EPR Technology Spectroscopic Investigation of Generation of Reactive Oxygen Species Free Radicals in Laccase-Activated Jute Fiber

Lignins in jute fibers can be activated by laccase to generate reactive oxygen species (ROS) free radicals for subsequent use in radical graft polymerization. The effect of incubation conditions on the generation of ROS free radicals when jute powders were incubated with laccase was investigated through spin-trapping technique to detect the spin adduct of N-tert-butyl-α-phenylnitrone and ROS free radical using electron paramagnetic resonance spectroscopy. Results revealed that the highest concentrations of ROS free radicals were generated when jute was incubated with laccase (0.54 U/mL) and copper ions (10 mM) in solution at pH 3.5 and a temperature of 60 °C for 1 h.     

小鼠甲醇氧化应激的电子顺磁共振的研究

建立了小鼠甲醇中毒的氧化应激模型,研究了甲醇诱导小鼠产生氧化应激状态,探讨了大黄中草药和维生素C对小鼠甲醇氧化应激的保护作用. 模型小鼠共分为5个组：空白组、对照组、甲醇应激组、大黄组、维生素C（Vc）组. 利用电子自旋捕捉技术研究了小鼠甲醇氧化应激不同模型组小鼠体内的肝、肾、脾、心、肺和脑中产生的自由基强度的变化. 结果表明： 甲醇诱发了小鼠体内自由基的产生,甲醇组和生理盐水组相比,自由基的强度明显增强（显著性差异统计指标P<0.01);而大黄和Vc对小鼠甲醇氧化应激有保护作用,大黄组、Vc 组和甲醇组相比自由基的强度则明显降低（P<0.01).     

辐射引发和热引发聚丙烯腈纤维的自由基研究

利用电子自旋共振波谱(ESR)研究了聚丙烯腈(PAN)纤维在真空以及空气气氛下经γ射线辐射引发和热引发产生的自由基. 结果显示,室温下辐射诱导产生的自由基为烷基自由基和聚亚胺自由基,辐射产生的自由基随温度升高而衰减,150 ℃时完全消失. 热引发的自由基则依赖于温度和氧气, 当PAN纤维在空气中加热至190 ℃时,开始产生多烯自由基,而且自由基浓度随温度升高而迅速增加;在真空条件下,PAN纤维经加热只产生极少量自由基. 据此推断,热引发自由基是通过热氧化反应产生的,这类自由基位于共轭结构上,其共轭长度也随温度的升高而增加.     

Generation of reactive oxygen species and oxidative stress in <Emphasis Type="Italic">Escherichia coli</Emphasis> and <Emphasis Type="Italic">Staphylococcus aureus</Emphasis> by a novel semiconductor catalyst

The objective of this study was to investigate antimicrobial mechanisms of a new catalytic material (charge transfer auto oxidation–reduction type catalyst, CT catalyst) that may have great potential for application in water/wastewater treatment. Generation of reactive oxygen species (ROS) in bacteria-free solution, induction of ROS and oxidative damage in bacteria (including E. coli and S. aureus) were examined for the CT catalyst. The results showed that significantly higher (p < 0.05, via t-test) amount of hydroxyl radicals was generated by the CT catalyst compared with the control, particularly after 6 h of contact time that more than twice of the amount of the control was produced. The generation of ROS in the bacteria was greater under higher pH and temperature levels, which closely related with the oxidative damage in cells. The results indicated that CT catalyst induced oxidative damage in the bacteria might serve as an important mechanism interpreting the anti-microbial function of the CT catalyst.     

