Nanoporous structured submicrometer carbon fibers prepared via solution electrospinning of polymer blends

A facile means for obtaining submicrometer carbon fibers with a nanoporous structure is presented. A mixture of polyacrylonitrile (PAN) and a copolymer of acrylonitrile and methyl methacrylate (poly(AN-co-MMA)) in dimethylformamide was electrospun into submicrometer fibers with a microphase-separated structure. During the followed oxidation process, the copolymer domains were pyrolyzed, resulting in a nanoporous structure that was preserved after carbonization. The microphase-separated structure of the PAN/poly(AN-co-MMA) electrospun fibers, the morphology, and porous structure of both the oxidized and the carbonized fibers were observed with scanning electron microscopy and transmission electron microscopy. The carbon fibers have diameters ranging from several hundred nanometers to about 1 microm. The nanopores or nanoslits throughout the fiber surface and interior with diameters of several tens of nanometers are interconnected and oriented along the longitudinal axis of the fibers. This unique nanoporous morphology similar to the microphase-separated structure in the PAN/poly(AN-co-MMA) fibers is attributed to the rapid phase separation, solidification, as well as the stretching of the fibers during electrospinning. The pore volume and pore size distribution of the carbonized fibers were investigated by nitrogen adsorption and desorption.     

Organotin perfluorooctanesulfonates as air-stable Lewis acid catalysts: synthesis, characterization, and catalysis

The reactions of 1,3-dichloro-1,1,3,3-tetrabutyldistannoxane and dialkyltin dihalides with silver perfluorooctanesulfonate provided the corresponding sulfonates as hydrates. The number of water molecules (n) of hydration was dependent on the conditions. The distannoxane derivative was identified as n from 0.5 to 6, while in the hydrated mononuclear species and DMSO complexes n varied widely from 4 to 13. 119Sn NMR spectroscopy and conductivity measurements indicated the ionic dissociation of these compounds in solution. These compounds exhibited unusually high solubility in polar organic solvents. The ionic dissociation together with facile hydration probably causes the unusual solubility. The Lewis acidity of these compounds was found to be high among organotin derivatives on the basis of ESR spectra of superoxide/metal-ion complexes. In contrast to well-known organotin triflates, these compounds suffered no hydrolysis upon storage in open air. The high catalytic activity of the distannoxane 1 was exemplified for various carbon-carbon bond-forming reactions, such as Mukaiyama-aldol as well as -Michael reactions and allylation of aldehydes.     

An algorithm for computing solutions of variational problems with global convexity constraints

We present an algorithm to approximate the solutions to variational problems where set of admissible functions consists of convex functions. The main motivation behind the numerical method is to compute solutions to Adverse Selection problems within a Principal-Agent framework. Problems such as product lines design, optimal taxation, structured derivatives design, etc. can be studied through the scope of these models. We develop a method to estimate their optimal pricing schedules.     

Enantioselective benzylic hydroxylation of indan and tetralin with Pseudomonas monteilii TA-5

A set of 22 toluene- and ethylbenzene-degrading strains were screened for the enantioselective benzylic hydroxylation of indan and tetralin, and Pseudomonas monteilii TA-5 was discovered as an active and selective biocatalyst for such hydroxylations. Cells of P. monteilii TA-5 can be easily grown to a high density and demonstrated a specific hydroxylation activity of 24 U/g cdw (cell dry weight). Conditions for the hydroxylation of indan 1a and tetralin 1b with resting cells of this strain were optimized, to give the corresponding (R)-1-indanol 2a and (R)-1-tetralol 2b in 99% ee and 62–67% yields, respectively. No significant product inhibition was observed, and biohydroxylation with cell-free extracts suggested that the responsible hydroxylase is a soluble enzyme depending on either NADH or NADPH. Preparative biohydroxylation was demonstrated with resting cells as biocatalysts, affording (R)-2a in 99% ee and 65% yield, and (R)-2b in 99% ee and in 63% yield, respectively.     

