Analysis of chemical calorific effect during reactive extrusion processes for free radical polymerization

In the reactive extrusion process for polymerization, the chemical calorific effect has a great influence on the temperature. In order to quantitatively analyze the polymerization trend and optimize the processing conditions, the phenomena of the chemical calorific effect during reactive extrusion processes for free radical polymerization were analyzed. Numerical computation expressions of the heat of chemical reaction and the reactive calorific intensity were deduced, and then a numerical simulation of the reactive extrusion process for the polymerization of n-butyl methacrylate was carried out. The evolutions of the heat of chemical reaction and the reactive calorific intensity along the! axial direction of the extruder are presented, on the basis of which reactive processing conditions can be optimized.

Investigation of the gel effect in reactive extrusion processes for free radical polymerization

The gel effect in the reactive extrusion process for free radical polymerization in a closely intermeshing co-rotating twin screw extruder was investigated. First the reaction kinetic model was constructed mainly on the basis of entanglement theory. Next, numerical calculation expressions for the initiator and monomer concentrations, monomer conversion, average molecular weight and apparent viscosity were deduced. Finally, the evolution of the above variables were shown and discussed for the example of butyl methacrylate. The simulated results of the monomer conversion are in good agreement with experimental results.

The antioxidative effect of icariin in human erythrocytes against free-radical-induced haemolysis

Icariin (2-(4'-methoxyl phenyl)-3-rhamnosido-5-hydroxyl-7-glucosido-8-(3'-methyl-2-butyleny"chromanone) is the major component in Herba Epimedii used in traditional Chinese medicine for the treatment of atherosclerosis. This work focuses on the antioxidative effect of icariin on freeradical-induced haemolysis of human erythrocytes, in which the initial free radical derives from the decomposition of 2,2'-azobis(2-amidinopropane hydrochloride) (AAPH) at physiological temperature. To reveal the structure-activity relationship of icariin, the antioxidant effects of two structural analogues of icariin, acacetin (2-(4'-methoxylphenyl)-5,7-dihydroxylchromone) and norwogonin (2-phenyl-5,7,8-trihydroxylchromone), on the same experimental system were examined as well. It was found that all these chromone derivatives (Chm-OHs) dose-dependently protected human erythrocytes against free-radical-induced haemolysis. The order of antioxidative activity was nonvogoni-n > acacetin > icariin by the analysis of the relationship between the concentration of Chm-OHs and the prolongation percentage of the lag time of haemolysis (PP%). It was also proved that the phenyl hydroxyl group attached to the chromone ring at 7-position cannot trap the free radical- On the contrary, phenyl hydroxyl groups at the 5- and 8-position in nonvogonin made it a significant antioxidant in AAPH-induced haemolysis.

Protective effect of nickel chloride on superoxide damage: enhancement of CuZn superoxide dismutase affinity to the oxygen free radical.

The effect of nickel from soluble NiCl2 on Cu-Zn superoxide dismutase (SOD) activity, as well as on rate of nitro blue tetrazolium reduction, was studied in vitro since lipid peroxidation has been implicated in cell damage by nickel insoluble compounds, whose toxicity and carcinogenicity are well established. The physical and chemical nature of nickel compounds is one of the key determinations of its toxicity. Soluble nickel freely enter cells, but is just as readily excreted reducing the opportunity for production of lipid damage. Nickel from NiCl2 strongly activated SOD activity. In vitro addition of nickel chloride to a crude lung preparation altered the KM for SOD without changing the Vmax. Nickel chloride produced increased enzyme affinity to the substrate, because decreased (O2-) concentration that yields half-maximal velocity. The combination of nickel and SOD may contribute to stabilization of the particular conformation of SOD responsible for maximal catalytically activity.

The effect of polymerization mode on monomer conversion, free radical entrapment, and interaction with hydroxyapatite of commercial self-adhesive cements

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of ambient levels of ozone on photosynthetic components and radical scavenging system in leaves of African cowpea varieties

Tropospheric ozone (O3), a main component of photochemical oxidants, adversely affects not only human health but also vegetation. To clarify the long-term effects of ambient levels of tropospheric ozone (O3) on photosynthetic components and radical scavenging system in the leaves of cowpea ( Vigna unguiculata L.), two African varieties, Blackeye and Asontem, were grown in open-top chambers and exposed to filtered air (FA), non-filtered air (NF) or non-filtered air with additional O3 of approximately 50 nl l-1. Ambient levels of O3 significantly reduced chlorophyll concentration, quantum yield and activity of ribulose 1,5-bisphosphate carboxylase/oxygenase (Rubisco), thus contributing to the reduction in net photosynthetic rate at the reproductive growth stage of both varieties; with no significant variety difference in the sensitivity to O3. The O3-induced significant reduction in catalase activity was observed in Blackeye at vegetative and reproductive growth stages; and in Asontem at reproductive growth stage. On the other hand, exposure to O3 significantly increased ascorbate peroxidase activity in Blackeye at reproductive stage and did not significantly affect that in Blackeye at vegetative growth stage and that in Asontem at both growth stages. At reproductive growth stage, activities of monodehydroascorbate reductase and glutathione reductase were significantly increased by the exposure to O3 in both varieties. The results obtained in this study suggest that, although ascorbate peroxidase, monodehydroascorbate reductase and glutathione reductase played important roles in scavenging O3-induced reactive oxygen species in the leaves, radical scavenging ability of these enzymes is not sufficient to avoid detrimental effects of ambient levels of O3 on photosynthesis in both African cowpea varieties.

