A Nonaqueous Redox-Matched Flow Battery with Charge Storage in Insoluble Polymer Beads**

We describe the nonaqueous redox-matched flow battery (RMFB), where charge is stored on redox-active moieties covalently tethered to non-circulating, insoluble polymer beads and charge is transferred between the electrodes and the beads via soluble mediators with redox potentials matched to the active moieties on the beads. The RMFB reported herein uses ferrocene and viologen derivatives bound to crosslinked polystyrene beads. Charge storage in the beads leads to a high (approximately 1.0–1.7 M) effective concentration of active material in the reservoirs while preventing crossover of that material. The relatively low concentration of soluble mediators (15 mM) eliminates the need for high-solubility molecules to create high energy density batteries. Nernstian redox exchange between the beads and redox-matched mediators was fast relative to the cycle time of the RMFB. This approach is generalizable to many different redox-active moieties via attachment to the versatile Merrifield resin.     

Titanosilicate beads with hierarchical porosity: synthesis and application as epoxidation catalysts

Porous titanosilicate beads with a diameter of 0.5-1.5 mm (TiSil-HPB-60) were synthesized from a preformed titanosilicate solution with a porous anion-exchange resin as template. The bead format of this material enables its straightforward separation from the reaction mixture in its application as a liquid-phase heterogeneous catalyst. The material displays hierarchical porosity (micro/mesopores) and incipient TS-1 structure building units. The titanium species are predominantly located in tetrahedral framework positions. TiSil-HPB-60 is a highly active catalyst for the epoxidation of cyclohexene with t-butyl hydroperoxide (TBHP) and aqueous H(2)O(2). With both oxidants, TiSil-HPB-60 gave higher epoxide yields than Ti-MCM-41 and TS-1. The improved catalytic performance of TiSil-HPB-60 is mainly ascribed to the large mesopores favoring the diffusion of reagents and products to and from the titanium active sites. The epoxide yield and selectivity could be further improved by silylation of the titanosilicate beads. Importantly, TiSil-HPB-60 is a stable catalyst immune to titanium leaching, and can be easily recovered and reused in successive catalytic cycles without significant loss of activity. Moreover, TiSil-HPB-60 is active and selective in the epoxidation of a wide range of bulky alkenes.     

Improved peak capacity for CE separations of enzyme inhibitors with activity‐based detection using magnetic bead microreactors

A technique for separating and detecting enzyme inhibitors was developed using CE with an enzyme microreactor. The on‐column enzyme microreactor was constructed using NdFeB magnet(s) to immobilize alkaline phosphatase‐coated superparamagnetic beads (2.8 μm diameter) inside a capillary before the detection window. Enzyme inhibition assays were performed by injecting a plug of inhibitor into a capillary filled with the substrate, AttoPhos. Product generated in the enzyme microreactor was detected by LIF. Inhibitor zones electrophoresed through the capillary, passed through the enzyme microreactor, and were observed as negative peaks due to decreased product formation. The goal of this study was to improve peak capacities for inhibitor separations relative to previous studies, which combined continuous engagement electrophoretically mediated microanalysis and transient engagement electrophoretically mediated microanalysis to study enzyme inhibition. The effects of electric field strength, bead injection time and inhibitor concentrations on peak capacity and peak width were investigated. Peak capacities were increased to ≥20 under optimal conditions of electric field strength and bead injection time for inhibition assays with arsenate and theophylline. Five reversible inhibitors of alkaline phosphatase (theophylline, vanadate, arsenate, L ‐tryptophan and tungstate) were separated and detected to demonstrate the ability of this technique to analyze complex inhibitor mixtures.     

Ethylene (Co)Polymerization with Metallocene Catalysts Encapsulated in Gel‐Type Poly(styrene‐co‐divinylbenzene) Beads

Gel‐type poly(styrene‐co‐divinylbenzene) beads (PS bead) were used as a carrier to encapsulate metallocene catalysts through a simple swelling‐shrinking procedure. The catalytic species were homogeneously distributed in the PS bead particle. The catalyst exhibited high and stable ethylene polymerization and ethylene/1‐hexene copolymerization activity affording uniform spherical polymer particles (1 mm). Polymerization rate profiles exhibited slow initiation and stable increase in polymerization activity with time.     

Green synthesis and enhanced photocatalytic activity of Ce-doped TiO2 nanoparticles supported on porous glass

A facile and green method to prepare Ce-doped TiO₂ nanoparticles supported on porous glass beads is reported. An ion exchange process and subsequent calcination yielded Ce-doped TiO₂ nanoparticles with a mean size of 4.8 ± 0.3 nm. The nanoparticles were dispersed on the surface of porous glass beads. The addition of Ce enhanced the visible light absorption of the TiO₂ nanoparticles in the 400–500 nm spectral window. The band gap of the as-prepared catalyst was 2.80 eV. The Ce-doped TiO₂ nanoparticles immobilized on porous glass beads exhibited excellent photocatalytic activity for the visible-light-degradation of methyl orange (MO) and rhodamine B (RhB); with rate constants of 0.095 and 0.230 min⁻¹; respectively. The effects of Ce dosage; reaction duration; and initial solution pH on the conversion of MO and RhB dyes were investigated. The green synthesis and favorable photocatalytic activity makes the Ce-doped TiO₂ nanoparticles immobilized on porous glass an attractive alternative for the efficient degradation of organic pollutants.     

