A Quantum State-Resolved Insertion Reaction: O((1)D) + H(2)(J = 0) --> OH((2) product operator product operator product operator, v, N) + H((2)S)

The O((1)D) + H(2) --> OH + H reaction, which proceeds mainly as an insertion reaction at a collisional energy of 1.3 kilocalories per mole, has been investigated with the high-resolution H atom Rydberg "tagging" time-of-flight technique and the quasiclassical trajectory (QCT) method. Quantum state-resolved differential cross sections were measured for this prototype reaction. Different rotationally-vibrationally excited OH products have markedly different angular distributions, whereas the total reaction products are roughly forward and backward symmetric. Theoretical results obtained from QCT calculations indicate that this reaction is dominated by the insertion mechanism, with a small contribution from the collinear abstraction mechanism through quantum tunneling.     

Atmospheric hydroxyl radical production from electronically excited NO2 and H2O

Hydroxyl radicals are often called the "detergent" of the atmosphere because they control the atmosphere's capacity to cleanse itself of pollutants. Here, we show that the reaction of electronically excited nitrogen dioxide with water can be an important source of tropospheric hydroxyl radicals. Using measured rate data, along with available solar flux and atmospheric mixing ratios, we demonstrate that the tropospheric hydroxyl contribution from this source can be a substantial fraction (50%) of that from the traditional O(1D) + H2O reaction in the boundary-layer region for high solar zenith angles. Inclusion of this chemistry is expected to affect modeling of urban air quality, where the interactions of sunlight with emitted NOx species, volatile organic compounds, and hydroxyl radicals are central in determining the rate of ozone formation.     

Experimental and theoretical differential cross sections for a four-atom reaction: HD + OH → H₂O + D

Quantum dynamical theories have progressed to the stage in which state-to-state differential cross sections can now be routinely computed with high accuracy for three-atom systems since the first such calculation was carried out more than 30 years ago for the H + H(2) system. For reactions beyond three atoms, however, highly accurate quantum dynamical calculations of differential cross sections have not been feasible. We have recently developed a quantum wave packet method to compute full-dimensional differential cross sections for four-atom reactions. Here, we report benchmark calculations carried out for the prototypical HD + OH → H(2)O + D reaction on an accurate potential energy surface that yield differential cross sections in excellent agreement with those from a high-resolution, crossed-molecular beam experiment.     

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。     

Interception of excited vibrational quantum states by O2 in atmospheric association reactions

Bimolecular reactions in Earth's atmosphere are generally assumed to proceed between reactants whose internal quantum states are fully thermally relaxed. Here, we highlight a dramatic role for vibrationally excited bimolecular reactants in the oxidation of acetylene. The reaction proceeds by preliminary adduct formation between the alkyne and OH radical, with subsequent O(2) addition. Using a detailed theoretical model, we show that the product-branching ratio is determined by the excited vibrational quantum-state distribution of the adduct at the moment it reacts with O(2). Experimentally, we found that under the simulated atmospheric conditions O(2) intercepts ~25% of the excited adducts before their vibrational quantum states have fully relaxed. Analogous interception of excited-state radicals by O(2) is likely common to a range of atmospheric reactions that proceed through peroxy complexes.     

