Interpretation of the polyelectrolyte and antipolyelectrolyte effects of poly(N‐vinylimidazole‐co‐sodium styrenesulfonate) hydrogels

Hydrogels of N‐vinylimidazole (VI) and sodium styrenesulfonate (SSS) were synthesized in aqueous solution by radical crosslinking copolymerization with N,N′‐methylene‐bis(acrylamide) as crosslinker. Swelling in several saline solutions was measured for hydrogel samples synthesized with different comonomer concentrations (C_T = 10, 25, or 40%) and with SSS mole fractions covering a broad range (f_SSS = 0–0.7), while the crosslinker ratio was 2 wt % in all cases. The degree of swelling in aqueous solution with a specific ionic strength (μ), plotted versus the SSS composition of the feed, shows a minimum for any set of samples synthesized with a fixed C_T. The dependence of swelling on μ shows both polyelectrolyte (f_SSS beyond the minimum) and antipolyelectrolyte behaviors (in the low f_SSS limit). It was found that the nonGaussian factor of the crosslinking density and the polymer‐solvent interaction parameter increase with f_SSS for any C_T. Moreover, in the low f_SSS limit, the osmotic swelling pressure is governed not only by the ionic contribution, but also by the polymer‐solvent mixing and, the concentration of mobile counterions inside the gel is not proportional to the net fixed charge but to the addition of cationic and anionic side groups, what discards the formation of ionic pairs. The antipolyelectrolyte effect is interpreted as due to the increasing protonation of VI as μ goes up. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1683–1693, 2007     

An existence theorem for neutral variational problems of Bolza

This note proves an existence theorem for a generalized Bolza-type problem that has time delays in both the state and velocity variables. The assumptions are stated in terms of a modification of the classical Hamiltonian, and extend ideas of Rockafellar to the delay case.     

Reflection of light by a slab containing electrically small dielectric spheres

Theoriginal and theenhanced Maxwell-Garnett estimates for the permittivity of a particulate medium are applied to the reflection of light by a composite dielectric slab. The reflection coefficients for incident s and p polarizations are calculated and some curves are plotted and discussed.     

Production,purification, and characterization of a low-molecular-mass xylanase from Aspergillus sp. and its application in baking

An extracellular xylanase produced by a Mexican Aspergillus strain was purified and characterized. Aspergillus sp. FP-470 was able to grow and produce extracellular xylanases on birchwood xylan, oat spelt xylan, wheat straw, and corncob, with higher production observed on corncob. The strain also produced enzymes with cellulase, amylase, and pectinase activities on this substrate. A 22-kDa endoxylanase was purified 30-fold. Optimum temperature and pH were 60 degrees C and 5.5, respectively, and isoelectric point was 9.0. The enzyme has good stability from pH 5.0 to 10.0, retaining >80% of its original activity within this range. Half-lives of 150 min at 50 degrees C and 6.5 min at 60 degrees C were found. K(m) and activation energy values were 3.8 mg/mL and 26 kJ/mol, respectively, using birchwood xylan as substrate. The enzyme showed a higher affinity for 4-O-methyl-D-glucuronoxylan with a K(m) of 1.9 mg/mL. The enzyme displayed no activity toward other polysaccharides, including cellulose. Baking trials were conducted using the crude filtrate and purified enzyme. Addition of both preparations improved bread volume. However, addition of purified endoxylanase caused a 30% increase in volume over the crude extract.     

Determination of vanadium by solid-phase spectrophotometry after its preconcentration as an Eriochrome Cyanine R complex on a dextran-type exchanger

A method is described for the determination by solid phase spectrophotometry (SPS) of trace amounts of vanadium in natural water and crude petroleum samples. The procedure is based on fixation on a dextran-type anion exchanger of the complex V(IV)-Eriochrome Cyanine R. The absorbance of the gel, at 563 and 750 nm, packed in a 1 mm cell, is measured directly. Vanadium can be determined in the 0.6-25.0 mug l(-1) range with a relative standard deviation of 2.2%. The comparison of the SPS method and the gallic acid persulphate method shows that the linearity, analytical sensitivity and precision were better for the SPS method, and that the latter method has lower detection and quantification limits than the gallic acid persulphate method.     

Möbius aromaticity in [12]annulene: cis-trans isomerization via twist-coupled bond shifting

Density functional and coupled cluster calculations show that facile thermal configuration change in [12]annulene occurs via a twist-coupled bond-shifting mechanism. The transition state for this process is highly aromatic with M?bius topology. At the CCSD(T)/cc-pVDZ//BH&HLYP/6-311+G** level, the isomerization of tri-trans-[12]annulene 1a (CTCTCT) to its di-trans isomer 2 (CCCTCT) via such a mechanism has a barrier of 18.0 kcal/mol, in good agreement with earlier experiments. Two other aromatic M?bius bond-shifting transition states were located that result in configuration change for other [12]annulene conformers. This mechanism contrasts sharply with diradical configuration change for acyclic polyenes and with planar bond-shifting mechanisms generally assumed for annulenes. This constitutes evidence that neutral M?bius aromatic annulenes play a role in the dynamic processes of neutral [4n]annulenes.     

Water-soluble chiral monosulfonamide-cyclohexane-1,2-diamine-RhCp complex and its application in the asymmetric transfer hydrogenation (ATH) of ketones

Monosulfonamide ligands with heteroatom/heterocyclic systems were derived from trans-(1R,2R)-cyclohexane-1,2-diamine and complexed with [Ru(benzene)Cl₂]₂, [Cp^∗RhCl₂]₂ in situ and used in the ATH of aromatic ketones with aqueous sodium formate as the hydrogen source. The chiral secondary alcohols were obtained with >93% enantioselectivity and >89% yield. Reduction in water was faster than in isopropanol/KOH. Addition of surfactants showed little or no effects.     

Synthesis of heteroleptic bis(diimine)carbonylchlororuthenium(II) complexes from photodecarbonylated precursors

The reactions of bidentate diimine ligands (L2) with binuclear [Ru(L1)(CO)Cl2]2 complexes [L1 not equal to L2 = 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (4,4'-Me2bpy), 5,5'-dimethyl-2,2'-bipyridine (5,5'-Me2bpy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (4,7-Me2phen), 5,6-dimethyl-1,10-phenanthroline (5,6-Me2phen), di(2-pyridyl)ketone (dpk), di(2-pyridyl)amine (dpa)] result in cleavage of the dichloride bridge and the formation of cationic [Ru(L1)(L2)(CO)Cl]+ complexes. In addition to spectroscopic characterization, the structures of the [Ru(bpy)(phen)(CO)Cl]+, [Ru(4,4'-Me2bpy)(5,6-Me2phen)(CO)Cl]+ (as two polymorphs), [Ru(4,4'-Me2bpy)(4,7-Me2phen)(CO)Cl]+, [Ru(bpy)(dpa)(CO)Cl]+, [Ru(5,5'-Me2bpy)(dpa)(CO)Cl]+, [Ru(bpy)(dpk)(CO)Cl]+, and [Ru(4,4'-Me2bpy)(dpk)(CO)Cl]+ cations were confirmed by single crystal X-ray diffraction studies. In each case, the structurally characterized complex had the carbonyl ligand trans to a nitrogen from the incoming diimine ligand, these complexes corresponding to the main isomers isolated from the reaction mixtures. The synthesis of [Ru(4,4'-Me2bpy)(5,6-Me2bpy)(CO)(NO3)]+ from [Ru(4,4'-Me2bpy)(5,6-Me2bpy)(CO)Cl]+ and AgNO3 demonstrates that exchange of the chloro ligand can be achieved.