Rate constants for the gas‐phase reaction of CF3CF2CF2CF2CF2CHF2 with OH radicals at 250–430 K

The rate constants k₁ for the reaction of CF₃CF₂CF₂CF₂CF₂CHF₂ with OH radicals were determined by using both absolute and relative rate methods. The absolute rate constants were measured at 250–430 K using the flash photolysis–laser‐induced fluorescence (FP‐LIF) technique and the laser photolysis–laser‐induced fluorescence (LP‐LIF) technique to monitor the OH radical concentration. The relative rate constants were measured at 253–328 K in an 11.5‐dm³ reaction chamber with either CHF₂Cl or CH₂FCF₃ as a reference compound. OH radicals were produced by UV photolysis of an O₃–H₂O–He mixture at an initial pressure of 200 Torr. Ozone was continuously introduced into the reaction chamber during the UV irradiation. The k₁ (298 K) values determined by the absolute method were (1.69 ± 0.07) × 10^?15 cm³ molecule^?1 s^?1 (FP‐LIF method) and (1.72 ± 0.07) × 10^?15 cm³ molecule^?1 s^?1 (LP‐LIF method), whereas the K₁ (298 K) values determined by the relative method were (1.87 ± 0.11) × 10^?15 cm³ molecule^?1 s^?1 (CHF₂Cl reference) and (2.12 ± 0.11) × 10^?15 cm³ molecule^?1 s^?1 (CH₂FCF₃ reference). These data are in agreement with each other within the estimated experimental uncertainties. The Arrhenius rate constant determined from the kinetic data was K₁ = (4.71 ± 0.94) × 10^?13 exp[?(1630 ± 80)/T] cm³ molecule^?1 s^?1. Using kinetic data for the reaction of tropospheric CH₃CCl₃ with OH radicals [k₁ (272 K) = 6.0 × 10^?15 cm³ molecule^?1 s^?1, tropospheric lifetime of CH₃CCl₃ = 6.0 years], we estimated the tropospheric lifetime of CF₃CF₂CF₂CF₂CF₂CHF₂ through reaction with OH radicals to be 31 years. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 26–33, 2004     

Investigation of multicomponent fluoride optical materials in the UV spectral region: I. Single crystals of Ca1−x R xF2+x (R = Sc, Y, La, Yb, Lu) solid solutions

Crystalline materials that are transparent in the vacuum UV spectral region and currently used have been reviewed. Transmission of crystals of solid solutions with the fluorite structure Ca_1?x R _xF_2+x (R = Sc, Y, La, Yb, Lu) in the UV and vacuum UV spectral regions has been investigated. It is shown that application of different methods of purification of fluorides from some impurities can significantly improve the optical quality of fluoride multicomponent crystals in the short-wavelength spectral region.     

K X-ray production cross sections for 40-180 keV protons

Considering the importance of the X-ray production cross sections for the determination of the element concentrations in a given material, we have measured them experimentally for Al Si, Sc, Ti, V, Fe, Co, Ni and Cu bombarded by protons with energies ranging from 40 to 180 keV. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structure of solid monolayers and multilayers of n -hexane on graphite

We present all-atom molecular dynamics simulations ofn-hexane on the basal plane of graphite at monolayer and multilayer coverages. In keeping with experimental data, we find the presence of ordered adsorbed layers both at single monolayer coverage and when the adsorbed layer coexists with excess liquid adsorbate. Using a simulation method that does not impose any particular periodicity on the adsorbed layer, we quantitatively compare our results to the results of neutron diffraction experiments and find a structural transition from a uniaxially incommensurate lattice to a fully commensurate structure on increasing the coverage from a monolayer to a multilayer. The zig-zag backbone planes of all the alkane molecules lie parallel to the graphite surface at the multilayer coverage, while a few molecules are observed to attain the perpendicular orientation at monolayer coverage. Dedicated to Professor C N R Rao on his 70th birthday     

Structure and properties of the mesophase of syndiotactic polystyrene. II. Effect of stepwise extraction on the preparation of the mesophase