Pd(Ⅱ)与漆树漆酶相互作用的研究

以 5 ,6 二溴 2 ,3 二氰基氢醌 (DDBQH2 )为底物 ,在pH 4 5和 30± 0 1℃条件下 ,用分光光度法考察了Pd(Ⅱ )与漆酶的结合时间对漆树漆酶催化活性的影响。结果表明 ,随着Pd(Ⅱ )与漆酶结合时间的延长 ,Pd(Ⅱ )对漆酶催化氧化反应的活化程度逐渐减弱 ,最终转变为抑制直至钝化作用 ,且这种转变的速度随Pd(Ⅱ )浓度的增大而加快。与Pd(Ⅱ )混合后的漆酶的吸收光谱表明 ,Pd(Ⅱ )可能是通过取代漆酶Ⅰ型位中的Cu(Ⅱ )而使漆酶的催化活性逐渐降低直至丧失的。     

卷烟烟气中活性自由基的自旋捕获ESR研究

卷烟烟气中的瞬态自由基对人体健康是相当有害的，而检测活性自由基最常用的方法是自旋捕获方法. 本研究中使用高效新型捕捉剂DEPMPO能够直接在水相中捕捉到烷基自由基与羟基自由基，并未发现烷氧自由基加合物. 考虑到DEPMPO对活性自由基的捕捉能力和加合物ESR谱图解析特征性都优于PBN与DMPO，且在有机溶剂中溶解较多的氧分子. 因此认为以往文献中所捕获的烷氧自由基来源于烷基自由基氧化后的次级自由基产物.     

Antioxidant Activities of Some New Chromonyl-2,4-Thiazolidinediones and Chromonyl-2,4-Imidazolidinediones Having Chromone Cores

The antioxidant properties of 11 new synthesized chromonyl-2,4-thiazolidinediones and chromonyl-2,4-imidazolidinediones (CBs) were investigated. The antioxidant activities and mechanisms of the CBs interaction with reactive oxygen species (ROS) were clarified using various in vitro antioxidant assay methods including superoxide anion radical ( $ \mathrm{O}\overline{{}_2^{\bullet }} $ ), hydroxyl radical (HO^?), 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH^?) scavenging activity and the iron (II)-ferrozine complex formation. The potassium superoxide/18-crown-6 ether dissolved in dimethylsulfoxide (DMSO) was applied as a source of superoxide anion radical. Hydroxyl radicals were produced in the Fenton-like reaction Fe(II)+H₂O₂. Chemiluminescence, spectrophotometry, and electron paramagnetic resonance (EPR) spectroscopy using 5,5-dimethyl-1-pyrroline-1-oxide (DMPO) as spin trap were applied as the measurement techniques. The CBs examined that exhibited good free radical scavenging activity also showed strong total antioxidant power capacity. Possible mechanisms of antioxidation are proposed to explain the differences in the experimental results between the chromone derivatives with imidazolidine-2,4-dione ring and those with thiazolidine-2,4-dione ring. In conclusion, some of the new CBs are promising to be applied as inhibitors of free radicals.     

Detection of free radicals produced by a pulsed electrohydraulic discharge using electron spin resonance

The detection of free radicals such as hydroxyl radical and hydrogen radical for plasma in solution induced by a pulsed electrohydraulic discharge are successfully performed using electron spin resonance measurement. The plasma reactor is a barrier-type and consists of a stainless needle high-voltage (+35 to 65 kV) electrode partially immersed in the solution and a Pyrex glass solution container around which an aluminum film grounded electrode is wrapped. Streamers are induced in the solution. After adding iron (II) sulfate or radical trapping agent before the plasma application, the spectrum for radicals is clearly detected. A reactive dye solution is dramatically decolorized.     

Spin concentration in a possible ESR dosimeter: An electron spin echo study on X-irradiated ammonium tartrate

Several single crystals and powder samples of ammonium tartrate, recently proposed as a possible ESR dosimeter, have been X-irradiated with different doses. The total radical concentration has been determined by quantitative cw ESR, by comparison with a standard. The samples have been studied by electron spin echo spectroscopy. The two-pulse echo decay has been obtained and simulated by a single exponential function for different values of the microwave power of the pulses and for different pulse lengths. The dependence of the phase memory time TM on the microwave power has been exploited to get information on the contribution of the instantaneous diffusion to spin dephasing. At room temperature in the range of radical concentrations of 10(18)-10(19) spins/cm3 the instantaneous diffusion is the dominant spin dephasing mechanism. The linear dependence of the instantaneous diffusion on the total concentration of the radicals is in agreement with the theory. From the latter result we conclude that the average radical-radical distance corresponds to a random distribution of the radicals in the matrix. A simple method of measuring the radical concentration by the ESE decays in powder samples of irradiated ammonium tartrate is described.     

