阿魏酸修饰的血红蛋白自氧化的研究

为研究FA-Hb的自氧化,以阿魏酸酯(FA-NBA)与血红蛋白(Hb)为原料,制备了阿魏酸血红蛋白(FA-Hb)。通过紫外光谱扫描、血氧分析仪分析了修饰前后血红蛋白的特征吸收峰的变化和氧饱和曲线的差别;研究了有无叠氮钠、黄嘌呤-黄嘌呤氧化酶介导下,血红蛋白和阿魏酸修饰的血红蛋白的自氧化速率的改变。结果表明,阿魏酸修饰血红蛋白,保持了血红蛋白的功能结构,仍具备血红蛋白的载氧活性,有效降低了自氧化速率。     

氮氧自由基定点修饰牛血红蛋白的制备和抗自氧化研究

摘要:以4-（N-马来酰亚胺基）-2,2,6,6-四甲基哌啶-1-氮氧自由基( Mal-Tempol) 与牛血红蛋白（Hb）为原料,制备了氮氧自由基定点修饰在巯基上的血红蛋白( Mal-Tempol-Hb)。利用分光光度法测定了氮氧自由基的修饰度,通过紫外光谱研究了有无叠氮化钠（NaN3）介导下,Hb和Mal-Tempol-Hb中高铁血红蛋白(MetHb)含量随时间变化的过程。结果表明,无介导下,3h时Mal-Tempol-Hb中MetHb的摩尔百分含量由修饰前的44%下降为修饰后的28%;在NaN3介导下,3h时Mal-Tempol-Hb中MetHb的摩尔百分含量从修饰前的50%下降为修饰后的32%。氮氧自由基的修饰有效地降低了血红蛋白的自氧化速率。     

氮氧自由基定点修饰牛血红蛋白的制备和抗自氧化性能

以4-(N-马来酰亚胺基)-2,2,6,6-四甲基哌啶-1-氮氧自由基(Mal-Tempol)和牛血红蛋白(Hb)为原料,制备了氮氧自由基定点修饰在巯基上的血红蛋白(Mal-Tempol-Hb)。利用分光光度法测定了氮氧自由基的修饰度,通过紫外光谱考察了有无叠氮化钠(NaN_3)介导下,Hb和Mal-Tempol-Hb中高铁血红蛋白(Met Hb)含量随时间变化的过程。结果表明,无NaN_3介导下,180 min时,Mal-Tempol-Hb中Met Hb的摩尔分数由修饰前的44%下降为修饰后的28%;在NaN_3介导下,180 min时,Mal-Tempol-Hb中Met Hb的摩尔分数从修饰前的50%下降为修饰后的32%。氮氧自由基的修饰有效地降低了血红蛋白的自氧化速率。     

碳纳米管修饰电极对阿魏酸的电化学分析测试研究

研究了阿魏酸在碳纳米管修饰玻碳电极上的电化学行为,优化了测定参数,建立了一种测定阿魏酸的电化学分析测试方法。阿魏酸在碳纳米管修饰玻碳电极上于醋酸盐缓冲溶液中在-0.2~0.8 V处产生一对氧化还原峰,氧化峰电流与阿魏酸的浓度在1×10~(-5)~1×10~(-3)mol/L之间有良好的线性关系,线性回归方程为:Ip=8.7788+0.8561C,相关系数R为0.9995,检出限为1×0~(-6)mol/L,适用于中成药及中药材中阿魏酸含量的测定。     

利用表面改性制备磷酸锰锂/石墨烯锂离子电池复合材料

3-氨丙基三甲氧硅烷（APS）改性的磷酸锰锂纳米片与氧化石墨烯通过静电自组装,经喷雾干燥和高温煅烧,得到磷酸锰锂/石墨烯复合材料。APS修饰后的磷酸锰锂带正电荷,并可通过红外光谱中3-氨丙基和Si-O-C官能团的存在证明磷酸锰锂成功被APS修饰,使得其与带负电荷的氧化石墨烯自组装形成磷酸锰锂/石墨烯复合材料。测试结果表明约25 nm的磷酸锰锂纳米颗粒均匀负载在石墨烯表面,石墨烯片层充当导电网络,提高了材料的电子电导率和锂离子扩散速率,缓解了LiMnPO₄在充放电过程中的体积变化。电性能测试发现,该材料的首次放电比容量为142.2 mA·h·g^-1,50个循环后容量保持率达到90.5%,较未经APS修饰的磷酸锰锂/石墨烯材料有大幅提高。     