A comparison of impedance models for the inverse estimation of the non-acoustical parameters of granular absorbers

An impedance model relates acoustic properties of porous materials with non-acoustical parameters. Although such parameters can be measured, specific equipment is required for each of them, so that numerical methods have been proposed for estimating their value from a more manageable measurement of the normal incidence absorption coefficient in an impedance tube. This inverse procedure requires both an impedance model and an inversion technique. This paper compares four impedance models, Miki, Hamet–Berengier, Johnson–Allard–Champoux and Champoux–Stinson, when Simulated Annealing is used for the inverse estimation of the non-acoustical parameters of three granular materials, consisting of packings of small spherical glass beads of different diameters. Some of these parameters have also been measured, so that they can be compared with these estimated by the proposed inverse method.     

二次彩虹法测量高折射率玻璃微珠折射率研究

基于米氏散射理论解释了激光照明下玻璃微珠的二次彩虹精细结构的成因,发现折射率的差异将直接影响二次彩虹精细结构的位置.对于实验中玻璃微珠半径变化引起二次彩虹精细结构间距变化的现象亦用米氏散射理论进行了模拟分析和实验研究.利用米氏散射的近似理论——艾里理论对玻璃微珠的折射率进行了测量.在对玻璃微珠二次彩虹精细结构所计算得到的折射率的统计分析基础上,通过校正测量误差后得到了玻璃微珠折射率的准确数据.     

Fine control of the porous structure and chromatographic properties of monodisperse macroporous poly(styrene-co-divinylbenzene) beads prepared using polymer porogens

The porous structure of monodisperse macroporous beads can be controlled by using soluble polymers with well-defined structural characteristics as part of the porogenic mixture. In general, the use of linear polystyrene as a porogen in the preparation of poly (styrene-co-divinylbenzene) beads shifts the pore size distribution towards larger pores. While a direct correlation between pore size and molecular weight of the porogen has been established, the chemical composition of the polymer porogen has no effect on the porous and chromatographic properties of the beads. These findings suggest that the average molar volume of the porogenic system is important while the miscibility of the polymer porogen with the crosslinked polymer that is formed is of little relevance. © 1994 John Wiley & Sons, Inc.     

Immobilization of penicillin acylase in porous beads of polyacrylamide gel

A procedure is described for the immobilization of benzylpenicillin acylase from Escherichia coli within uniformly spherical, porous polyacrylamide gel beads. Aqueous solutions of the enzyme and sodium alginate and of acrylamide monomer, N,N'-methylene-bis-acrylamide, N,N,N,N'-tetramethylethylenediamine (TEMED) and sodium alginate are cooled separately, mixed, and dropped immediately into ice-cold, buffered calcium formate solution, pH 8.5, to give calcium alginate-coated beads. The beads are left for 30-60 min in the cold calcium formate solution for polyacrylamide gel formation. The beads are then treated with a solution of glutaraldehyde and the calcium alginate subsequently leached out with a solution of potassium phosphate. Modification of the native enzyme with glutaraldehyde results in a slight enhancement in the rate of hydrolysis of benzylpenicillin at pH 7.8 and 0.05M substrate concentration. The enzyme entrapped in porous polyacrylamide gel beads shows no measurable diffusional limitation in stirred reactors, catalyzing the hydrolysis of the substrate at a rate comparable to that of the glutaraldehyde-modified native enzyme. The immobilized enzyme preparation has been used in batch mode over 90 cycles without any apparent loss in hydrolytic activity.     

Chromatography of functional polymers: A new approach to the characterization of reactive polymers obtained by chemical modification

High-performance liquid chromatography (HPLC) has been used to complement size-exclusion (gel permeation) chromatography (SEC) for the characterization of functional polymers. Whereas SEC is unable to detect compositional changes, HPLC in an appropriate interacting medium can provide detailed information on compositional changes occurring during chemical modification of a polymer. The method has been demonstrated using a normal-phase column consisting of porous monodisperse 10 μm poly(2,3-dihydroxypropyl methacrylate-co-ethylene dimethacrylate) beads that have a homogeneous coverage of aliphatic hydroxyl groups for the analysis of brominated poly(isobutylene-co-4-methylstyrene). Differences of well below 1 mol % of bromomethylstyrene units are easily detected and quantified. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1173–1180, 1997