Frog skins keep redox homeostasis by antioxidant peptides with rapid radical scavenging ability

The question of how amphibians can protect themselves from reactive oxygen species when exposed to the sun in an oxygen-rich atmosphere is important and interesting, not only from an evolutionary viewpoint, but also as a primer for researchers interested in mammalian skin biology, in which such peptide systems for antioxidant defense are not well studied. The identification of an antioxidant peptide named antioxidin-RL from frog (Odorrana livida) skin in this report supports the idea that a peptide antioxidant system may be a widespread antioxidant strategy among amphibian skins. Its ability to eliminate most of the 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) radical tested within 2 s, which is much faster than the commercial antioxidant factor butylated hydroxytoluene, suggests that it has a potentially large impact on redox homeostasis in amphibian skins. Cys10 is proven to be responsible for its rapid radical scavenging function and tyrosines take part in the binding of antioxidin-RL to radicals according to our nuclear magnetic resonance assay. (C) 2010 Elsevier Inc. All rights reserved.

Neodymium oxide co-catalyzed melt free radical grafting of maleic anhydride onto co-polypropylene by reactive extrusion

Rare earth oxide, neodymium oxide (Nd2O3), CO-catalyzed melt grafting of maleic anhydride (MAH) onto co-polypropylene (co-PP) in the presence of dicumyl peroxide (DCP) was carried out by reactive extrusion. The experimental results reveal that the addition of Nd2O3 as a coagent leads to an enhancement in both MFR and the grafting degree of MAH, along with a simultaneous decrease in the gel content. When the Nd2O3 concentration is 6.0 mmol%, the increment of the grafting degree of MAH maximally is up to about 20% compared with the related system without adding Nd2O3, and the gel content decreases simultaneously to a very low level of about 3%. Attenuated total reflection FTIR (ATR-FTIR) indicates that the gel in the graft copolymers mainly arise from the cross-linking reaction between ethylene units of co-PP. A reasonable reaction mechanism has been put forward on the basis of our experimental results and other mechanisms reported in the literature. We also tentatively explain above results by means of synergistic effect between DCP and Nd2O3, which causes a higher concentration of the macroradical, in particular the tertiary macroradical.

Neodymium oxide-assisted melt free-radical grafting of maleic anhydride on isotactic-polypropylene by reactive extrusion

Rare earth oxide, neodymium oxide (Nd2O3), -assisted melt free-radical grafting of maleic anhydride (MAH) on isotactic-polypropylene (i-PP) was carried out by reactive extrusion. The experimental results reveal that the addition of Nd2O3 into reactive system leads to an enhancement of the grafting degree of MAH, along with an elevated degradation of i-PP matrix. When Nd2O3 content is 4.5 mmol %, the increment of the grafting degree of MAH (maximally) is up to about 30% compared with that of the related system without adding Nd2O3, while the severest degradation of i-PP matrix simultaneously occurs. On the basis of the reaction mechanism of PP-g-MAH proposed before, the sequence of beta-scission and grafting reaction is discussed in detail. It is found that, for the reactive system studied, most tertiary macroradicals first undergo beta-scission, and then, grafting reaction with MAH takes place at the new radical chain ends. The imported Nd2O3 has no effect on the aforementioned reaction mechanism, whereas it enhances the initiating efficiency of the initiator, dicumyl peroxide (DCP).

An ESR study on (OH)-O-center dot-radical scavenging activity of water-soluble fullerenols

Water-soluble polyhydroxylated fullerene derivatives (fullerenol) were synthesized, and their scavenging ability for (OH)-O-.-radical was studied by the combination of ESR spectroscopy and spin-trapping technique with phenyl-t-butyl-nitrone. It was found that fullerenols showed an excellent efficiency in eliminating (OH)-O-. free radicals generated by UV photolysis of H2O2. At an applied fullerenol concentration of 0, 3 mg/mL in the final solution, a radical scavenging efficiency of approximate 95% was achieved, revealing the potential use of these compounds as novel potent free radical scavengers in biological systems.