多因素影响下的煤低温氧化特性试验研究

为研究氧浓度、粒度和挥发分对采空区遗煤低温氧化过程的影响,利用油浴式程序升温试验装置设计了煤低温氧化试验,研究了不同影响因素条件下煤的耗氧速率和放热强度,验证了氧浓度、粒度和挥发分等对煤低温氧化特性的影响,通过对试验数据分析,得到了煤低温氧化特性受各因素影响的变化规律。试验结果表明:在一定范围内,氧浓度的增加会加快煤的耗氧速率,提高反应的放热强度,促进煤的氧化,但不会改变氧化反应的趋势;粒度较大的煤耗氧速率低,反应释放的热量小,氧化过程缓慢且强度较低;煤的挥发分降低后,耗氧速率和反应的放热强度也随之减小,其自燃临界温度将显著提高。     

干喷湿纺聚丙烯腈原丝的预氧化和碳化工艺

分析了预氧化时间、温度对预氧丝密度的影响,研究了预氧丝密度和牵伸率以及张力、碳化升温速率与碳纤维抗拉强度之间的关系。试验结果证明:延长预氧化时间和提高预氧化温度,预氧丝密度提高;当预氧丝密度为1.355 g/cm3时,得到的碳纤维的强度最高;当预氧化牵伸率为0.93%时,对应的碳纤维强度为4.84 GPa;在300℃/min低温碳化升温速率和1000℃/min高温碳化升温速率下,可以得到高性能碳纤维。     

天然橡胶抗热氧老化性能的快速评价

采用差示扫描量热法考察了天然橡胶硫化胶的抗热氧老化性能,得到氧化反应的表观活化能、反应速率常数（KT）和氧化诱导期（ti）,并与热空气老化箱试验结果进行了对比。结果表明,KT和ti能够表征天然橡胶硫化胶的抗热氧老化性能,所得结果与热空气老化箱试验结果一致。含苯胺类防老剂和对苯二胺类防老剂复配物的天然橡胶硫化胶的抗热氧老化性能较好。     

仲丁基苯液相氧化反应动力学

非催化条件下仲丁基苯（SBB）液相氧化制备过氧化氢仲丁基苯（SBBHP）是生产苯酚和甲乙酮的关键步骤。基于烃类链式自由基反应机理,分别建立了氧充足和限氧条件下SBB氧化动力学模型,模型包含了反应物SBB、主产物SBBHP、副产物苯乙酮（ACP）、2-苯基-2-丁醇（PBO）等。通过分别拟合不同条件下的实验数据（388~403 K）,得到了相应的基元反应速率常数和活化能。结果表明,由于空间位阻效应,主反应生成SBBHP的活化能大于异丙苯（IPB）生成过氧化氢异丙苯（CHP）的活化能。连续实验进一步验证了动力学模型的可靠性。相关研究结果可用于仲丁基苯液相氧化过程的设计和优化,并且基元反应相关结果有利于丰富对烷基芳烃氧化反应机理的认识。     

CuO修饰的赤泥载氧体废弃活性炭化学链燃烧

以拜耳法赤泥为基体,采用浸渍法制备了CuO修饰的赤泥载氧体（Cu0.5RM1、Cu1RM1）。利用SEM-EDSmapping、XRD对其进行物化表征,并在高温流化床反应器及热重分析仪中考察了赤泥载氧体的废弃活性炭化学链燃烧特性。结果表明,浸渍法可准确制备定量CuO修饰的赤泥载氧体;相比于纯赤泥载氧体,CuO修饰的赤泥载氧体具有化学链燃烧载氧体与化学链氧解耦燃烧载氧体的双重特性,能够加快碳转化速率,有效提高出口气体中CO₂浓度;Cu1RM1反应活性较高,875℃为其较优的反应温度,此时t₉₅为28min,出口气体中CO₂浓度为92.9%（体积分数）,燃烧效率达93.0%。10次循环实验表明Cu1RM1载氧体具有相对稳定的循环反应特性。     

On the kinetics of the autoxidation of fats. II. Monounsaturated substrates

The autoxidation of methyl oleate and oleic acid shows some differences as compared to the autoxidation of linoleate,e.g., the formation of water at an early stage. Linearization of experimental data on the autoxidation to high oxidation degrees of methyl oleate and other monounsaturated substrates shows that the rate equations previously derived for methyl linoleate in the range of 1–25% oxidation are valid, provided the correct expression for the remaining unreacted substrate is used. With monounsaturated substrates, part of the oxygen is consumed by a secondary oxidation reaction almost from the beginning, and only a certain constant fraction α of the total O₂ consumption is consumed in hydroperoxide formation. The fraction α is different for methyl oleate, oleyl alcohol, oleic acid andcis 9-octadecene, but the rate constant for the hydroperoxide formation is the same for all of them when experimental conditions are the same. The main difference between oleate and linoleate autoxidation is the much faster decomposition of the oleate hydroperoxides relative to their slow formation.     

