Radical scavenging activity of canola hull phenolics

Possible use of canola hulls as a source of natural anti-oxidants was explored. Cyclone canola hulls were extracted with methanol (30 to 80%, vol/vol) and acetone (30 to 80%, vol/vol). The free radical-scavenging activity of phenolic extracts so prepared was evaluated using the 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulfonate) (ABTS) radical ion (ABTS^o−), 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical, and chemiluminescence assays. The total content of phenolics in prepared extracts from canola hulls ranged from 15 to 136 mg sinapic acid equivalents per gram of extract. Higher levels of condensed tannins were detected in the acetone extracts than in the corresponding methanolic counterparts. Seventy and 80% (vol/vol) acetone extracts displayed markedly stronger antioxidant activity than any of the other extracts investigated. Statistically significant linear correlations were found between TEAC (Trolox equivalent antioxidant capacity) values (expressed in mM of Trolox equivalents per gram of extract) and total pehnolics, TEAC and total condensed tannins (i.e., determined using the modified vanillin and pronthocyanidin assays), as well as TEAC and protein precipitation activity of phenolic extracts (i.e., measured using the dye-labeled assay). The antioxidant activities of extracts as determined by the ABTS^o− radical ion assay correlated highly with those of the chemiluminescence and DPPH radical assays.     

Studies on polyacrylates containing pendant ligand with carbonyl and hydroxyl functions and their divalent metal complexes

A series of monomers were prepared by reacting (meth)acryloyl chloride with 2,4‐dihydroxybenzophenone, 2,4‐dihydroxybenzaldehyde, and 2,4‐dihydroxyacetophenone, respectively. The monomers were polymerized in dimethylformamide (DMF) at 70°C using benzoyl peroxide as an initiator. Polymer–metal complexes were obtained from DMF solutions of polymers with an aqueous solution of metal ions. The polymers and polymer–metal complexes were characterized by elemental analysis and spectral studies. The IR spectra of these complexes suggest that the metals are coordinated through the oxygen of the carbonyl group and the oxygen of the phenolic–OH group. The electronic spectra, electron paramagnetic resonance (EPR) spectra, and magnetic moments of polychelates showed an octahedral and square planar structure for Ni(II) and Cu(II) complexes, respectively. X‐ray diffraction studies revealed that polychelates are highly crystalline. The thermal and electrical properties, catalytic activity, and structure–property relationships are discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2083–2090, 2003     

Controlled radical polymerization of p-(iodomethyl)styrene—a route to branched and star-like structures

p-(Iodomethyl)styrene was polymerized under the action of a radical initiator (AIBN). The polymerization proceeds with degenerative chain transfer and leads to well defined branched polymers with functional primary and secondary iodomethyl groups as revealed by NMR studies. The obtained polymer can be further used as macroinitiator for radical polymerization of styrene. This polymerization proceeds in controlled way to polystyrene star polymers with reactive groups at the end of their arms. The characterization of branched and star structures was performed by NMR and GPC with absolute molar mass detection (MALLS).     

超声、臭氧、光催化及其组合工艺处理苯酚废水

研究了在一定条件下,超声、臭氧、光催化等高级氧化技术的不同组合方法对苯酚的降解效果。结果表明,对于质量浓度为100 mg/L的苯酚溶液,反应时间为1 h时,超声、臭氧氧化、光催化三者单独降解率分别为8%、36%、35%。紫外光光催化分别与超声波或臭氧组合对苯酚降解有一定的协同作用,降解率分别为50%、78%;而声光催化技术与臭氧三者组合降解苯酚的效果尤佳,降解率达到85%。这归功于超声波的机械作用对臭氧扩散引起的积极作用以及声光催化协同产生的H2O2,从而生成的羟基自由基。     

角蛋白基药物载体的发展及应用探讨

从毛发中提取角蛋白，开发具有独特功能的角蛋白基药物载体材料，提高药物的活性和生物利用率，既能够增加毛发的利用价值，又能够实现节能减排，符合可持续发展战略要求。对毛发中提取角蛋白进行二硫键重建、自由基聚合、多糖改性和烷基化等改性处理，赋予角蛋白基药物载体优异地功能特性，进一步拓宽其作为角蛋白基药物载体的应用范围。角蛋白基药物载体可被加工成纳米粒子、纤维支架、水凝胶等各种形式用于药物的递送。作为一种高硫含量且具有良好细胞相容性的结构蛋白，角蛋白基药物载体在组织工程、再生医学等领域扮演着重要的角色。     

The beneficial effect of small amount of water in the ambient temperature atom transfer radical homo and block co-polymerization of methacrylates

ATRP of several methacrylates viz. methyl methacrylate (MMA), ethyl methacrylate (EMA), n-butyl methacrylate (nBMA), t-butyl methacrylate (tBMA), benzyl methacrylate (BzMA) and (N,N-dimethylamino)ethyl methacrylate (DMAEMA) has been studied in neat as well as aqueous (up to 12 vol% water) acetone at 35 °C using CuCl/bipyridine (bpy) catalyst and ethyl 2-bromoisobutyrate as the initiator. Addition of water significantly enhances the rate of polymerization without losing control. Unlike CuCl/bpy the CuBr/bpy catalyst gives poor control which is attributed to the lower solubility and consequent heterogeneity in the latter case. Of the other ligands used with the CuCl catalyst viz. o-phenanthroline (o-phen), 1,1,4,7,7-pentamethyldiethylenetriamine (PMDETA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA), Me₆TREN only o-phen offers reasonably good control. The CuCl/bpy catalyst system has been used also in preparing some di- and tri-block copolymers with reasonably low polydispersity index (PDI) at ambient temperature (35 °C) using aqueous acetone as the solvent. The following block copolymers have been prepared PMMA-tBMA, PMMA-b-tBMA-b-MMA, PMMA-DMAEMA, by this method.     

