ESR study on molecular motion of peroxy radicals of polytetrafluoroethylene

Temperature variations of the line shapes of e.s.r. spectra from the peroxy radicals of polytetrafluoroethylene ( ) were investigated in detail and the results were quantitatively analysed based on Kneubühl's theory on the line shape. It was found that there were two kinds of rapid molecular motions, of which the correlation times were about 10⁻⁹ s, for the peroxy radicals of ; one was the rotational motion related to the peroxy chain radical, the other was the three dimensional motion associated with the peroxy end radical. The activation energies of these molecular motions were estimated as 0·52 kcal/mol and 0·26 kcal/mol for the rotational motion and the three dimensional motion, respectively. Origins of such rapid motions were discussed in connection with the other molecular motions of polymers, which were found by other experimental methods.     

Conversion of alkyl radicals to allyl radicals in irradiated single crystal mats of polyethylene

The decay of alkyl radicals, the conversion of alkyl radicals to allyl radicals and the trapping of allyl radicals in irradiated single crystal mats of polyethylene have been studied by electron spin resonance (e.s.r.). It has been suggested that in the crystal core alkyl radicals react with trans-vinylene double bonds and are converted into trans-vinylene allyl radicals; at the crystal surface, alkyl radicals react with vinyl end groups and are converted into allyl radicals with vinyl end groups. The decay of radical pairs and the formation of trans-vinylene double bonds are discussed.     

酚酸结构对酚酸-g-聚甘露糖醛酸抗氧化性能的影响

以海藻酸钠水解产物聚甘露糖醛酸(PM)为原料,通过聚甘露糖醛酸-乙二胺(PM-EDA)中间体与酚酸接枝共聚,制备了8种PM的酚酸(PA)接枝共聚物酚酸-g-聚甘露糖醛酸(PA-g-PM),并探究了PA结构对8种PA-g-PM抗氧化活性的影响。在n_PM:n_EDA=1:1.5,PM与两种活化剂碳二亚胺(EDC)、N-羟基琥珀酰亚胺(NHS)的摩尔比1:2:1,活化0 h,pH 8.0条件下,反应24 h,获得最高取代度(17.27%)的PM-EDA。PM的PA-g-PM接枝率在4.171±0.16 ~ 8.880±0.32 mg GA/g之间。UV-vis、FT-IR、XRD表征证实酚酸已成功接枝到PM上获得PA-g-PM。相比PM,8种PA-g-PM的对DPPH的清除率和对铁的还原力均显著提升。PA-g-PM的抗氧化性能与其中的酚羟基个数呈正相关关系,对位酚羟基PA-g-PM的抗氧化性能优于邻位酚羟基PA-g-PM的抗氧化性能,PA-g-PM中的酚羟基被甲氧基取代其抗氧化性能减弱。以期本研究结果为海藻酸钠在食品、化妆品、医药等行业高值开发利用奠定理论基础。     

A study of the interaction of mechanically generated polypropylene radicals with phenolic antioxidant in the absence of oxygen using ESR spectroscopy

Polypropylene (PP) was mechanically degraded in the absence and in the presence of a phenolic antioxidant, 2,6-di-t-butyl-p-cresol. The interaction of macroradicals of PP with the antioxidant was studied by ESR spectroscopy in the temperature region between 77 and 303 K and at antioxidant concentrations of 0.1, 0.5, and 1.5 wt % in the absence of oxygen. In the absence of the antioxidant, the end macroradicals of PP are formed which decay with increase in temperature. In the presence of antioxidant both macroradicals of PP and phenoxy radicals are generated. The PP macroradicals are very stable up to the temperature close to T_g of the polymer. Beyond this temperature they decay via bimolecular mechanism—according to the second-order kinetics. The rate constants for PP macroradicals decay were determined, and the apparent activation energies for the regions of slow and fast decay were calculated.     

A study of the interaction of mechanically generated polypropylene radicals with phenolic antioxidant in the presence of oxygen by EPR spectroscopy

Isotactic polypropylene (iPP) was mechanically degraded in the absence and presence of a phenolic antioxidant at liquid nitrogen temperature in the presence of oxygen. The interaction of the primarily formed iPP macroradicals with oxygen and phenol was studied by EPR spectroscopy in the temperature region between 77 and 303 K at antioxidant concentrations of 0.1, 0.5, and 3.0 wt%. It was found that iPP macroradicals react at low temperature with oxygen, yielding peroxy radicals, and with antioxidant, with a simultaneous formation of phenoxy radicals. The development and decay of all kinds of radicals was studied. The rate constants for peroxy radical decay were determined and the apparent activation energies for the regions of slow and fast decay were calculated. © 1993 John Wiley & Sons, Inc.     