EPR study of the toxicological effects of gas-phase cigarette smoke and the protective effects of grape seed extract on the mitochondrial membrane

Electron paramagnetic resonance spin trapping and spin labeling techniques were used to study the effects of grape seed extract on the biophysical propertiers of the mitochondrial membrane exposed to gas-phase cigarette smoke. The spin trapping results indicated that grape seed extract can effectively scavenge free radicals in cigarette smoke and the lipid free radicals generated from the lipid peroxidation of mitochondrial membrane caused by gas-phase cigarette smoke. The spin labeling results showed that grape seed extract can protect the mitochondrial membrane from the toxicological damage caused by gas-phase cigarette smoke.     

Spectroscopic investigation on the sonodynamic activity of Safranine T to bovine serum albumin damage

In this paper, the Safranine T (ST) was used as sonosensitive compound to study the sonodynamic damage to bovine serum albumin (BSA) under ultrasonic irradiation using fluorescence and UV–vis spectroscopy. The experimental results revealed the obvious synergetic effect of Safranine T (ST) and ultrasonic irradiation during the damage of BSA molecules. In addition, some influencing factors such as ultrasonic irradiation time, Safranine T (ST) concentration, pH value and ionic strength on the sonodynamic damage of BSA molecules were also considered. Finally, the generation of reactive oxygen species (ROS) in sonodynamic process was estimated by the method of Oxidation-Extraction Photometry (OEP). Meanwhile, several radical scavengers were used to determine the kind of generated ROS. Experiments showed that under ultrasonic irradiation the Safranine T (ST) can generate several kinds of ROS at the same time, at least including singlet oxygen (¹O₂) and hydroxyl radicals (OH).     

Renal Clearable Luminescent WSe2 for Radioprotection of Nontargeted Tissues during Radiotherapy

High‐energy ionizing radiation is widely used in medical diagnosis and cancer radiation therapy. However, high‐energy radiation can also impose significant damages in healthy tissues during medical treatments via direct DNA damages and indirect damages from production of reactive oxygen species (ROS). Therefore, it is urgent to develop highly effective radioprotectants with low toxicities that can meet the increasing needs for alleviating the adverse effects from cancer radiation therapy and nuclear emergency. In this work, strongly catalytic ultrasmall (sub‐5 nm) cysteine‐protected WSe₂ dots are employed to protect healthy tissues against radiation via diminishing radiation‐induced free radicals. The WSe₂ dots with high surface activities can recover radiation‐induced DNA damages and eliminate the excessive ROS generated from radiation. In vivo experiments confirm that the survival rate of mice treated with WSe₂ dots is significantly elevated with radiation damages postponed under exposure to high‐dose ionizing radiation. Furthermore, the free radicals in major organs and hematological system can be appreciably omitted, suggesting their unique role as free radical scavengers. These WSe₂ dots in ultrasmall size show rapid renal clearance of ≈74% injection dose via urine excretion in 24 h and do not cause any apparent toxicity in vivo for up to 30 d.     