Effects of ion group content and polyol molecular weight on physical properties of HTPB‐based waterborne poly(urethane‐urea)s

A series of waterborne poly(urethane‐urea)s, WPUUs, based on using nonpolar hydroxyl‐terminated polybutadiene (HTPB) as the soft segment, were successfully synthesized in this article. The effects of the COOH group content and soft‐segment molecular weight (Mn_s) on the dispersion, morphology, and physical properties were investigated. Variations of the particle size, viscosity, and zeta potential were first governed by the hydrophilicity of the polymer chain, and then by the swelling derived from water. Fourier transfer infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) indicated that the degree of phase separation decreased as the COOH group content increased or as Mn_s decreased. However, the hydrogen bonding between the soft and hard segments and the two‐phase mixing could not occur in this nonpolar HTPB‐based WPUU system, indicating that the hard segments tended to form smaller domains and to pack more loosely. It was attributed to the fact that the presence of bulky ionic salt groups destroyed the ordered arrangement of the hard segments. In this case, the increases of the interface area between the soft and hard phases resulted in that the present behaviors were similar to the phase mixing. In tensile properties, HTPB‐based WPUUs exhibited higher tensile stress, elongation at break, and modulus as the COOH group content decreased or as Mn_s decreased. In thermal degradation, the introduction of HTPB polyol improved the thermal stability of WPUU. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and characterization of poly(vinyl chloride‐co‐vinyl acetate)‐graft‐poly[(meth)acrylates] by atom transfer radical polymerization

The graft polymerization of methyl methacrylate and butyl acrylate onto poly(vinyl chloride‐co‐vinyl acetate) with atom transfer radical polymerization (ATRP) was successfully carried out with copper(I) thiocyanate/N,N,N′,N′,N″‐pentamethyldiethylenetriamine and copper(I) chloride/2,2′‐bipyridine as catalysts in the solvent N,N‐dimethylformamide. For methyl methacrylate, a kinetic plot of ln([M]₀/[M]) (where [M]₀ is the initial monomer concentration and [M] is the monomer concentration) versus time for the graft polymerization was almost linear, and the molecular weight of the graft copolymer increased with increasing conversion, this being typical for ATRP. The formation of the graft polymer was confirmed with gel permeation chromatography, ¹H‐NMR, and Fourier transform infrared spectroscopy. The glass‐transition temperature of the copolymer increased with the concentration of methyl methacrylate. The graft copolymer was hydrolyzed, and its swelling capacity was measured. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 183–189, 2005     

Synthesis of well-defined poly(styrene)-b-poly(p-tert-butoxystyrene) multiblock copolymer from poly(alkoxyamine) macroinitiator

The stepwise insertion reaction of styrene (St) and p-tert-butoxystyrene (BOSt) into poly(alkoxyamine) macroinitiator was carried out to provide well-defined poly(St)-b-poly(BOSt) multiblock copolymers. Structural confirmation of the multiblock copolymers was accomplished by NMR and IR measurements. The model reaction also supported that the monomer insertion into the macroinitiator proceeded in accordance with a living fashion.     

Interaction of methane with surfaces of silica,aluminas and HZSM-5 zeolite. A comparative FT-IR study

Infrared investigations on the interaction of methane with silica, aluminas (, and ) and HZSM-5 zeolite have been carried out. At low temperature (173 K), methane adsorption was observed over these oxides and HZSM-5 zeolite. Our findings featured that the infrared inactive ₁ band (2917 cm^–1) of a gaseous methane molecule became active and shifted to lower frequencies (2900 and 2890 cm^–1) when it adsorbed on the surfaces of these adsorbents. Our results also demonstrate that hydroxyl groups played a very important role in methane adsorption over the acidic oxides and the HZSM-5 zeolite. When interaction between the hydroxyl groups and methane took place, the band shift of the hydroxyl groups varied with different oxides. The strength of the interaction decreased according to the following sequence, Si-OH-Al>Al-OH>Si-OH, which is in accordance with the order of their acidities. At higher temperatures, methane interacted quite differently with various oxides and HZSM-5 zeolite. It has been observed that the hydroxyl groups of silica, -alumina and HZSM-5 zeolite could exchange with CD₄ at temperatures higher than 773K, while those on -alumina could exchange at a temperature as low as 573 K. Another interesting observation was the formation of formate species over Al₂O₃ (both and ) at temperatures higher than 473 K. The formate species would decompose to CO₂, or produce carbonate at much higher temperatures. Formation of formate species was not observed over silica and HZSM-5 under similar conditions, -Al₂O₃ did not adsorb or react with methane in any case.