滴灌水肥一体化配施有机肥对土壤N2O排放与酶活性的影响

【目的】 通过在有机肥基础上增施不同量无机氮,研究滴灌水肥一体化条件下温室番茄土壤N₂O排放和脲酶（UR）、硝酸还原酶（NR）、亚硝酸还原酶（Ni R）以及羟胺还原酶（Hy R）活性的动态变化,分析各处理土壤N₂O排放特征及土壤UR、NR、Ni R和Hy R活性对土壤N₂O排放的影响,揭示在滴灌水肥一体化下N₂O排放过程机制。【方法】 试验共设CK（不施氮）、N1（200 kg·hm ^-2有机氮）、N2（200 kg·hm ^-2有机氮+ 250 kg·hm ^-2无机氮）、N3（200 kg·hm ^-2有机氮+ 475 kg·hm ^-2无机氮）4个处理。采用静态箱-气相色谱法,对番茄生育期内土壤N₂O排放、土壤酶活性、土壤温湿度等进行监测。【结果】 滴灌水肥一体化,各施氮处理均在施肥+灌溉后第1天出现N₂O排放高峰,随着时间推移不断下降,不同处理番茄整个生育期N₂O排放通量在0.98—1 544.79 μg·m ^-2·h ^-1。土壤N₂O排放总量差异显著,依次为N3（（7.13±0.11）kg·hm ^-2）>N2（（4.87±0.21）kg·hm ^-2）>N1（（2.54±0.17）kg·hm ^-2）>CK（（1.56±0.23）kg·hm ^-2）,与N3相比,处理N1、N2土壤N₂O排放总量分别降低了64.38%、31.70%。番茄生育期内N₂O季节排放特征明显,秋季高,冬季低。土壤氮素转化相关酶活性大致随施氮量的升高而增高。土壤N₂O排放通量与5 cm土壤温度、0—10 cm土层硝态氮含量、土壤NR活性及土壤Hy R活性均呈极显著正相关（P＜0.01）。【结论】 滴灌水肥一体化下,土壤微生物处于好气环境,土壤N₂O主要来自于硝化过程,减少了由反硝化过程所产生的N₂O排放。综合考虑番茄产量、品质、N₂O排放等因素,推荐北方温室秋冬茬番茄施用200 kg·hm ^-2有机氮+250 kg·hm ^-2无机氮,75 kg·hm ^-2 P₂O₅,450 kg·hm ^-2 K₂O较为适宜。     

邓恩桉胸径生长对模拟硫、氮复合沉降的响应

应用二次回归旋转设计方法,安排硫、氮复合沉降对邓恩桉幼林影响的模拟实验,研究邓恩桉幼龄林胸径增长量对模拟硫、氮复合沉降的响应。排除年龄生长的影响,建立邓恩桉胸径生长响应的回归方程:■=0.776 3+0.193 5x1-0.125 6x2-0.510 0x1x2-0.245 0x12-0.597 5x22,分析硫、氮复合沉降对胸径增长的影响。结果表明,硫编码值为0.394 9(纯硫为28.20 kg.hm-2.a-1)和氮编码值为-0.105 1(纯氮为64.78 kg.hm-2.a-1)时,邓恩桉胸径年增长量可望达到最大0.84 cm。     

Imaging nucleophilic substitution dynamics

Anion-molecule nucleophilic substitution (S(N)2) reactions are known for their rich reaction dynamics, caused by a complex potential energy surface with a submerged barrier and by weak coupling of the relevant rotational-vibrational quantum states. The dynamics of the S(N)2 reaction of Cl- + CH3I were uncovered in detail by using crossed molecular beam imaging. As a function of the collision energy, the transition from a complex-mediated reaction mechanism to direct backward scattering of the I- product was observed experimentally. Chemical dynamics calculations were performed that explain the observed energy transfer and reveal an indirect roundabout reaction mechanism involving CH3 rotation.     

施肥模式对菠萝产量及农田氧化亚氮排放的影响

为探究不同施肥模式下菠萝（Ananas comosus）种植地土壤氧化亚氮（N₂O）的排放特征,筛选出既高产又减少N₂O排放的施肥方法。本试验以热带地区菠萝农田为研究对象,设置不施肥（CK）、常规施肥（NPK）、减量单施化肥（INF）、无机肥+有机肥配施（INF+M）、无机肥+有机肥+缓控肥配施（INF+M+S）等5个处理,利用静态暗箱?气相色谱法对菠萝整个生育期土壤的N₂O排放特征进行监测,并分析不同施肥模式下土壤温度、土壤含水量、硝态氮和铵态氮对N₂O排放的影响及菠萝产量间的差异。结果表明:INF+M+S,INF+M和INF处理下的菠萝产量比NPK处理的分别增加16.77%、6.66%和6.53%,且INF+M+S显著高于NPK。整个菠萝生育期,N₂O累积排放量和平均通量表现为NPK>INF>INF+M>INF+M+S>CK,且处理间差异显著;N₂O排放强度依次为NPK>INF>INF+M>INF+M+S>CK,处理间也表现出显著差异;同时,INF+M+S处理的排放系数也显著低于其他施肥处理;相关性分析发现,土壤硝态氮和铵态氮含量与N₂O排放通量呈极显著正相关。INF+M+S处理能够显著提高菠萝产量,降低菠萝整个生育期农田N₂O的排放量与排放强度,可作为菠萝较优的施肥模式。     