EPR and UV spectrometry investigation of sucrose irradiated with carbon particles

Solid state/EPR (SS/EPR) dosimeters of carbon ions irradiated sucrose are studied with EPR, and their water solutions – with UV spectroscopy. Doses between 20 and 200 Gy are used with linear energy transfer (LET) values for carbon ions of 63, 77, 96 and 230 keV μm^?1. After irradiation all samples show typical for irradiated sucrose EPR and UV spectra. The obtained data are compared with those previously reported for nitrogen particles and gamma rays irradiated sucrose. The identical shape of both the EPR and UV spectra of irradiated with various type radiation samples suggests that generated free radicals are not influenced by the nature of radiation. The lack of difference in the line width of the separate lines or the whole EPR spectrum, obtained for gamma and heavy particles irradiation, suggests negligible spin–spin interaction among the radiation-generated free radicals in the samples. The linear dependence of the EPR response on the absorbed dose radiation is found to be higher when generated by gamma rays, than by the same absorbed dose of heavy particles. In addition, the EPR response for carbon ions is higher than that for nitrogen ions. Water solutions of irradiated sucrose exhibit UV spectrum with absorption maximum at 267 nm, attributed to the recombination products of free radicals. The UV band intensity depends on the absorbed dose radiation. The UV spectra obtained for carbon, nitrogen and gamma rays irradiated sucrose are also compared.     

硒对钝顶螺旋藻氧化损伤的拮抗作用的光谱学特性及机制

研究了亚硒酸钠预处理对H2O2氧化胁迫下钝顶螺旋藻(Spirulina platensis)的生长、藻丝体形态、谱学特性以及细胞内活性氧(ROS)水平的影响,探究硒拮抗氧化胁迫保护螺旋藻的机制。结果显示,H2O2氧化胁迫明显抑制螺旋藻的生长,藻丝体严重受损,可见光吸收440nm峰增强,620和680nm峰降低;荧光发射和激发光谱特征峰强度明显降低,藻胆蛋白特征发射峰由660nm蓝移至650nm;红外光谱透射峰没有发生位移,蛋白质和多肽的特征谱带酰胺Ⅰ带和酰胺Ⅱ带相对强度降低;细胞内ROS相对含量显著性升高。硒预处理24h呈剂量效应地减轻由H2O2胁迫引起的氧化损伤,有效地抑制胞内ROS的过度累积,提高螺旋藻的抗氧化能力,缓解了氧化胁迫对光能捕获和传递等重要生理功能的影响。     

紫外光下毛竹的自由基与光电子能谱分析

分析了紫外光照射下毛竹自由基的变化规律和表面化学组成及结构的变化.利用电子自旋共振波谱和X射线光电子能谱技术,分别测量紫外光辐照后毛竹颗粒的自由基波谱和X射线光电子能谱.结果表明:毛竹自由基的光谱分裂因子g=2.003 3,自由基的强度随着辐照时间按Y=1-e-b,Pt规律增加;紫外光照60 min后毛竹表面O/C原子比稍有增加,C-C和C-H含量增加,C-O和C=O含量减少,-O-C=O含量增加为原来的3倍左右,说明毛竹表面生成了一些含氧官能团或碳的氧化态增高.     

Spectroscopic study on the sonodynamic and sonocatalytic damage of anthraquinone derivants to bovine serum albumin under ultrasonic irradiation

In this work, three anthraquinone derivants (Alizarin: 1,2-dihydroxy-9, 10-anthraquinone, Alizarin–DA: 1,2-dihydroxy-9, 10-anthraquinone-3-aminomethyl-N, N-diacetic acid and Alizarin–DA–Fe: 1,2-dihydroxy-9, 10-anthraquinone-3-aminomethyl-N, N-diacetate-Ferrous(III)) were used to study the sonodynamic and sonocatalytic damage of bovine serum albumin (BSA) molecules according to the hyperchromic effect of UV–vis spectra and quenching effect of intrinsic fluorescence. Meanwhile, some influencing factors such as ultrasonic irradiation time, anthraquinone derivants concentration and ionic strength on the damage of BSA molecules were also considered. The results show that the synergetic effect of anthraquinone derivants and ultrasonic irradiation can efficiently damage the BSA molecules. Finally, some special radical scavengers were used to determine the kind of generated reactive oxygen species (ROS) in the presence of three anthraquinone derivants under ultrasonic irradiation. The results show that the ROS, at least, including singlet oxygen (¹O₂) and hydroxyl radicals (OH) are generated during the sonodynamic and sonocatalytic processes. It is wished that this paper could offer some valuable references for the application of anthraquinone derivants in sonodynamic therapy (SDT) and sonocatalytic therapy (SCT) for tumor treatment.     

