高效氯氟氰菊酯在田间环境中的消解行为研究

本文选择了我国从吉林到海南5个重要的农业生产区,对常用杀虫剂高效氯氟氰菊酯在玉米、大豆、甘蓝、土豆、苹果等农作物上的降解规律进行了研究,并对其在这几种作物上的使用安全性进行了评价.研究包括:建立了基于气相色谱-电子捕获检测方法的高效氯氟氰菊酯的检测方法;在对高效氯氟氰菊酯在土壤中的降解规律进行研究,发现在施药后的前五天,消解速率比较快,并且农药在土壤中的消解行为在统计意义上是没有显著差别.高效氯氟氰菊酯在五地土壤中的半衰期在1.56到5.30天的范围内;在对作物上农药残留的消解过程的研究中发现,其在苹果上的降解速率明显低于其他作物,其半衰期在北京为10.3天,安徽为17.7天.北京的其他作物中高效氯氟氰菊酯的半衰期在1.32至2.74天之间,安徽的其他作物中在2.07到3.80天之间.高效氯氟氰菊酯在作物中的传递性比较差,在直接接触农药的甘蓝和苹果中能够检测到农药残留,而在不直接接触喷施农药的玉米、大豆和土豆上检测不到残留.     

浅谈有机化学课程教学中的兵法与谋略

介绍在有机化学课程教学中融入兵法与谋略的讲授心得,包括在有机合成题的讲解、在有机化学反应机理的介绍中及在有机化学反应方程式的介绍中融入谋略思想的方法。     

铁丝在氧气中燃烧的实验改进

“铁丝在氧气中燃烧”是初中化学教材中证明氧气化学性质的一个演示实验,该实验证明了氧气比较活泼,在一定条件下可以和金属发生剧烈反应。但是与木炭在氧气中燃烧、硫在氧气中燃烧、蜡烛在氧气中燃烧的演示实验相比,铁丝在氧气中燃烧的实验存在着一些不足的地方,针对这些不足,对铁丝在氧气中燃烧的实验进行了改进。1实验存在的问题按照教材要求,铁丝在氧气中燃烧的实验,须将铁丝绕成螺旋状,并在铁丝的末端绑上一根火柴杆,实验时先将火柴杆点燃,待火柴杆将燃尽时,迅速伸入盛满氧气的集气瓶中。这样的操作存在2个问题:第一,火柴燃烧的程度不…     

甲烷在氧化铁表面还原NO的特性与反应机理研究

在程序控温电加热水平陶瓷管反应器中,在300~1 050 ℃,对N₂气氛中甲烷在氧化铁(充分氧化后的铁丝网卷)表面还原NO的特性进行了实验研究,测试了NO脱除效率、CO生成量以及反应后铁样品表面组分和微观状态的变化特点,分析了甲烷在氧化铁表面还原NO的反应机理。在此基础上,在1 000 ℃时,对模拟烟气条件下甲烷在氧化铁表面还原NO的持久性进行了实验研究。结果表明,甲烷在氧化铁表面能够高效地还原NO。在N₂气氛下,在850 ℃以上达到100%的NO脱除效率。在模拟烟气中,甲烷在氧化铁表面脱除NO的能力具有很好的持久性。实验结果表明,在1 000 ℃时,采用由体积分数为2.0%的O₂、16.8%的 CO₂和524×10^-6的 NO,N₂配平的模拟烟气,1.17% CH₄能够在连续100 h内保持100%的NO脱除效率,而未出现下降的趋势。对反应机理的研究结果表明,甲烷在氧化铁表面还原NO的机理包括甲烷通过再燃机理还原NO以及甲烷通过在氧化铁表面还原氧化铁为金属铁、金属铁进而直接还原NO两种主要反应机理。其中,后者为主要反应机理。     

高压化学

高压化学在现代科学中占有重要的地位,并在过去二十几年中取得了快速的发展。本文简要介绍了高压化学及高压化学研究领域在诸多方面的研究进展,其中包括高压无机化学和高压有机化学,以及高压在化学合成和化学过程研究中的应用,展示了高压化学的研究现状及其在许多方面的应用前景。     

制备溶液的方法、相关设备以及该方法和设备的应用

为制备至少一种固体在溶剂中的溶液，该固体贮存于空腔中。其中在溶剂中可溶的固体首先用在该溶剂中不溶的介质所覆盖或包封，以阻止该固体的溶解。接着将溶剂导入空腔，并如此处理在该溶剂中不溶的介质，以使在溶剂和可溶的固体之间进行接触，由此使该固体在溶剂中溶解。可以有利方法制备含两种或多种固体的溶液。     

Ho3＋对吸附CO电化学氧化的促进作用

研究了吸附在Pt/C催化剂上的Ho3＋对吸附CO的电氧化的影响.结果表明,无论在中性和酸性溶液中,在较大的温度范围内,Ho3＋对CO在Pt/C催化剂上的电氧化都有促进作用,其原因是吸附Ho3＋的存在减弱了CO在Pt/C催化剂上的吸附强度.其次,在中性溶液中,Ho3＋对吸附CO的电氧化的促进作用比在酸性溶液中大.第三,无论在酸性还是中性溶液中,温度的升高有利于发挥Ho3＋对吸附CO的电氧化的促进作用.     

