Super impact strength of blends prepared from regular HIPS and poly(butyl acrylate)‐block‐poly(styrene) obtained by RAFT polymerization

S‐allyl‐4‐methyldithiobenzoate was synthesized and used as a chain transfer agent for the RAFT polymerization of butyl acrylate to produce a functionalized acrylic rubber. A solution of 8 wt% of this functionalized rubber was prepared in styrene and polymerized to generate a material called acrylic rubber‐modified polystyrene (AMP) constituted by well‐dispersed particles of poly(butyl acrylate)‐block‐poly(styrene) into a polystyrene matrix. Impact strength of injection‐molded samples of AMP was measured and compared with the general purpose polystyrene (GPPS) and the high impact polystyrene (HIPS). AMP itself showed an impact strength value similar to GPPS; however, when AMP was blended with conventional HIPS, the resulting material exhibited an improvement of 76–91% as compared to HIPS by itself, without affecting negatively tensile properties. Transmission electron microscopy analysis revealed both kinds of dispersed phases, i.e. the typical salami particles of polybutadiene coming from HIPS (size: 0.5–2 µ) and small particles from poly(butyl acrylate)‐block‐poly(styrene) (size: ～50 nm). We clearly showed that such a bimodality of the particle size distribution caused the positive synergistic effect on impact strength. Copyright © 2011 John Wiley & Sons, Ltd.     

19F NMR analyses of some cyclopropane derivatives

Structural assignments of all possible diastereoisomers of 1-chloro- 2-ethoxy-1-fluoro-alkylcyclopropanes have been achieved through their ¹⁹F NMR spectra. The previously unreported effect of an ethoxyl group on the fluorine signal has been studied and found to promote in most cases a shielding effect in the vicinal $\text{cis}$-fluorine and a deshielding effect when $\text{trans}$ to this halogen.     

Solution of sparse quasi-square rectangular systems by Gaussian elimination

We present a general method for the linear least-squares solutionof overdetermined and underdetermined systems. The method isparticularly efficient when the coefficient matrix is quasi-square,that is when the number of rows and number of columns is almostthe same. The numerical methods for linear least-squares problemsand minimum-norm solutions do not generally take account ofthis special characteristic. The proposed method is based onLU factorization of the original quasi-square matrix A, assumingthat A has full rank. In the overdetermined case, the LU factorsare used to compute a basis for the null space of A^T. The right-handside vector b is then projected onto this subspace and the least-squaressolution is obtained from the solution of this reduced problem.In the case of underdetermined systems, the desired solutionis again obtained through the solution of a reduced system.The use of this method may lead to important savings in computationaltime for both dense and sparse matrices. It is also shown inthe paper that, even in cases where the matrices are quite small,sparse solvers perform better than dense solvers. Some practicalexamples that illustrate the use of the method are included.     

Photolysis of mortonin

Irradiation of mortonin (2a), gave an isomeric photoproduct called photomortonin, whose structure was proved to be 3a.     

Flow-injection analysis-spectrophotometric determination of nitrite and nitrate in water samples by reaction with proflavin

A flow-injection manifold is proposed for determination of nitrite based on the reaction with 3,6-diamino acridine (proflavin sulfate) in hydrochloride acid medium. The assembly is adapted for nitrate determination by including a reductive column filled with copperized cadmium. The influence of foreign substances is also studied. The method gives a linear calibration graph over the range 0.06-4 mg 1(-1) nitrite, with an RSD <0.5%. The method was applied to nitrite and nitrate determinations in either waste water or coastal marine water samples.     

Thermodynamic study of binary mixtures containing 1-butylpyridinium tetrafluoroborate and methanol, or ethanol

Densities and speeds of sound have been determined for the binary mixture (1-butylpyridinium tetrafluoroborate + methanol, or ethanol) over the temperature range 293.15 K to 323.15 K. From experimental values, excess volume and excess isentropic compressibility have been calculated. The mixtures give negative values for the excess properties. Besides, (vapour + liquid) equilibrium in isothermal conditions has been obtained for these systems at T = 303.15 K and T = 323.15 K, which has allowed us to derive activity coefficients and excess Gibbs functions. Positive deviations from Raoult’s law have been found. A detailed analysis and interpretation of results have been carried out in structural and energetic terms using thermodynamic information of the pure compounds.     