Expression of heme oxygenase-1 due to intracellular reactive oxygen species induced by ultrasound

The present study was undertaken to elucidate the mechanism by which ultrasound induces the expression of heme oxygenase-1 (HO-1). When human lymphoma U937 cells were exposed to a 1 MHz continuous wave for 1 min, HO-1 expression examined by real-time quantitative polymerase chain reaction and immunoblotting was observed at intensities above the cavitational threshold. No induction of HO-1 expression was observed in the cells exposed for 1 min to 42 degrees C, a temperature higher than that during sonication. When a potent antioxidant, N-acetyl-l-cysteine, was added to the culture medium before or after sonication, the induction was attenuated, indicating that reactive oxygen species (ROS) are involved. However, the addition of catalase did not affect the induction, and no HO-1 was observed on the addition of pre-sonicated medium, suggesting that hydrogen peroxide due to the recombination of hydroxyl radicals generated extracellularly was not involved. The addition of free radical scavengers, glutathion-monoethyl ester, dimethyl sulfoxide and D(-)-mannitol, suppressed the induction. A decrease in mitochondrial membrane potential and the generation of superoxide were also observed in the sonicated cells, suggesting that mitochondria were the source of intracellularly generated ROS. These results indicate that superoxide secondarily generated from damaged mitochondria, not hydroxyl radicals generated in medium directly by sonication, give rise to intracellular oxidative stress inducing HO-1 expression.     

Electron paramagnetic resonance study of free radicals inγ-irradiated single crystal of tris(glycine) calcium(II) dibromide

Tris(glycine) calcium(II) dibromide single crystal has been irradiated with aγ-source to produce free radicals and the irradiated sample has been subjected toepr studies. The observed spectra reveal that an NH₄ radical is formed by rupturing glycine molecule due to irradiation. The unpaired electron is localized on the C-N bond. The proton hyperfine interaction on the unpaired spin shows orthorhombic symmetry and the spectroscopic splitting factor remains isotropic.     

人发自由基的ESR研究

用ESR方法系统地研究了癌症与癌症以外的各种疾病患者头发的自由基,发现各种疾病对人发自由基的I和P值都产生很大影响,因而不能仅仅由某个人的人发自由基I和P值与相同年龄健康人发的差别来判断患有癌症.对633例健康人发自由基的ESR测试再次表明了作者曾提出的人发自由基浓度随人生长年龄变化的统计规律.     

ESR Study on Scavenging Effect of Squalene on Free Radicals in Mainstream Cigarette Smoke

Radicals in mainstream cigarette smoke (MCS) have been proposed to contribute to the harm caused by cigarette smoking. In the present study, we used natural antioxidant, squalene, to treat cigarette filters and tobacco for scavenging gas- and particulate-phase free radicals in MCS. The scavenging activities of cigarette filter and tobacco containing squalene against gas and particulate-phase free radicals were detected and quantified using spin-trapping or directly electron spin resonance spectroscopy method. The results revealed that squalene could significantly scavenge gas- and particulate-phase free radicals in MCS in a dose-dependent manner. The radical-scavenging activity of cigarette filter treatment was higher than that of tobacco treatment, irrespective of either gas-phase free radicals, or particulate-phase free radicals in MCS. Among them, 3 mg squalene/filter treatment showed that the highest scavenging effects against gas- and particulate-phase free radicals were 35.9 and 35.4%, respectively. The use of squalene as potential scavenger for reducing free radicals in cigarette smoke is discussed.