测氧法研究受阻酚抗氧剂的抗氧化活性及反应动力学

采用测氧法考察了4种市售受阻酚抗氧剂的抗氧化活性,同时对其清除ROO·反应进行了动力学分析。结果表明:4种受阻酚抗氧剂对ROO·均具有良好的清除作用,并且抗氧化活性随着酚羟基浓度增加而增大。在同等的酚羟基浓度下,抗氧剂的抑制速率常数kinh值从大到小的顺序为抗氧剂1098、抗氧剂BHT、抗氧剂1010、抗氧剂1076。抗氧剂的抗氧化活性与功能基团的个数和对位取代基的供电性密切相关,酚胺复合型抗氧剂体现出更高的抗氧化活性。     

E.s.r. studies of peroxy radicals in polyethylene: 2. Peroxy radicals in urea — polyethylene complexes

Temperature dependent e.s.r. spectra of peroxy radicals in urea—polyethylene complex materials (UPEC) were discussed. Peroxy radicals in UPEC were much more stable than in normal polyethylene. Change of anisotropic g-values of the radicals with temperature were investigated and it was found that the g₁-axis, which was assigned to be parallel to the chain axis, seemed to be almost unchanged throughout the temperature range in the present study, but the g₂- and g₃-axes changed drastically. Using these results, it was concluded that the main motion of the radical sites was rotation around the chain axis and this motion was found to be much faster than in normal polyethylene, which we have already studied and which we reported recently. This is a reflection of the properties of the materials studied, i.e. interaction between molecular chains in UPEC must be much weaker than in normal polyethylene because of the presence of the wall of urea molecules in the former.     

Reaction of α-tocopherol with alkyl and alkylperoxyl radicals of methyl linoleate

α-Tocopherol was reacted with alkyl and alkylperoxyl radicals at 37°C in bulk phase. The lipid-free radicals were generated by the reaction of methyl linoleate with the free radical initiator, 2,2′-azobis(2,4-dimethylvaleronitrile) (AMVN) under air-insufficient conditions. The products were isolated by high-performance liquid chromatography. Their structures were identified as 2-(α-tocopheroxy)-2,4-dimethylvaleronitrile (1), a mixture of methyl 9-(8a-peroxy-α-tocopherone)-10(E),12(Z)-octadecadienoate and methyl 13-(8a-peroxy-α-tocopherone)-9(Z),11(E)-octadecadienoate (2), methyl 9-(α-tocopheroxy)-10(E),12(Z)-octadecadienoate (3a), methyl 13-(α-tocopheroxy)-9(Z),11(E)-octadecadienoate (3b), α-tocopherol spirodiene dimer (4) and α-tocopherol trimer (5). When methyl linoleate containing α-tocopherol was oxidized with AMVN under airsufficient conditions, the main products were 8a-alkyl-peroxy-α-tocopherones (2). In addition to these compounds, 6-O-alkyl-α-tocopherols (1, 3a and 3b) were formed when the reaction was carried out under air-insufficient conditions. The results indicate that α-tocopherol can react with both alkyl and alkylperoxyl radicals during the autoxidation of polyunsaturated lipids.     

Ascorbate and phenolic antioxidant interactions in prevention of liposomal oxidation

Efficient prevention of membrane lipid peroxidation by vitamin E (α-tocopherol) may involve its regeneration by vitamin C (ascorbate). Conceivably, the efficacy of antioxidants designed as therapeutic agents could be enhanced if a similar regeneration were favorable; thus, a model membrane system was developed which allowed assessment of interaction of phenolic antioxidants with ascorbate and ascorbyl-6-palmitate. Ascorbate alone (50–200 μM) potentiated oxidation of soybean phosphatidylcholine liposomes by Fe²⁺/histidine-Fe³⁺, an effect which was temporally related to reduction of Fe³⁺ generated during oxidation. Addition of 200 μM ascorbate to α-tocopherol-containing liposomes (0.1 mol%) resulted in marked, synergistic protection. Accordingly, in the presence but not absence of ascorbate, α-tocopherol levels were maintained relatively constant during Fe²⁺/histidine-Fe³⁺ exposure. Probucol (4,4′-[(1-methylethylidine)bis(thio)]bis[2,6-bis(1,1-dimethylethyl)]phenol), and antioxidant which prevents oxidation of low density lipoproteins, and its analogues MDL 27,968 (4,4′-[(1-methylethylidene)bis(thio)]-bis[2,6-dimethyl]phenol) and MDL 28,881 (2,6-bis(1,1-dimethylethyl)-4-[(3,7,11-trimethyldodecyl)thio]phenol) prevented oxidation but exhibited no synergy with ascorbate. Ascorbyl-6-palmitate itself was an effective antioxidant but did not interact synergistically with any of the phenolic antioxidants. Differential scanning calorimetry revealed significant differences among the antioxidants in their effect on the liquid-crystalline phase transition of dipalmitoyl phosphatidylcholine (DPPC) liposomes. Both α-tocopherol and MDL 27,968 significantly reduced the phase transition temperature and the enthalpy of the transition. MDL 28,881 had no effect while probucol was intermediate. The potential for ascorbate or its analogues to interact with phenolic antioxidants to provide a more effective antioxidant system appears to be dictated by structural features and by the location of the antioxidants in the membrane.     