碳氮源对灵芝液体发酵胞外糖肽产量的影响

为寻找适合灵芝胞外糖肽(EPSP)液体深层发酵工艺商业化生产的经济高效的培养基原料,在摇瓶水平上比较研究了不同类型的碳源和氮源(各6种)对灵芝胞外糖肽(EPSP)产量的影响。试验表明:玉米粉是最适合灵芝EPSP生产((2.664±0.801)g/L)和菌丝生长((4.559±0.150)g/L)的碳源;尿素是最适合灵芝EPSP生产((0.636±0.040)g/L)的氮源,豆粕粉则是最适合灵芝菌丝生长的氮源((2.222±0.256)g/L);玉米粉与豆粕粉组合是最适合灵芝EPSP生产((4.366±0.434)g/L)的碳氮源组合。本研究结果可为灵芝EPSP液体深层发酵工艺的工业化生产提供科学指导。     

在二氯甲烷溶液里〔Cu(CH_3CN)_4〕〔MF_6〕与碘化四丁铵的反应

在本实验中,研究了［Ｃｕ（ＣＨ３ＣＮ）４］［ＭＦ６］（Ｍ＝Ｍ０或Ｗ）与碘化四丁铵（Ｃ４Ｈ９）４ＮＩ在二氯甲烷（ＣＨ２Ｃｌ２）中的反应。研究结果表明,在ＣＨ２Ｃｌ２里,（Ｃ４Ｈ９）４ＮＩ未能把［Ｃｕ（ＣＨ３ＣＮ）４］［Ｍ０Ｆ６］和［Ｃｕ（ＣＨ３ＣＮ）４］［ＷＦ６］中的Ｍ０Ⅴ和ＷⅤ还原成Ｍ０Ⅳ和ＷⅣ盐。通过分析得知,反应产物是ＣｕＩ和（Ｃ４Ｈ９）４ＮＭＦ６,配位体ＣＨ３ＣＮ被解脱出来,反应中并没有产生Ｉ２。     

Understanding reactivity at very low temperatures: the reactions of oxygen atoms with alkenes

A remarkable number of reactions between neutral free radicals and neutral molecules have been shown to remain rapid down to temperatures as low as 20 kelvin. The rate coefficients generally increase as the temperature is lowered. We examined the reasons for this temperature dependence through a combined experimental and theoretical study of the reactions of O(3P) atoms with a range of alkenes. The factors that control the rate coefficients were shown to be rather subtle, but excellent agreement was obtained between the experimental results and microcanonical transition state theory calculations based on ab initio representations of the potential energy surfaces describing the interaction between the reactants.     

长期施用含氯化肥对稻-麦轮作体系土壤生物肥力的影响

【目的】氯是植物必需的微量营养元素,但是含氯化肥（氯化钾和氯化铵）中氯离子含量和盐指数都较高,关于长期施用含氯化肥对土壤肥力影响的研究较少,尤其对土壤生物肥力的影响未见报道。论文旨在明确长期施用含氯化肥土壤微生物群落结构和酶活性的变化,探明含氯化肥对土壤生物肥力的影响机理,为含氯化肥的科学施用和土壤肥力的保育提供依据。【方法】利用已开展22年的紫色土肥力与肥料效益长期定位试验,采集含氯处理（含氯化肥配合稻草还田,(NPK)Cl+S）与不含氯处理（NPK+S）、以及不施肥对照（CK）和单施化肥（NPK）的土壤,采用磷脂脂肪酸法（PLFA）研究土壤微生物群落结构,并分析含氯化肥对土壤微生物量、种类及土壤酶活性和作物产量的影响。【结果】长期施用含氯化肥显著降低了土壤脲酶、碱性磷酸酶、过氧化氢酶的活性,与等养分的不含氯处理（NPK+S）相比,含氯化肥(NPK)Cl+S稻季土壤脲酶、碱性磷酸酶、过氧化氢酶的活性分别降低为不含氯处理（NPK+S）的35.7%、18.0%、69.8%,麦季土壤分别降低为不含氯处理的31.6%、24.5%、75.6%。主成分分析表明,脲酶、碱性磷酸酶、过氧化氢酶作为土壤生物活性的综合评价指标优于酸性和中性磷酸酶、硝酸盐还原酶。PLFA分析表明,含氯处理微生物量和种类最低,比等养分不含氯处理PLFA生物量降低24.7%,比对照降低43.2%;施用含氯化肥显著影响了土壤微生物的组成及数量,G+细菌显著降低,对真菌和放线菌影响较小;微生物种群量的减少与含氯处理土壤pH降低和酶活性下降有关。长期施用含氯化肥作物产量有降低的趋势,含氯处理比等养分的不含氯处理水稻季产量和周年产量22年平均下降6.8%、3.3%。【结论】长期施用双氯化肥（氯化钾和氯化铵）引起了土壤微生物群落结构改变及土壤生物活性降低,并表现出一定的减产趋势。建议不要长期施用双氯化肥,尤其要避免长期施用氯离子含量高的氯化铵。     

