O3与O3/H2O2两个体系降解除草剂2,4-D反应特性研究

分别采用O3、O3/H2O2体系降解苯氧羧酸类除草剂2,4-D,探讨了降解过程中反应温度、pH值、O3混合气流量、有机物初始浓度等操作条件的变化对降解动力学的影响。结果发现,温度和pH值的影响较大,O3流量影响最小,温度升高、pH值增大、臭氧流量增加、2,4-D初始浓度降低均有助于降解速率的提高。O3/H2O2体系中,H2O2能促进O3分解产生大量自由基,导致2,4-D反应活化能降低。和O3相比,O3/H2O2体系降解效果好,降解时间短,反应条件温和,操作费用低,是很有发展前景的高级氧化技术。     

Kinetics of the OH Reaction with Methyl Chloroform and Its Atmospheric Implications

The rate coefficients for the reaction of hydroxyl (OH) radicals with methyl chloroform (CH(3)CCI(3)) were measured between 243 and 379 kelvin with the pulsed photolysis-laserinduced fluorescence method. The measured rate coefficients at 298 and 277 kelvin were approximately 20 and approximately 15%, respectively, lower than earlier values. These results will increase the tropospheric OH concentrations derived from the CH(3)CCI(3) budget analysis by approximately 15%. The predicted atmospheric lifetimes of species whose main loss process is the reaction with OH in the troposphere will be lowered by 15% with consequent changes in their budgets, global warming potentials, and ozone depletion potentials.     

Direct kinetic measurements of Criegee intermediate (CH₂OO) formed by reaction of CH₂I with O₂

Ozonolysis is a major tropospheric removal mechanism for unsaturated hydrocarbons and proceeds via "Criegee intermediates"--carbonyl oxides--that play a key role in tropospheric oxidation models. However, until recently no gas-phase Criegee intermediate had been observed, and indirect determinations of their reaction kinetics gave derived rate coefficients spanning orders of magnitude. Here, we report direct photoionization mass spectrometric detection of formaldehyde oxide (CH(2)OO) as a product of the reaction of CH(2)I with O(2). This reaction enabled direct laboratory determinations of CH(2)OO kinetics. Upper limits were extracted for reaction rate coefficients with NO and H(2)O. The CH(2)OO reactions with SO(2) and NO(2) proved unexpectedly rapid and imply a substantially greater role of carbonyl oxides in models of tropospheric sulfate and nitrate chemistry than previously assumed.     

猕猴桃根提取物体外抗氧化活性研究

[目的]探讨猕猴桃根提取物的体外抗氧化作用。[方法]采用DPPH自由基、超氧阴离子、羟基自由基、过氧化氢和还原力反应体系,测定猕猴桃根提取物的体外抗氧化作用,并用维生素C进行对照试验。[结果]试验条件下,ERHM对DPPH自由基、超氧阴离子（O2-.）、羟基自由基（.OH）、过氧化氢（H2O2）等均有较强的清除或抑制作用,且显示较好的量效关系,同时具有一定的还原力。其消除DPPH自由基的EC50为8.03μg/ml,清除超氧阴离子（O 2-.）的EC50为1.28 mg/ml,抑制羟基自由基（.OH）能力可达69.4%,浓度为100μg/ml时,对过氧化氢（H2O2）的清除率为42%。[结论]猕猴桃根提取物具有较强的还原力,能有效清除DPPH和超氧阴离子自由基,并抑制羟基自由基的产生。所以,ERHM有效成分具有较为显著的抗氧化作用。     

Coupling of nitrous oxide and methane by global atmospheric chemistry

Nitrous oxide (N(2)O) and methane (CH(4)) are chemically reactive greenhouse gases with well-documented atmospheric concentration increases that are attributable to anthropogenic activities. We quantified the link between N(2)O and CH(4) emissions through the coupled chemistries of the stratosphere and troposphere. Specifically, we simulated the coupled perturbations of increased N(2)O abundance, leading to stratospheric ozone (O(3)) depletion, altered solar ultraviolet radiation, altered stratosphere-to-troposphere O(3) flux, increased tropospheric hydroxyl radical concentration, and finally lower concentrations of CH(4). The ratio of CH(4) per N(2)O change, -36% by mole fraction, offsets a fraction of the greenhouse effect attributable to N(2)O emissions. These CH(4) decreases are tied to the 108-year chemical mode of N(2)O, which is nine times longer than the residence time of direct CH(4) emissions.     