水中受拉伸负载下单壁纳米碳管机械性质的分子动力学研究

利用分子动力学方法研究了(5,5)扶手椅型和(10,10)锯齿型纳米碳管在水中受拉伸负载下的机械性质.通过计算纳米碳管中氧和氢原子的局部密度分布研究了限制效应.结果表明,碳管在水中的杨式系数与在真空下相同,而碳管在水中的拉伸应力小于在真空中的.     

O_2存在下NO在固体电解质电池上分解机理

研究了在O_2存在条件下,NO在Pd |YSZ| Pd固体电解质电池和RuO_2 |Pd|YSZ| Pd固体电解质电池上的分解性质,在O_2存在条件下650 ～ 700 ℃之间 ,在0 ～ 4.4 V直流电压作用下,NO在Pd |YSZ| Pd电池和RuO_2|Pd|YSZ| Pd电池 上的分解不以电解机制进行,而以电催化机理进行的。即在直流电压下,阴极催化 剂上的O~(2-)被直流电压通过YSZ固体电解质转移到阳极,以O_2的形式放出,以此 保持催化剂的活性状态。在Pd|YSZ|Pd 固体电解质电池上,Pd金属表面是催化NO分 解的主要活性位。RuO_2 |Pd|YSZ| Pd固体电解质电池上,某特定还原态的RuO_x (0 < x < 2)是NO分解的主要活性位。在O_2存在下,该电池在1 ～ 4 V间合适的电 压下,在650 ～ 700 ℃能选择性地对NO进行电催化分解。     

两嵌段共聚物反相溶剂中组装结构转变动力学的模拟研究

利用耗散粒子动力学方法,分别研究了不同结构的组装体在改变溶剂的选择性后,在溶液及界面上的结构演变动力学.模拟结果表明,在改变溶剂的选择性后,大球形胶束在溶液中转变形成反向球形胶束,而在界面上则转变形成反向环状胶束,当前模拟结果与已有的实验结果一致.此外,模拟结果还预测出,在改变溶剂的选择性后,环状胶束在溶液中转变形成反向环状胶束,而在界面处受限形成反向的支化蠕虫状胶束;蠕虫状胶束则在溶液中转变形成反向环状胶束,而在界面处受限形成多层纳米球结构;囊泡在溶液中转变形成分散的小胶束聚集体,而在界面处受限形成球形的补丁纳米粒子.     

The heat of dissolution of uranyl nitrate in aqueous nitrate solutions

Conclusions A model has been suggested to explain the observed relationship between the measured heats of dissolution of uranyl nitrate in aqueous nitrate solutions and the concentration of the salting-out agent. The model describes the change in the structure of water in the solution with change in its concentration. On the one hand, a destruction of the water structure by ions occurs, which is weakened with increase in the distance from the ion, and leads to such irregularity in the distribution of water molecules in the solution that the mean number of molecules of water in unit volume is increased with increase in the distance from the ions. In experiments on the heat of dissolution this increase leads to increased hydration of the uranyl cation and reduction in the endothermicity of the dissolution with increase in the concentration of the solution. On the other hand, an interaction occurs between the ions of the salting-out agent and the water molecules in the solution, leading to the opposite result: There is an increase in the mean number of water molecules of the solution in unit volume in the direction of these ions. In experiments on the heat of dissolution this is revealed in the dehydration of the uranyl cation, and correspondingly in an increase in the endothermicity of the dissolution with increase in the concentration of the solution. The proposed model is in harmony with data on vapor pressure above the solutions (the relationship between the activity coefficient of the water and the concentration of the solution).Translated from Zhurnal Strukturnoi Khimii. Vol. 3, No. 2, pp. 143–150, March–April. 1962     

微波制样的应用

介绍了微波制样在分析化学中的应用，包括微波试样消解，微波加热水样测定CODcr，微波加热水解蛋白质测定各种氨基酸，以及微波萃取等。特别是对微波试样消解在应用中的一些问题，作了较详细的叙述。     