The kinetics of the autoxidation of polyunsaturated fatty acids

The kinetics of the autoxidation of a series of polyunsaturated fatty acids (PUFA) with increasing degrees of unsaturation and the mono-, di-and triglycerides of linoleate have been studied in homogeneous chlorobenzene solution at 37 C under 760 torr of oxygen. The autoxidations were initiated by thermal decomposition of azo initiators and followed by measuring the rate of oxygen uptake. The rate of chain initiation was determined by the induction period method using α-tocopherol as the chainbreaking antioxidant. The measured oxidizabilities of the PUFA are linearly dependent on the number of doubly allylic positions present in the molecule. Thus, the oxidizability of linoleate is 2.03×10⁻² M^−1/2 sec^−1/2, and the value for docosahexaenoate is five times greater, 10.15×10⁻² M^−1/2 sec^−1/2. The rate of autoxidation for all PUFA studied and for the mono- and diglyceride is proportional to the substrate concentration and to the square root of the rate of chain initiation, implying that the autoxidation of these compounds follows the usual kinetic rate law. The autoxidation of the triglyceride is more complex and does not appear to follow the same rate law at all substrate concentrations. This deviation from the usual kinetic rate expression may be due to lipid aggregation at low concentrations of the triglyceride.     

Formation of peroxides in fatty esters. II. Methyl linoleate: application of the polarographic and direct oxygen methods

Summary This study of the prolonged autoxidation of methyllinoleate at 80°C. has included polarographic identification and determination of hydroperoxides, the direct determination of oxygen contents, and catalytic micro-hydrogenation for the determination of unsaturation. The polarographic method has further substantiated the observations of other workers that the principal peroxidic substance formed during the autoxidation of methyl linoleate at 80°C. is a hydroperoxide. The direct oxygen measurements have shown that most of the oxygen absorbed in the initial stages of autoxidation can be accounted for as hydroperoxide. During the latter stages there was a continuous increase of oxygen uptake, half of which can be accounted for as free acid and half as forms other than hydroperoxide, ester, or free acid. By means of the catalytic micro-hydrogenation method it has further been shown that as the autoxidation progresses there is a continuous decrease in unsaturation.     

Phenothiazine derivatives as new antioxidants for the autoxidation of methyl linoleate and their reaction mechanisms

The effect of new antioxidants, such as phenothiazine derivatives, on the autoxidation of methyl linoleate was evaluated by estimating the induction period using the weighing method. Peroxide values (iodometry and IR), refractive indices, mol wts, and UV and IR spectra were measured to investigate the extent of the autoxidation. The induction period evaluated from the weighing method gives almost the same value as that from the peroxide values. It was shown that some new phenothiazine derivatives are remarkably effective antioxidants, and, besides, the mechanism for the autoxidation of methyl linoleate containing phenothiazine derivatives as antioxidants is probably of the same type as that for the substrate alone. This study also investigated the reaction mechanism of phenothiazine derivative antioxidants by determining the electron spin resonance spectra for the antioxidants in the autoxidation of methyl linoleate. Then, the following mechanism was proposed. That is, within the induction period, these inhibitors hold stable nitroxide radicals (>NO*) in the reaction between the antioxidant amino radical (>N*), produced by the reaction of the antioxidant with ROO* or O₂, and the peroxy radical (ROO*). Besides, the more superior the phenothiazine derivative antioxidant, the more inactive the antioxidant makes oxygen and the peroxy radical for the methyl linoleate autoxidation and also for the antioxidant oxidation. Presented at the 12th World Congress of ISF, Milan, 1974.     

Kinetic model for autoxidation of β-carotene in organic solutions

Autoxidation of β-carotene was studied experimentally using n-decane as a solvent under various reaction conditions of temperature and dissolved oxygen concentration A novel kinetic model was proposed on the basis of an autocatalytic free-radical chain reaction mechanism. A secondary initiation reaction by decomposition of hydroperoxide and reactions concerned with a β-carotene-derived C-centered radical in propagation and termination processes were taken into consideration in the model. There were four unknown kinetic constants, and the constants were estimated by fitting the model with the experimental data. The fitted results are in good agreement with the experimental data in all stages of the kinetics of autoxidation and over a wide range of oxygen concentrations. The model described not only the appearance of the induction stage but also the effect of the oxygen concentration on the autoxidation rate. In addition, the model predicted the behavior of autoxidation in another solvent at low temperature that had been reported by other researchers.     