Hydrogen radicals, nitrogen radicals, and the production of O3 in the upper troposphere

The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3 in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HOx required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of O3 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day. This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more O3 than expected.     

Atmospheric trends in methylchloroform and the global average for the hydroxyl radical

Frequent atmospheric measurements of the anthropogenic compound methylchloroform that were made between 1978 and 1985 indicate that this species is continuing to increase significantly around the world. Reaction with the major atmospheric oxidant, the hydroxyl radical (OH), is the principal sink for this species. The observed mean trends for methylchloroform are 4.8, 5.4, 6.4, and 6.9 percent per year at Aldrigole (Ireland) and Cape Meares (Oregon), Ragged Point (Barbados), Point Matatula (American Samoa), and Cape Grim (Tasmania), respectively, from July 1978 to June 1985. These measured trends, combined with knowledge of industrial emissions, were used in an optimal estimation inversion scheme to deduce a globally averaged methylchloroform atmospheric lifetime of 6.3 (+ 1.2, -0.9) years (1sigma uncertainty) and a globally averaged tropospheric hydroxyl radical concentration of (7.7 +/- 1.4) x 10(5) radicals per cubic centimeter (1sigma uncertainty). These 7 years of gas chromatographic measurements, which comprise about 60,000 individual calibrated real-time air analyses, provide the most accurate estimates yet of the trends and lifetime of methylchloroform and of the global average for tropospheric hydroxyl radical levels. Accurate determination of hydroxyl radical levels is crucial to understanding global atmospheric chemical cycles and trends in the levels of trace gases such as methane.     

DNA damage and oxygen radical toxicity

A major portion of the toxicity of hydrogen peroxide in Escherichia coli is attributed to DNA damage mediated by a Fenton reaction that generates active forms of hydroxyl radicals from hydrogen peroxide, DNA-bound iron, and a constant source of reducing equivalents. Kinetic peculiarities of DNA damage production by hydrogen peroxide in vivo can be reproduced by including DNA in an in vitro Fenton reaction system in which iron catalyzes the univalent reduction of hydrogen peroxide by the reduced form of nicotinamide adenine dinucleotide (NADH). To minimize the toxicity of oxygen radicals, the cell utilizes scavengers of these radicals and DNA repair enzymes. On the basis of observations with the model system, it is proposed that the cell may also decrease such toxicity by diminishing available NAD(P)H and by utilizing oxygen itself to scavenge active free radicals into superoxide, which is then destroyed by superoxide dismutase.     

红毛五加叶水提液对羟自由基清除率的测定

[目的]测定红毛五加叶水提液对羟自由基的清除率并评价其抗氧化活性。[方法]利用Fenton反应产生羟自由基,用二甲亚砜（DMSO）捕获羟自由基并与之反应生成甲醛,甲醛经2,4-二硝基苯肼衍生成相应的苯腙,通过HPLC检测加或不加样品时该苯腙的峰面积的变化,从而计算红毛五加叶水提液对羟自由基的清除率。色谱条件：色谱柱为Diamonsil C18（250 mm×4.6 mm5,μm）,流动相为乙腈-水（65∶35,V/V）,流速为0.8 ml/min,检测波长为365 nm。[结果]Fenton反应体系为2.0 mmol/L Fe2＋＋107.7 mmol/L H2O2＋225.2 mmol/L DMSO;在该反应体系中红毛五加叶水提液清除羟自由基的IC50为0.67 mg/ml（即每1 ml含药材量为0.67 mg）;红毛五加叶总皂苷是清除羟自由基的活性成分。[结论]红毛五加叶水提液能够清除Fenton反应产生的羟自由基,具有较强的抗氧化活性。     

Hydroxyl radical photoproduction in the sea and its potential impact on marine processes

Photochemical production rates and steady-state concentrations of hydroxyl radicals (.OH) were measured in sunlight-irradiated seawater. Values ranged from 110 nanomolar per hour and 12 x 10(-18) molar in coastal surface water to 10 nanomolar per hour and 1.1 x 10(-18) molar in open ocean surface water. The wavelengths responsible for this production are in the ultraviolet B region (280 to 320 nanometers) of the solar spectrum. Dissolved organic matter (DOM) appears to be the main source for .OH over most of the oceans, but in upwelling areas nitrite and nitrate photolysis may also be important. DOM in the deep sea is degraded more readily by .OH (and its daughter radicals), by a factor of 6 to 15, than is DOM in open-ocean surface water. This finding may in part bear on major discrepancies among current methods for measuring dissolved organic carbon in seawater.     

