymer); no ring‐opened product was observed. Thermogravimetric analysis indicated that the polynorbornenes were stable up to 400 °C under nitrogen. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2095–2106, 2003     

Role of water vapor and CO2 in the paleoclimatic fluctuations along northwestern and southern Syria, and the adjacent Mediterranean Sea

Microscopic petrified grains were collected from a mafic–ultramafic pipe, NE of Dreikeesh, NW Syria. The grains were identified as anthers/gynoecia in herb/grass flowers. Three of the grains showed evidence of magnetism, two slowly dissolved in concentrated HCl, and three microprobed grains showed a montmorillonitic composition. Iron originating from pyroxene was oxidized to magnetite. Released silica formed the mineral suite agate–chalcedony–opal. Warm/cold paleoclimatic fluctuations, occurring during late Pliocene–Holocene, depended on water vapor, CO₂ production, and cinders in the atmosphere. Most of these were associated with changing volcanic/tectonic events. Fluctuations were controlled by heat reflected from the Earth's surface being absorbed by water vapor and CO₂, which both re-reflected the heat back to the surface, thus, raising the temperature. This cycle was repeated several times during late Pliocene–Holocene.     

Degradation of Metal 2-Acrylamido-2-methylpropanesulfonate-N-Vinylpyrrolidine Copolymers in Aqueous Solutions Containing Different Cations

The influence of single- and double-charged cations on degradation of metal 2-acrylamido-2-methylpropanesulfonate-N-vinylpyrrolidine copolymers in aqueous solutions in the presence of potassium peroxodisulfate, K₂S₂O₈, at 50 and 70°C was studied by viscosimetry.