Radical scavenging activity of protein from tentacles of jellyfish Rhopilema esculentum

In this study, radical scavenging activity of protein from tentacles of jellyfish Rhopilema esculentum (R. esculentum) was assayed including superoxide anion radical and hydroxyl radical scavenging. The protein samples showed strong scavenging activity on superoxide anion radical and values EC50 of full protein (FP), first fraction (IFF), second fraction (SF), and 30% (NH4)(2)SO4 precipitate (Fr-1) were 2.65, 7.28, 1.10, and 22.51 mu g/mL, respectively, while values EC50 of BHA, BHT, and alpha-tocopherol were 31, 6 1, and 88 pg/mL, respectively. Also, the protein samples had strong scavenging effect on hydroxyl radical and the values EC50 of FP, FF, SF, Fr-1, and Fr-2 were 48.91, 27.72, 1.82, 16.36, and 160.93 mu g/mL, but values EC50 of Vc and mannitol were 1907 and 4536 mu g/mL, respectively. Of the five protein samples, SF had the strongest radical scavenging activity and may have a use as a possible supplement in the food and pharmaceutical industries. The radical scavenging activity was stable at high temperature so that R. esculentum may be used as a kind of natural functional food. (c) 2005 Elsevier Ltd. All rights reserved.

Sulfation of genistein alters its antioxidant properties and its effect on platelet aggregation and monocyte and endothelial function

Soy isoflavones have been extensively studied because of their possible benefits to human health. Genistein, the major isoflavone aglycone, has received most attention; however, it undergoes extensive metabolism (e.g. conjugation with sulfuric acid) in the gut and liver, which may affect its biological proper-ties. This study investigated the antioxidant activity and free radical-scavenging properties of genistein, genistein-4'-sulfate and genistein-4'-7-disulfate as well as their effect on platelet aggregation and monocyte and endothelial function. Electron spin resonance spectroscopy (ESR) and spin trapping data and other standard antioxidant assays indicated that genistein is a relatively weak antioxidant compared to quercetin and that its sulfated metabolites are even less effective. Furthermore, genistein-4'-sulfate was less potent than genistem, and genistein-4'-7-disulfate even less potent, at inhibiting collagen-induced platelet aggregation, nitric oxide (NO) production by macrophages, and secretion by primary human endothelial cells of monocyte chemoattractant protein 1 (MCP-1), intercellular adhesion molecule 1 (ICAM-1) and vascular cell adhesion molecule 1 (VCAM-1). The current data suggest that sulfation of genistein, with the associated loss of hydroxyl groups, decreases its antioxidant activity and its effect on platelet aggregation, inflammation, cell adhesion and chemotaxis. (C) 2004 Elsevier B.V All rights reserved.

Sulfation of genistein alters its antioxidant properties and its effect on platelet aggregation and monocyte and endothelial function

Soy isoflavones have been extensively studied because of their possible benefits to human health. Genistein, the major isoflavone aglycone, has received most attention; however, it undergoes extensive metabolism (e.g. conjugation with sulfuric acid) in the gut and liver, which may affect its biological proper-ties. This study investigated the antioxidant activity and free radical-scavenging properties of genistein, genistein-4'-sulfate and genistein-4'-7-disulfate as well as their effect on platelet aggregation and monocyte and endothelial function. Electron spin resonance spectroscopy (ESR) and spin trapping data and other standard antioxidant assays indicated that genistein is a relatively weak antioxidant compared to quercetin and that its sulfated metabolites are even less effective. Furthermore, genistein-4'-sulfate was less potent than genistem, and genistein-4'-7-disulfate even less potent, at inhibiting collagen-induced platelet aggregation, nitric oxide (NO) production by macrophages, and secretion by primary human endothelial cells of monocyte chemoattractant protein 1 (MCP-1), intercellular adhesion molecule 1 (ICAM-1) and vascular cell adhesion molecule 1 (VCAM-1). The current data suggest that sulfation of genistein, with the associated loss of hydroxyl groups, decreases its antioxidant activity and its effect on platelet aggregation, inflammation, cell adhesion and chemotaxis. (C) 2004 Elsevier B.V All rights reserved.

Myeloperoxidase inhibitory and radical scavenging activities of flavones from Pterogyne nitens

Two new flavone glucosides, nitensosides A and B (1, 2), together with four known compounds, sorbifolin (3), sorbifolin 6-O-β-glucopyranoside (4), pedalitin (5), and pedalitin 6-O-β-glucopyranoside (6) were isolated from Pterogyne nitens. Their structures were elucidated from 1D and 2D NMR analysis, as well as by high resolution mass spectrometry. All the isolated flavones were evaluated for their myeloperoxidase (MPO) inhibitory activity. The most active compound, pedalitin, exhibited IC 50 value of 3.75 nM on MPO. Additionally, the radical-scavenging capacity of flavones 1-6 was evaluated towards ABTS and DPPH radicals and compared to standard compounds quercetin and Trolox®. © 2008 Pharmaceutical Society of Japan.