Autoxidation of fatty materials in emulsion. II. Factors affecting the histidine-catalyzed autoxidation of emulsified methyl linoleate

Several factors which affect autoxidation of methyl linoleate in emulsion have been examined. Data are presented which indicate: 1) In the presence of histidine, the ionic (anionic) emulsifiers examined promote autoxidation of emulsified methyl linoleate, but nonionic emulsifiers do not. 2) The concentration of an emulsifier affects the rate of oxygen absorption. 3) Inorganic salts (0.1 M or less) such as sodium chloride, sodium acetate and sodium sulfate affect oxygen absorption of emulsified methyl linoleate prepared with either ionic or nonionic emulsifiers. In histidine-catalyzed autoxidation there is a suppressing effect in the case of the ionic and a promotional effect in the case of the nonionic. In uncatalyzed autoxidation, these salts have a promotional effect in ionic emulsions and none in nonionic emulsions. 4) Sodium phosphate buffers completely suppress autoxidation due to histidine catalysis, but do not suppress the normal uncatalyzed autoxidation of emulsified methyl linoleate. 5) The pro-oxidative effects of histidine and histidine-metal ion complexes on emulsified unsaturated materials is not limited to polyolefins but also includes mono-olefinic compounds. Presented at the AOCS meeting in Toronto, October, 1962. E. Utiliz. Res. and Dev. Div., ARS, USDA.     

Effects of surface concentration,metals and acid synergists on autoxidation of linoleic acid monolayers on silica

To approximate in a model system the autoxidation of monomolecular layers of lipids on the cell surfaces of freeze-dried foods, the autoxidation of presumed monolayers of linoleic acid adsorbed from solution onto silica gel has been studied as a function of time and α-tocopherol and acid synergist content. The method of Honn, Bezman and Daubert was used, modified by the substitution of linoleic acid for soybean oil and the use of gas chromatography to follow oxygen disappearance at 80 C. It was found that adsorption of linoleic acid onto silica gel from petroleum ether solution conforms to a Langmuir isotherm, consistent with the formation of a monolayer. Confirming the finding of Honn et al. with soybean oil, it was found that the most rapid uptake of oxygen occurred at a linoleic acid-silica ratio close to that for the monolayer. Without included antioxidant, oxidation commences at a nearly linear rate without observable induction period. Time for consumption of one-half mole of oxygen per mole of linoleic acid is ca. 60 min on acid-washed silica. If very small amounts of α-tocopherol are included in the layer, virtually no oxygen uptake measurable in this system occurs during an induction period, the length of which is approximately proportional to tocopherol content. The inflection point at the commencement of rapid oxidation is very sharp; the ensuing oxidation rate approximates that of the unprotected acid. The induction period of linoleic acid with the same tocopherol content is as much as 100% longer when exposed in monolayer than in a bulk form. However the rate after commencement of rapid oxidation is 8–10 times greater in the monolayer. Acid washing of the silica reduced its iron content by 75%. Acid washing also reduced by 60% the rate of autoxidation without α-tocopherol and increased the length of the induction period four-fold when α-tocopherol was present. The effect of pretreatment of the silica by adsorption of the acid synergists, ascorbic, phosphoric, citric and ethylenediamine tetraacetic acid was qualitatively similar to the effect of acid washing. The synergists extended the induction period in increasing order as listed, EDTA producing a 100-fold extension. For ascorbic acid the rate reduction and increase of induction period were not found on unwashed silica and were dependent on the extent of washing. These findings are consistent with synergist sequestration of metals in a complex that is ineffective in new chain generation by perioxide decomposition.     

On the kinetics of the autoxidation of fats: influence of pro‐oxidants,antioxidants and synergists

The influence of minor amounts of pro‐ and anti‐oxidants on the kinetics of the autoxidation of fat has been evaluated. The reaction rates of oxygen with the substrates were found to follow the same basic equation, hitherto established for pure substrates. There is evidence that the surface of the reaction vessel also acts as a reaction catalyst and its effect is proportional to the area of glass in contact with lipids. Oxidation is enhanced by trace metal ions as well as by surface‐active compounds (e.g. hydroperoxides and sterols). Antioxidants such as α‐tocopherol and butylated hydroxyanisole inhibit the oxidation by delaying the start of oxygen consumption (the induction period) while retarders like amino acids only decrease the rate of oxidation. Thus pro‐ and anti‐ oxidants affect either the start or the rate of oxygen consumption. The empirical formula dx/dt = k [O₂] (1‐x/n) f′(t) was found applicable to the different stages of oxidation.     

On the Autoxidation of Vitamin D Preparations II: The Autoxidation of Ergocalciferol

Ergocalciferol was used as a model for the autoxidation studies of vitamins D. It was shown that ergocalciferol is sensitive to light, moisture and heat in the addition of oxygen. The autoxidation proceeds through isomerisation to carbonyl compound formation without the development of peroxidic groups.