Free radicals trapped in polyethylene matrix: 1. Location of the alkyl radicals in irradiated polyethylene

Two types of alkyl radicals were found to be trapped in irradiated crystals grown from polyethylene solution. One of them corresponds to the broad sextet pattern of the e.s.r. spectrum and the other corresponds to the sharp sextet pattern. The free radicals attributed to the broad sextet began to disappear at a lower temperature than the temperature at which the free radicals attributed to the sharp sextet disappeared. When butadiene molecules were brought into contact with the specimen, the decay of the free radicals corresponding to the broad sextet was accelerated. When the specimen was subjected to fuming nitric acid treatment, no broad sextet was observed. The mat of the crystals, was aligned so that the c-axes of its crystallites were perpendicular to its surface. The broad sextet showed no anisotropy when the angle between the direction of applied magnetic field and that of the c-axis of the crystallite was varied. On the other hand, the sharp component of the spectrum showed apparent anisotropy. Consequently, it can be concluded that the broad component comes from the free radicals trapped in the lamellar surface and the sharp component is attributed to the free radicals trapped in the inner part of the crystallite. Hence, the locations of these two types of free radicals have been clarified with much more certainty than before.     

聚合型受阻酚抗氧剂的合成及应用

研究了以对甲酚为主要原料合成聚合型受阻酚抗氧剂的工艺。结果表明，树脂缩合反应条件是对甲酚与双环戊二烯为3：1～1．25，ZnCl2催化剂为对甲酚质量分数的2．0％，反应温度为75～80℃，双环戊二烯滴加时间为2h。烷基化反应温度为70～75℃，H2S04催化剂为缩合树脂质量分数的2．0％。制得的聚合型受阻酚抗氧剂产品对聚氨酯泡沫用聚醚2802具有较好的抗氧化性，起燃温度达224℃。     

Reactions of alkyl radicals with metal powders immersed in aqueous solutions

The mechanism of dehalogenation is investigated in reactions between alkyl radicals and metal powders immersed in aqueous solutionsOriginal Russian Text Copyright © 2005 by Fizika i Khimiya Stekla, Rusonik, Zidky, Cohen, Meyerstein.     

Total phenolic contents and antioxidant capacities of herbal and tea infusions

In order to supply new information on the antioxidant function of selected beverages for nutritionists and the general public, total phenolic contents of 51 kinds of herbal and tea infusions made in China were measured by the Folin-Ciocalteu method, and their antioxidant capacities were evaluated using ferric reducing antioxidant power (FRAP) and Trolox equivalent antioxidant capacity (TEAC) assays. A significant correlation between FRAP and TEAC values suggested that antioxidant components in these beverages were capable of reducing oxidants and scavenging free radicals. The high correlation between antioxidant capacities and total phenolic contents indicated that phenolic compounds could be one of the main components responsible for antioxidant activities of these beverages. Generally, these beverages had high antioxidant capacities and total phenolic contents, and could be important dietary sources of antioxidant phenolics for prevention of diseases caused by oxidative stress.     

An e.s.r. study of the motion of peroxy radicals in isotactic and atactic polypropylenes

E.s.r. spectra of peroxy radicals trapped in isotactic and atactic polypropylenes have been observed at various temperatures. The spectrum observed at 77 K was shown to be composed of one component by comparing it with that at 4 K. The spectra observed at higher temperatures comprised of two spectra arising from the rigid peroxy radicals and the mobile peroxy radicals. All of the observed spectra have been reconstructed by means of computer simulation and the changes in anisotropic g-values with temperature were estimated. The motion of the mobile fraction was shown to be rotation or rotatory vibration of the radicals around the chain axis both in the isotactic polypropylene and in the atactic polypropylene as well as in polyethylene and poly(tetrafluoroethylene) although the structures of the polymers are different, that is helical (polypropylene) or planar zigzag (polyethylene, poly(tetrafluoroethylene)).     

多乙烯多胺桥联受阻酚类抗氧剂的合成及其清除DPPH·性能

以二乙烯三胺和三乙烯四胺为桥联基,β-(3,5-二叔丁基-4-羟基苯基)丙酰氯为抗氧化功能基团,通过酰胺化缩合反应合成了两类具有不同对位桥联基团的受阻酚类抗氧剂。采用傅里叶红外光谱和核磁共振氢谱证实了合成的多乙烯多胺桥联受阻酚类抗氧剂的化学结构。DPPH法研究了多乙烯多胺桥联受阻酚类抗氧剂清除自由基的性能,并探索了酚羟基个数和对位桥联基结构对受阻酚类抗氧剂清除自由基性能的影响。结果表明,多乙烯多胺桥联受阻酚类抗氧剂具有良好的清除DPPH·能力,且随着抗氧剂分子中酚羟基个数的增加,清除DPPH·的活性增加,分子中含有4个酚羟基的三乙烯四胺受阻酚类抗氧剂的抗氧化效率（AE）达到2.65×10^-2 L/(mol·s)。对位桥联基结构对受阻酚类抗氧剂清除DPPH·能力有较大影响,季戊四醇为桥联基的受阻酚类抗氧剂1010清除DPPH·能力最强,其抗氧化效率（AE）为3.08×10^-2L/(mol·s);乙二胺为核的1.0代树枝状受阻酚类抗氧剂清除DPPH·能力最弱,其抗氧化效率（AE）为2.60×10^-2 L/(mol·s)。