Hydroxyl radical reactivity with diethylhydroxylamine

Diethylhydroxylamine (DEHA) reacts with gas-phase hydroxyl radicals on every third collision, whereas the corresponding reaction in aqueous solution is considerably slower. The high gas-phase reactivity explains the predicted inhibitory effect of DEHA in atmospheric smog processes. Results from the studies in the aqueous phase are helpful in predicting the mechanism of the reaction of DEHA with hydroxyl radicals.     

Antibody catalysis of the oxidation of water

Recently we reported that antibodies can generate hydrogen peroxide (H2O2) from singlet molecular oxygen (1O2*). We now show that this process is catalytic, and we identify the electron source for a quasi-unlimited generation of H2O2. Antibodies produce up to 500 mole equivalents of H2O2 from 1O2*, without a reduction in rate, and we have excluded metals or Cl- as the electron source. On the basis of isotope incorporation experiments and kinetic data, we propose that antibodies use H2O as an electron source, facilitating its addition to 1O2* to form H2O3 as the first intermediate in a reaction cascade that eventually leads to H2O2. X-ray crystallographic studies with xenon point to putative conserved oxygen binding sites within the antibody fold where this chemistry could be initiated. Our findings suggest a protective function of immunoglobulins against 1O2* and raise the question of whether the need to detoxify 1O2* has played a decisive role in the evolution of the immunoglobulin fold.     

H_2O_2清洗对蔬菜中农药去除效果及机制的研究

为了提高蔬菜在清洗过程中的农药去除率,利用低浓度的H_2O_2清洗不同类型的蔬菜。结果表明,在酸性(p H=4.0)条件下,含铁量较高的蔬菜能较明显提高H_2O_2氧化去除敌敌畏的效率。通过叔丁醇试验发现,敌敌畏去除率的提高主要原因可能是由于蔬菜基质自身的Fe~(2+)或Fe~(3+)催化H_2O_2有效地产生了高活性的羟基自由基。试验进一步探讨了H_2O_2清洗几种典型的有机磷、有机氯和氨基甲酸酯类农药的降解,结果表明该体系针对不同类型的农药都具有降解效率。     

海芦笋黄酮类化合物抗氧化活性研究

[目的]为海芦笋的进一步开发利用提供一定的理论依据。[方法]以海芦笋为原料,研究其中的黄酮类化合物抑制植物油脂的自氧化和清除DPPH自由基、羟自由基、氧自由基的效果,评价海芦笋黄酮类化合物的体外抗氧化活性。[结果]海芦笋黄酮类化合物具有较强的抑制植物油自氧化、清除DPPH自由基、Fenton反应中产生的羟自由基、邻苯三酚氧化产生的氧自由基的作用,且抑制作用与海芦笋黄酮类化合物的浓度呈正相关。[结论]海芦笋黄酮类化合物可以作为天然的食品抗氧化剂进行开发。     

甘薯叶中清除自由基活性物质的提取·保存与定性分析

[目的]为甘薯叶提取物应用于抗衰老化妆品提供理论依据。[方法]利用正交试验对甘薯叶中清除自由基的活性物质的提取及保存条件进行优化,并通过相关性分析对提取物中清除自由基能力的活性成分进行探讨。[结果]结果表明:甘薯叶中含有清除DPPH自由基和羟自由基的活性物质,提取剂种类是影响活性物质提取效率的最重要因素,其中最佳提取与保存条件为:以水为提取溶剂,提取液pH值为8,最佳保存温度为25℃。甘薯叶提取物总酚含量与其DPPH和羟自由基清除率呈正比关系且具有良好的线性关系;提取物总黄酮含量仅与羟自由基清除率有较好线性关系。[结论]提取物中的酚类物质能有效地清除DPPH自由基和羟自由基;提取物中的黄酮类物质仅能有效清除羟自由基。     