In this study, a novel stepwise extraction method has been examined. The guest molecules housed between the helices of the clathrate δ form of syndiotactic polystyrene can be removed completely with this method. A systematic study of the preparation of a solvent‐free mesophase (emptied clathrate) membrane, its helical and residual solvent contents, and its structural transformations has been performed. In this first attempt, an enhancement in the TTGG helical content has been observed in the extracted membrane, and a conceptual mechanism is proposed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 269–273, 2003     

Anionic iron(II) alkoxides as initiators for the controlled ring‐opening polymerization of lactide

Hetero‐bimetallic Fe(II) alkoxide/aryloxides were evaluated as initiators for the ring‐opening polymerization of rac‐lactide. [(THF)NaFe(O^tBu)₃]₂ ( 1 ) and [(THF)₄Na₂Fe(2,6‐diisopropylphenolate)₄] ( 2 ) (THF = tetrahydrofuran) both polymerized lactide efficiently at room temperature, with complex 1 affording better control over the molecular weight parameters of the resultant polymer. At conversions below 70%, a linear increase in molecular weight with conversion was observed, indicative of a well‐controlled polymerization process. Complex 2 is the first example of a dianionic Fe(II) alkoxide and has been structurally characterized to reveal a distorted square planar FeO₄ array in which both Na counterions bridge two aryloxide ligands and are further complexed by two THF ligands. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3798–3803, 2003     

Numerical approximation of generalized Newtonian fluids using Powell–Sabin–Heindl elements: I. theoretical estimates

In this paper we consider the numerical approximation of steady and unsteady generalized Newtonian fluid flows using divergence free finite elements generated by the Powell–Sabin–Heindl elements. We derive a priori and a posteriori finite element error estimates and prove convergence of the method of successive approximations for the steady flow case. A priori error estimates of unsteady flows are also considered. These results provide a theoretical foundation and supporting numerical studies are to be provided in Part II. Copyright © 2003 John Wiley & Sons, Ltd.     

Sulfobetaine‐containing diblock and triblock copolymers via reversible addition‐fragmentation chain transfer polymerization in aqueous media

A novel bifunctional acrylamido‐based reversible addition–fragmentation chain transfer (RAFT) chain‐transfer agent (CTA), N,N′‐ethylenebis[2‐(thiobenzoylthio)propionamide] (CTA2), has been synthesized and used for the controlled free‐radical polymerization of N,N‐dimethylacrylamide (DMA). A comparative study of CTA2 and the monofunctional CTA N,N‐dimethyl‐s‐thiobenzoylthiopropionamide (CTA1) has been conducted. Polymerizations mediated by CTA1 result in poly(N,N‐dimethylacrylamide) (PDMA) homopolymers with unimodal molecular weight distributions, whereas CTA2 yields unimodal, bimodal, and trimodal distributions according to the extent of conversion. The multimodal nature of the PDMAs has been attributed to termination events and/or chains initiated by primary radicals. The RAFT polymerization of DMA with CTA2 also results in a prolonged induction period that may be attributed to the higher local concentration of dithioester functionalities early in the polymerization. A series of ω‐ and α,ω‐dithioester‐capped PDMAs have been prepared in organic media and subsequently employed as macro‐CTAs for the synthesis of diblock and triblock copolymers in aqueous media with the zwitterionic monomer 3‐[2‐(N‐methylacrylamido)‐ethyldimethylammonio] propane sulfonate (MAEDAPS). Additionally, an ω‐dithioester‐capped MAEDAPS homopolymer has been used as a macro‐CTA for the block polymerization of DMA. To our knowledge, this is the first example of a near‐monodisperse, sulfobetaine‐containing block copolymer prepared entirely in aqueous media. The diblock and triblock copolymers form aggregates in pure water that can be dissociated by the addition of salt, as determined by ¹H NMR spectroscopy and dynamic light scattering. In pure water, highly uniform, micellelike aggregates with hydrodynamic diameters of 71–93 nm are formed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1262–1281, 2003