γ-irradiation of polypropylene in vacuum and in air

Polypropylene films were irradiated with ⁶⁰Co γ-rays in vacuum or in air and stored in air. Just after irradiation, the concentration of carbonyl group of the sample irradiated in air only increased with dose. The concentrations of both samples increased with storage time. The more the absorbed doses, the higher the increasing rates. The increasing rate of the concentration of carbonyl group during irradiation in air was higher than those during storage in air. Just after irradiation, the tensile strengths and the elongations of the both samples somewhat increased with dose at the doses less than 5 Mrad, but decreased at doses more than 13 Mrad. The tensile strength and the elongation of the sample irradiated in air decreased with storage time. Those of the sample irradiated in vacuum also decreased with storage time but the decreasing rates were much smaller than those in the sample irradiated in air. The gel fractions of the samples irradiated in vacuum and annealed in vacuum were somewhat higher than those irradiated in vacuum and not annealed. To elucidate high oxidation rate in the sample irradiated in air during and after irradiation, reaction mechanisms were discussed. To clarify the difference of mechanical properties between the samples irradiated in vacuum and in air, the effect of crosslink was considered, together with the oxidation.     

Study of the mobility of lattice oxygen in complex oxide catalysts for partial oxidation of propylene to acrolein

The amount of oxygen in the lattice of solids that participates in the elementary stages of partial propylene oxidation is determined for two types of Co-Mo-Bi-Fe-Sb-K-O catalysts (I, II) differing in the method of introduction of antimony and potassium. Two independent methods are used: (1) on the basis of the yield of the oxygen-containing products of propylene oxidation by oxygen of the catalyst in a pulse regime and (2) with the use of Möessbauer spectroscopy. Coincidence of the results obtained by both methods indicates that the active oxygen of the catalyst lattice is formed during redox transformations of iron(III) molybdate entering the composition of the catalysts. Data on the reduction of the catalysts in a pulse regime at various temperatures, which were processed in the framework of the diffusion model, allowed the estimation of the rate constants for diffusion of the lattice oxygen. An increase in the mobility of the lattice oxygen in catalyst I, which is modified with a small amount of antimony as compared to catalyst II, results in an increase in the overall productivity of the sample and in a decrease in the selectivity of propylene oxidation to acrolein. This correlates with the increase in the total amount of the lattice oxygen participating in the process.     

Organization of mixed monomolecular layers formed with the xanthophyll pigments lutein or zeaxanthin and dipalmitoylphosphatidylcholine at the argon-water interface

Two-component monomolecular layers were formed with two xanthophyll pigments, lutein and zeaxanthin and dipalmitoylphosphatidylcholine (DPPC), at the argon-water interface. Analysis of the mean molecular area parameters versus molar fraction of the xanthophyll component shows large overadditivity (ca. 50 A2 in the case of zeaxanthin and 150 A2 in the case of lutein) in the region of low molar fractions of carotenoids (maximum at 5 mol% in the case of zeaxanthin and at 20 mol% in the case of lutein). The experimental values of a mean molecular area are in good agreement with the values expected, based on the additivity rule at high molar percentages of the xanthophylls. Absorption spectroscopy of a single monolayer at the argon-water interface in the UV-Vis region has also been applied to analyze the formation of molecular assemblies of lutein in monomolecular films. The differences in the organization of lutein-DPPC and zeaxanthin-DPPC monolayers are interpreted in terms of the aggregation of xanthophyll pigments in the layers and different orientation of both xanthophylls at the interface. The results are discussed in relation to possible physiological functions of lutein and zeaxanthin in the membranes of the retina of an eye.     

Simultaneous liquid chromatographic determination of 39 polycyclic aromatic hydrocarbons in indoor and outdoor air and application to a survey on indoor air pollution in Fuji, Japan

An analytical method was established for the simultaneous determination of 39 polycyclic aromatic hydrocarbons (PAHs) in air. The method was applied to a survey of gaseous and particulate PAHs in household indoor air. The survey was performed in 21 houses in the summer of 1999 and in 20 houses in the winter of 1999-2000 in Fuji, Japan. Thirty-eight PAHs were determined in indoor and outdoor air in the summer, and 39 PAHs were determined in indoor and outdoor air in the winter. The concentrations of gaseous PAHs in indoor air tended to be higher than those in outdoor air in the summer and winter. The concentrations of particulate PAHs in indoor air were the same as or lower than those in outdoor air in the summer and winter. PAH profiles, correlations between PAH concentrations, and multiple regression analysis were used to determine the factors affecting the indoor PAH concentrations. These results showed that gaseous PAHs in indoor air were primarily from indoor emission sources, especially during the summer, and that indoor particulate PAH concentrations were significantly influenced by outdoor air pollution.     