醇提板栗壳色素对羟自由基和超氧阴离子自由基的清除作用

以30%乙醇溶液从板栗壳中提取得到板栗壳色素CSPⅠ,并以Fenton反应产生.OH模型、邻苯三酚自氧化反应产生O2-.模型,用紫外和可见分光光度法试验了CSPⅠ对模型中产生的.OH和O2-.的清除作用。结果表明,CSPⅠ具有良好的清除.OH作用,且清除作用与色素浓度呈正相关性,EC50为75.65 mg/L;而CSPⅠ对O2-.没有明显的清除作用。     

蛋白核小球藻多糖的酶解辅助提取及抗氧化活性

利用纤维素酶对蛋白核小球藻多糖进行辅助提取,并在单因素的基础上,通过响应面试验对提取时间、提取温度、料液比和酶浓度等4个因素进行优化。结果表明:酶法辅助提取蛋白核小球藻多糖的最佳条件为:提取时间为2h、提取温度为93℃、料液比为1∶30和酶浓度为2%,在该条件下多糖提取率可达6.13%,实际为(5.87±0.24)%。同时研究其对DPPH自由基、超氧阴离子自由基及羟基自由基的清除能力,结果表明蛋白核小球藻多糖能有效清除超氧阴离子自由基及羟基自由基。     

Carbon Monoxide in the Earth's Atmosphere: Increasing Trend

The results of an analysis of more than 60,000 atmospheric measurements of carbon monoxide taken over 3(1/2) years at Cape Meares, Oregon (45 degrees N, 125 degrees W), indicate that the background concentration of this gas is increasing. The rate of increase, although uncertain, is about 6 percent per year on average. Human activities are the likely cause of a substantial portion of this observed increase; however, because of the short atmospheric lifetime of carbon monoxide and the relatively few years of observations, fluctuations of sources and sinks related to the natural variability of climate may have affected the observed trend. Increased carbon monoxide may deplete tropospheric hydroxyl radicals, slowing down the removal of dozens of man-made and anthropogenic trace gases and thus indirectly affecting the earth's climate and possibly the stratospheric ozone layer.     

Nitrogen-15 and oxygen-18 characteristics of nitrous oxide: a global perspective

The global budget of N(2)O shows a significant imbalance between the known rate of destruction in the stratosphere and the estimated rates of natural and anthropogenic production in soils and the ocean. Measurements of the (15)N/(14)N and (18)O/(16)O ratios in two major tropospheric sources of N(2)O, tropical rain forest soils and fertilized soils, show that soil N(2)O from a tropical rain forest in Costa Rica and from sugar-cane fields in Maui is strongly depleted in both (15)N and (18)O relative to mean tropospheric N(2)O. A major source of heavy N(2)O, enriched in both (15)N and (18)O, must therefore be present to balance the light N(2)O from soils. One such source is the back-mixing flux of N(2)O from the stratosphere, which is enriched in (15)N and (18)O by photolysis and chemistry. However these return fluxes of (15)N and (18)O are so great that a large oceanic flux of N(2)O is required to balance the heavy isotope-enriched stratospheric flux. All these effects will be reflected in climatically related isotopic variations in trapped N(2)O in polar ice cores.     

7种不同来源灵芝热水提物体外抗氧化活性研究

[目的]比较不同地区灵芝热水提物的体外抗氧化活性。[方法]分别从总还原力、清除羟基自由基(·OH)、超氧阴离子自由基(O_2~-·)和DPPH自由基4个方面对7种灵芝子实体热水提物的体外抗氧化活性进行了初步研究。[结果]在相同浓度下,猫儿山野生灵芝热水提物的总还原力最强,吸光度高达2.48;·OH清除能力最高,清除率99.46%;清除DPPH自由基能力最强,清除率为96.62%;清除O_2~-·能力排第三。[结论]猫儿山野生灵芝热水提取物在总还原力、清除·OH、DPPH自由基3个方面的抗氧化能力表现出最强,说明猫儿山野生灵芝具有非常好的开发潜力。