Preparation and characterization of N‐methyl‐substituted polyurethane

We prepared N‐methyl‐substituted polyurethanes with different substitution degrees from sodium hydride, methyl p‐toluene sulfonate, and polyether–polyurethane containing poly(oxytetramethylene) glycol, 4,4′‐diphenylmethane diisocyanate, and 1,4‐butanediol. The chemical structures were characterized with Fourier transform infrared and ¹H NMR. To investigate the effects of the N‐substitution degree on the morphology, thermal stability, and mechanical properties, we used differential scanning calorimetry, thermogravimetric analysis, and a universal testing machine. As the substitution degree increased, the new free (1708 cm^?1) and bonded (1650 cm^?1) carbonyl peaks increased. There was no bonded carbonyl peak in fully substituted polyurethane because the urethane groups had no hydrogen. At a small substitution degree, we observed a slight increase in the glass‐transition temperature and decrease in the endotherms of soft‐segment and hard‐segment domains due to the decrease in the hard‐segment domain and the increase in the urethane groups in the soft‐segment domain. The hard‐segment domain decreased and then disappeared as the N‐methyl substitution degree increased. These changes in the morphology resulted (1) in decreased modulus and tensile strength for the films because of the decrease in physical crosslinking points and (2) improved thermal stability as the substitution degree increased. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4077–4083, 2002     

Electrochemical characterization of poly(vinyl alcohol)/formyl methyl pyridinium (PVA-FP) anion-exchange membranes

To explore electrodialysis for purification of negatively charged large organic molecules (e.g., amino acids and medicine), water-swollen formyl methyl pyridinium-immobilized polyvinyl alcohol (PVA-FP) anion-exchange membranes were prepared and characterized in terms of their electrochemical properties. The PVA-FP membranes exhibited low electrical resistance (1.0–3.0 Ω cm²), high swelling properties (water content ratio, 0.62–0.73), and reasonable transport number ( for Cl⁻). For glutamic acid solutions, the electrical resistance of the PVA-FP membrane was low (1.0–3.0 Ω cm²) in a wide pH range, with no membrane fouling. Since the resonance effect of quaternary aromatic ammonium contributed to the structural stability of the PVA-FP membrane, the water-splitting with the PVA-FP membrane was approximately one order of magnitude lower than that with a commercial ion-exchange membrane at a same current density.     

Photodissociation of singly protonated peptides at 193 nm investigated with tandem time-of-flight mass spectrometry

Photodissociation at 193 nm of some singly protonated peptides generated by matrix-assisted laser desorption/ionization was investigated using tandem time-of-flight mass spectrometry. For peptides with arginine at the C-terminus, x, upsilon, and w fragment ions were generated preferentially while a and d fragment ions dominated for peptides with arginine at the N-terminus. These are the same characteristics as photodissociation at 157 nm reported previously. Overall, the photodissociation spectra obtained at 157 and 193 nm were strikingly similar.     

Enzymatic production of xylooligosaccharides from corn stover and corn cobs treated with aqueous ammonia

A novel method of producing food-grade xylooligosaccharides from corn stover and corn cobs was investigated. The process starts with pretreatment of feedstock in aqueous ammonia, which results delignified and xylan-rich substrate. The pretreated substrates are subjected to enzymatic hydrolysis of xylan using endoxylanase for production of xylooligosaccharides. The conventional enzyme-based method involves extraction of xylan with a strong alkaline solution to form a liquid intermediate containing soluble xylan. This intermediate is heavily contaminated with various extraneous components. A costly purification step is therefore required before enzymatic hydrolysis. In the present method, xylan is obtained in solid form after pretreatment. Water-washing is all that is required for enzymatic hydrolysis of this material. The complex step of purifying soluble xylan from contaminant is essentially eliminated. Refining of xylooligosaccharides to food-grade is accomplished by charcoal adsorption followed by ethanol elution. Xylanlytic hydrolysis of the pretreated corn stover yielded glucan-rich residue that is easily digestible by cellulase enzyme. The digestibility of the residue reached 86% with enzyme loading of 10 filter paper units/g-glucan. As a feedstock for xylooligosaccharides production, corn cobs are superior to corn stover because of high xylan content and high packing density. The high packing density of corn cobs reduces water input and eventually raises the product concentration.     

Preorganized ligand arrays based on spirotetrahydrofuranyl motifs. Synthesis of the stereoisomeric 1,8,14-trioxatrispiro[4.1.4.1.4. 1]octadecanes and the contrasting conformational features and ionic binding capacities of these belted ionophores

The cis,trans trispiro ether 4 is accessible from several synthetic directions as a consequence of a crossover in reaction selectivity when proceeding from nucleophilic attack on the cis dispiro ketone to oxygenation of the alpha,beta-unsaturated ester 17. Its cis,cis isomer 3 was obtained in 17 steps and 14.6% overall yield from 3, 5-dimethoxybenzoic acid by making use of the alicyclic side chain in N as a "conformational lock". Although 4 shows no measurable tendency to complex with alkali metal ions, 3 binds strongly to Li(+) and Na(+) ions, as well as to CH(3)NH(3)(+). Whereas the 3eq conformation is populated in the solid state and in solution, complex formation occurs readily. (13)C NMR studies have defined slow exchange limits as the 2:1 sandwich complex with lithium ion is initially formed and transformed progressively into a 1:1 species upon the addition of more LiClO(4). Only the 2:1 complex with sodium ion is formed during comparable titration with NaClO(4). Association constants, molecular mechanics calculations, and X-ray crystallographic studies provide insight into the binding capacity of this belted tridentate ionophore.     