Alteration in photosystem II photochemistry of thylakoids isolated from senescing leaves of wheat seedlings

Wheat seedlings, grown for 7 days in the light, were allowed to senesce in the light or dark, and the change in the photosystem II (PS II) photochemistry of chloroplasts isolated from the primary leaves of these seedlings was investigated. The decrease in oxygen evolution and the fast fluorescence results indicated that the impairment of PS II in the leaves of seedlings senescing in the light was different from that in the leaves of seedlings senescing in the dark. Thermoluminescence studies showed a structural modification in the Q_B protein of chloroplasts isolated from leaves senescing in the light and an alteration in the S state transition of chloroplasts isolated from leaves senescing in the dark.     

POLARIZED TIME-RESOLVED FLUORESCENCE SPECTRA OF PHYCOBILISOMES ISOLATED FROM Tolypothrix tenuis EMBEDDED IN POLY(VINYL ALCOHOL) FILM

–Time-resolved fluorescence spectra in the ps time range were measured on phycobilisome (PBS) embedded in poly(vinyl alcohol) films. The cyanobacterium Tolypothrix tenuis was used as a source of PBS because the pigment composition and the structure of the PBS are well defined. Isotropic PBS in the unstretched film and PBS uniaxially oriented in the stretched film were investigated. Diameters of PBS hemidiscs were oriented parallel to the film-stretching direction. The time-resolved fluorescence spectra of the unstretched sample and of the two polarized components in the stretched samples showed several differences in the rise and decay. The delay time, estimated from the time span between the maximum laser pulse and maximal intensity of the phycocyanin and allophycocyanin fluorescence, was much longer than that reported in the aqueous media. This suggests occurrence of a higher thermal deactivation of PBS in polymer film than in aqueous media. The excitation energy transfer from excited phycocrythrin to allophycocyanin was more efficient in the unstretched than in the stretched samples, and it was greater in the parallel polarized component of the stretched sample than in the perpendicular component. The present results are in agreement with a previous suggestion which states that there are two independent pathways of excitation energy transfer in PBS and that there is more than one final emitter of fluorescence. The molecules taking part in various pathways of energy transfer differ in their orientation within PBS.     

Voltammetric determination of platinum in perfusate and blood: Preliminary data on pharmacokinetic study of arterial infusion with oxaliplatin

Because Platinum Group Elements have found widespread use in catalytic converters in cars and as chemotherapeutic agent, interest in the development of reliable analytical methods is carried out in order to monitor these analita in humans to protect the citizen's health.Considering that information on the levels of many trace elements in biological matrices is scarce and for many non-essential elements, baseline levels in the population, and especially in those particularly exposed to the risk are lacking, in this paper we optimize an analytical method for biological matrices, using a voltammetric technique to measure the concentration of Pt in blood and perfusate.The amount of Pt recovered from the blood and perfusate samples spiked with analita was observed to be meanly of 95% with 5–6% of R.S.D. These results indicated that proposed method for the determination of platinum in biological materials is accurate and reproducible.The amounts of platinum found in the blood samples of common ranged citizen were similar to quantification limit while in the patients the concentration ranged from 1.5 to 360 μg/L, in perfusate ranged from 0.7 to 9700 μg/l. The concentrations of Pt of populace and in patients before of infusion are in agreement with the level measured in the blood of unexposed patients.The proposed analytical method permits to determine the amount of Pt in the perfusate and subsequently absorbed by the target organs in order to determine the dose and timing of treatment and to avoid overdoses with related undesired effects.     

Sol-gel Transition of Methylcellulose Solution in the Coexistence of Hexadecyltrimethylammonium Bromide and Sodium Chloride

The sol-gel transition of methylcellulose (MC) solution in the presence of NaCl and hexade-cyltrimethylammonium bromide (HTAB), together with MC/NaCl solution in the presence of HTAB and MC/HATB solution in the presence of NaCl, was investigated by the rheolog-ical measurements. It has been found that the sol-gel transition temperature of MC solution decreases linearly with the concentration of NaCl in solution but increases linearly with the concentration of HTAB in solution, respectively. However, the sol-gel transition temperature of MC/NaCl solution in the presence of HTAB keeps the same value, independent of theconcentration of HTAB in solution. On the other hand, the sol-gel transition temperature of MC/HTAB solution decreases linearly with the concentration of NaCl in solution. The experimental results suggest that, for MC/NaCl solution in the presence of HTAB, the salt-induced spherical micelles of HTAB should have formed in bulk solution. For MC solution in the absence of NaCl, no spherical micelles have been formed in bulk solution, though the concentration of HTAB in our experiment is almost one order of magnitude higher than the critical micelle concentration of HTAB in polymer-free solution. In fact, due to adsorption of HTAB on MC chains, the realconcentration of HTAB in bulk solution, is much less than the apparent concentration of HTAB dissolved in MC solution.