Spectroscopic Properties of 4‐Pyridoxic Acid as a Function of pH and Solvent

The photophysical properties and acid/base equilibria of 4‐pyridoxic acid (=3‐hydroxy‐5‐(hydroxymethyl)‐2‐methylpyridine‐4‐carboxylic acid), the final product of the catabolism of vitamin B₆, have been studied in aqueous solutions. The ground state of 4‐pyridoxic acid exhibits the different protonated forms A – D in the range of H₀=?6 to pH 11.5. HMQC‐ and HMBC‐NMR Studies allowed the pH‐dependent assignment of the different C‐atoms, and the evaluation of the deprotonation sequence. The 3‐OH group in the ground state has a ‘pK_a’ of H₀=?0.64, which is much lower than that found for other vitamin B₆ related compounds. The pK_a value of the 4‐COOH group is 5.4. Fluorescence studies showed that the same species exist at the lowest excited singlet state, but in different pH ranges. The 3‐OH group is four pH units more acidic in the lowest excited singlet state than in the ground state. Excitation spectra and emission decays in the pH range of 8 to 11.5 indicate that the pyridine N‐atom is more basic in the excited singlet state than in the ground state. The emission spectra are red‐shifted in protic solvents, in agreement with an intramolecular H‐bond between the ionized 3‐OH group and the nonionized 4‐COOH group.     

Single‐Electron Self‐Exchange between Cage Hydrocarbons and Their Radical Cations in the Gas Phase

We show that the radical cations of adamantane (C₁₀H₁₆^.+, 1 H^.+) and perdeuteroadamantane (C₁₀D₁₆^.+, 1 D^.+) are stable species in the gas phase. The radical cation of adamantylideneadamantane (C₂₀H₂₈^.+, 2 H^.+) is also stable (as in solution). By using the natural ¹³C abundances of the ions, we determine the rate constants for the reversible isergonic single‐electron transfer (SET) processes involving the dyads 1 H^.+/ 1 H, 1 D^.+/ 1 D and 2 H^.+/ 2 H. Rate constants for the reaction 1 H^.++ 1 D? 1 H+ 1 D^.+ are also determined and Marcus’ cross‐term equation is shown to hold in this case. The rate constants for the isergonic processes are extremely high, practically collision‐controlled. Ab initio computations of the electronic coupling (H_DA) and the reorganization energy (λ) allow rationalization of the mechanism of the process and give insights into the possible role of intermediate complexes in the reaction mechanism.     

CONFORMATIONAL AND ELECTRONIC INTERACTION STUDIES OF α-SUBSTITUTED CARBONYL COMPOUNDS. XV. α-(ARYLSULFINYL)-p-SUBSTITUTED ACETOPHENONES

Abstract

The v_CO IR analysis of α-(p-phenylsulfinyl)-p-substituted acetophenones X-φC(O)CH₂S(O)φ-Y 1–8, being X and Y = NO₂, H and OMe substituents, supported by ab initio calculations of the α-methylsulfinyl/acetophenone (model compound) along with the X-ray geometrical data for 1,7 and 8, indicates the existence of the cis ₂ and gauche rotamers for compounds 1-4 and 6. Compounds 5,7 and 8 present another less stable and more polar cis ₁ rotamer. The cis ₂ rotamer concentration for 4 (ca. 97% in CCl₄) is reduced to ca. 50% for 2,3,5-7 and to ca. 20% for 1 and 8. This behavior is discussed in terms of O^δ- _(CO—S^δ+ _(SO) charge transfer and Coulombic interactions, which stabilize the cis ₁ rotamer, and the π*_CO/δ_C-S, π_CO/n_s and π*_CO/δ_C-S orbital interactions, which stabilize the gauche rotamers. The progressive more negative carbonyl cis ₂ shifts (Δv_c), when X varies from NO₂ to H and to OMe for the same Y, along with the unexpected NAE values of the α-methylene carbon chemical shifts for compounds 1–8 give further support for the existence of a strong intramolecular complex betwen C=O and S=O dipoles which stabilizes the cis ₂ rotamer. The progressive more negative carbonyl gauche shifts (Δv_g), when X varies from NO₂ to H and to OMe for the same Y, is in line with the higher contibution of the interaction π_CO/δ*_C-S, which stabilizes the gauche rotamer of the title compounds.