A bimodal particle dynamics model considering coagulation, coalescence and surface growth, and its application to the growth of titania aggregates

A simple bimodal particle dynamics model was proposed to describe a particle system undergoing simultaneous particle formation, coagulation, coalescence, and surface growth. We extended our previous bimodal model, which used two discrete modes, to account for the surface growth of nonspherical particles. Surface reaction from TiCl4 was considered and its effects on the formation and growth of TiO2 particles were investigated. Simulation results of the present bimodal model considering surface growth showed very good agreement with those of the moving sectional model for the growth of spherical TiO2 in the literature. Surface growth of TiO2 aggregates was also simulated by using this bimodal model and a new design diagram indicating the significance of surface reaction of TiCl4 was proposed.     

Interplay between cubic and hexagonal phases in block copolymer solutions

The phase behavior of a symmetric styrene-isoprene (SI) diblock copolymer in a styrene-selective solvent, diethylphthalate, was investigated by in situ small-angle X-ray scattering on isotropic and shear-oriented solutions and by rheology and birefringence. A remarkable new feature in this phase diagram is the coexistence of both body-centered cubic (bcc) and hexagonally close-packed (hcp) sphere phases, in a region between close-packed spheres (cps) and hexagonally packed cylinders (hex) over the concentration range phi approximately 0.33-0.45. By focusing on the transitions among these various ordered phases during heating and cooling cycles, we observed a strong hysteresis: supercooled cylinders persisted upon cooling. The stability of these supercooled cylinders is quite dependent on concentration, and for phi > or = 0.40, the supercooled cylinders do not revert to spheres even after quiescent annealing for 1 month. The spontaneous formation of spheres due to the dissociation of cylinders is kinetically hindered in this case, and the system is apparently not amenable to any pretransitional fluctuations of cylinders prior to the cylinder-to-sphere transition. This contrasts with the case of cylinders transforming to spheres upon heating in the melt. The application of large amplitude shear to the supercooled cylinders is effective in restoring the equilibrium sphere phases.     

Prostaglandin E2 stimulates angiogenesis by activating the nitric oxide/cGMP pathway in human umbilical vein endothelial cells

Prostaglandin E2 (PGE2), a major product of cyclooxygenase, has been implicated in modulating angiogenesis, vascular function, and inflammatory processes, but the underlying mechanism is not clearly elucidated. We here investigated the molecular mechanism by which PGE2 regulates angiogenesis. Treatment of human umbilical vein endothelial cells (HUVEC) with PGE2 increased angiogenesis. PGE2 increased phosphorylation of Akt and endothelial nitric oxide synthase (eNOS), eNOS activity, and nitric oxide (NO) production by the activation of cAMP-dependent protein kinase (PKA) and phosphatidylinositol 3-kinase (PI3K). Dibutyryl cAMP (DB-cAMP) mimicked the role of PGE2 in angiogenesis and the signaling pathway, suggesting that cAMP is a down-stream mediator of PGE2. Furthermore, PGE2 increased endothelial cell sprouting from normal murine aortic segments, but not from eNOS-deficient ones, on Matrigel. The angiogenic effects of PGE2 were inhibited by the inhibitors of PKA, PI3K, eNOS, and soluble guanylate cyclase, but not by phospholipase C inhibitor. These results clearly show that PGE2 increased angiogenesis by activating the NO/cGMP signaling pathway through PKA/PI3K/Akt-dependent increase in eNOS activity.     

Asymmetric synthesis of α,β-epoxysulfones via phase-transfer catalytic Darzens reaction

Described is the asymmetric synthesis of α,β-epoxysulfones by the catalytic phase-transfer Darzens reaction of chloromethyl phenyl sulfone with various aromatic aldehydes in the presence of the cinchona alkaloid-derived chiral phase-transfer catalysts bearing N-2,3,4-trifluorobenzyl moiety. The trans-(αR,βR)-epoxysulfones were obtained in good chemical yields (81-95%) with high enantioselectivities (up to 97% ee) in the presence of N-(2,3,4-trifluorobenzyl)quinidinium bromide.     

Adsorption of organic matter at mineral/water interfaces: 5. Effects of adsorbed natural organic matter analogues on mineral dissolution

The effects of the adsorption of pyromellitate, an analogue for natural organic matter, on the dissolution behavior of corundum (alpha-Al2O3) have been examined over a wide range of pyromellitate concentrations (0-2.5 mM) and pH conditions (2-10). The adsorption modes of pyromellitate on corundum have first been examined using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and are shown to be dominated by a fully deprotonated, outer-sphere pyromellitate species ([triple bond]AlOH2+. . .Pyr4-) at pH >/= 5.0. At lower pH conditions, however, an additional protonated outer-sphere species ([triple bond]AlOH2+. . .H2Pyr2-) and an inner-sphere species are also evident. In accordance with the ATR-FTIR findings, modeling of macroscopic pyromellitate adsorption data using an extended constant capacitance treatment was possible using two outer-sphere ([triple bond]AlOH2+. . .Pyr4- and [triple bond]AlOH2+. . .H2Pyr2-) and one inner-sphere ([triple bond]AlPyr3-) adsorbed pyromellitate species. The presence of adsorbed pyromellitate strongly inhibited the dissolution of corundum under acidic (pH < 5) conditions, consistent with a mechanism previously proposed by Johnson et al. whereby outer-spherically adsorbed Pyr4- species sterically protect dissolution-active surface sites from attack by dissolution-promoting species such as protons. A reduction in the protolytic dissolution rate of corundum results. A reference Suwannee River fulvic acid, which also adsorbs to aluminum (oxyhydr)oxide surfaces in a predominantly outer-sphere manner, was similarly shown to strongly inhibit the dissolution of corundum at pH = 3.