Luminescent mesogen jacketed poly(1‐alkyne) bearing lateral terphenyl with hexyloxy tail

Mesogen jacketed liquid crystalline poly(1‐alkyne) and poly(1‐phenyl‐1‐alkyne) linked pendants of terphenyl mesogens with hexyloxy tails at the waist position (? {RC?C? [(CH₂)₃OOC‐terpheyl‐(OC₆H₁₃)₂]}_n? , where R?H, PHATP(OC6)2 ; R?C₆H₅, PPATP(OC6)2 ) were synthesized. The influences of structural variations on the thermal, mesomorphic, and luminescent properties were investigated. Polymerizations of all monomers are carried out by WCl₆‐Ph₄Sn catalysts successfully. The polymers are stable (T_d ≥ 340 °C) and soluble in common solvents. The monomers and polymers show enantiotropic SmA phases in the heating and cooling processes, and the lateral side chains of the mesogenic units are perpendicular to the main chain. The “jacket effect” of chromophoric terphenyl core “shell” around the main chain also contributes to polymers with high photoluminescence, and the pendant‐to‐backbone energy transfer path is involved in the luminescence process of this polymers. In comparison with monosubstituted polyacetylene PHATP(OC6)2 , the disubstituted polyacetylene PPATP(OC6)2 shows better photoluminescence in both THF solution and film, and exhibited about 40 nm red‐shifted than PHATP(OC6)2 , indicating that the “jacket effect” of terphenyl mesogens forces poly(1‐phenyl‐1‐alkyne) backbone to extend in a more planar conformation with a better conjugation. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

有机物添加剂对碱性锌电极的影响

通过腐蚀实验,测量了锌在碱性溶液中的腐蚀速度,比较了几种有机物添加剂的缓蚀效果 用恒电位极化的方法研究了锌的沉积电流随时间的变化企图用该方法考查一些有机物添加剂对二次碱性锌电极枝晶生长的抑制作用 测量了多孔锌电极在含有各种有机物添加剂的碱液中的阴,阳极极化曲线结果发现,季胺盐型有机表面活性剂 Ｃ Ｔ Ｍ Ｂ在碱性溶液中对锌具有一定的缓蚀作用还可以抑制二次锌电极上枝晶的生长 又不会严重影响锌电极的阳极放电行为为碱性电池中锌电极代汞缓蚀剂的研究提供了一种新的途径     

A Dimensional Splitting Method for Quasilinear Hyperbolic Equations with Variable Coefficients

A numerical method is presented for the variable coefficient, nonlinear hyperbolic equation u _t + _i=1 ^d V _i(x, t)f _i(u) _{x i} = 0 in arbitrary space dimension for bounded velocities that are Lipschitz continuous in the x variable. The method is based on dimensional splitting and uses a recent front tracking method to solve the resulting one-dimensional non-conservative equations. The method is unconditionally stable, and it produces a subsequence that converges to the entropy solution as the discretization of time and space tends to zero. Four numerical examples are presented; numerical error mechanisms are illustrated for two linear equations, the efficiency of the method compared with a high-resolution TVD method is discussed for a nonlinear problem, and finally, applications to reservoir simulation are presented.     

Elastic constants of layers in isotropic laminates

The individual laminae elastic constants in multilayer laminates composed of dissimilar isotropic layers were determined using ultrasonic-resonance spectroscopy and the linear theory of elasticity. Ultrasonic resonance allows one to measure the free-vibration response spectrum of a traction-free solid under periodic vibration. These frequencies depend on pointwise density, laminate dimensions, layer thickness, and layer elastic constants. Given a material with known mass but unknown constitution, this method allows one to extract the elastic constants and density of the constituent layers. This is accomplished by measuring the frequencies and then minimizing the differences between these and those calculated using the theory of elasticity for layered media to select the constants that best replicate the frequency-response spectrum. This approach is applied to a three-layer, unsymmetric laminate of WpCu, and very good agreement is found with the elastic constants of the two constituent materials.     

Enantioselective Michael addition to vinyl phosphonates via hydrogen bond-enhanced halogen bond catalysis

An asymmetric Michael addition of malononitrile to vinyl phosphonates was accomplished by hydrogen bond-enhanced bifunctional halogen bond (XB) catalysis. NMR titration experiments were used to demonstrate that halogen bonding, with the support of hydrogen-bonding, played a key role in the activation of the Michael acceptors through the phosphonate group. This is the first example of the use of XBs for the activation of organophosphorus compounds in synthesis. In addition, the iodo-perfluorophenyl group proved to be a better directing unit than different iodo- and nitro-substituted phenyl groups. The developed approach afforded products with up to excellent yields and diastereoselectivities and up to good enantioselectivities.

An asymmetric Michael addition of malononitrile to vinyl phosphonates was accomplished by hydrogen bond-enhanced bifunctional halogen bond (XB) catalysis.