Mechanisms of nitrogen dioxide reactions: initiation of lipid peroxidation and the production of nitrous Acid

The reactions of nitrogen dioxide with cyclohexene have been studied as a model for the reactions that occur between nitrogen dioxide in smoggy air and unsaturated fatty acids in pulmonary lipids. As predicted from earlier studies at high nitrogen dioxide concentrations, this gas reacts with cyclohexene predominantly by addition to the double bond at nitrogen dioxide concentrations of 1 percent (10,000 parts per million) to 40 percent in nitrogen; in the presence of air or oxygen, this reaction initiates the autoxidation of the alkene. However, at concentrations below 100 parts per million in nitrogen, nitrogen dioxide reacts with cyclohexene almost exclusively by abstraction of allylic hydrogen; this unexpected reaction also initiates the autoxidation of the alkene in the presence of oxygen or air, but it leads to the production of nitrous acid rather than of a product containing a nitro group attached to a carbon atom. The nitrous acid can react with amines to produce nitrosamines. Moreover, the nitrite ion produced by the hydrogen abstraction mechanism would be expected to diffuse throughout the body, unlike nitrated lipids that would be confined to the pulmonary cavity. These findings have been confirmed with methyl oleate, linoleate, and linolenate; some of the kinetic features of the nitrogen dioxide-initiated autoxidation of these unsaturated fatty acids have been studied.     

Theoretical study of geometric phase effects in the hydrogen-exchange reaction

The crossing of two electronic potential surfaces (a conical intersection) should result in geometric phase effects even for molecular processes confined to the lower surface. However, recent quantum simulations of the hydrogen exchange reaction (H + H2 --> H2 + H) have predicted a cancellation in such effects when product distributions are integrated over all scattering angles. We used a simple topological argument to extract reaction paths with different senses from a nuclear wave function that encircles a conical intersection. In the hydrogen-exchange reaction, these senses correspond to paths that cross one or two transition states. These two sets of paths scatter their products into different regions of space, which causes the cancellation in geometric phase effects. The analysis should generalize to other direct reactions.     

降低总氮测定中空白吸光值的研究

就碱性过硫酸钾消解紫外分光光度法测定总氮时空白吸光值过高的现象进行了研究，确定蒸馏水和K2S2O8纯度是影响试验结果的关键因素。选用普通蒸馏水双蒸去离子后的高纯水及纯度大于99．0％的进口K2S1O8或国产分析纯K2S2O8二次重结晶配制成的溶液，其余步骤参照国标介绍的方法，即可保证空白吸光值小于0.030。当蒸馏水和K2S2O8纯度不高时，适当改进试验的操作过程，如对所配碱性K2S2O8溶液加微量HCl（1＋9）处理、延长消解时间至50min、消解完取出比色管后迅速冷却等方法也可适当降低空白吸光值，但不能确保在0．030以下。消解仪器与分光光度计的不同对分析结果无显著影响。     

降低总氮测定中空白吸光值的研究

就碱性过硫酸钾消解紫外分光光度法测定总氮时空白吸光值过高的现象进行了研究,确定蒸馏水和K2S2O8纯度是影响试验结果的关键因素。选用普通蒸馏水双蒸去离子后的高纯水及纯度大于99．0％的进口K2S1O8或国产分析纯K2S2O8二次重结晶配制成的溶液,其余步骤参照国标介绍的方法,即可保证空白吸光值小于0.030。当蒸馏水和K2S2O8纯度不高时,适当改进试验的操作过程,如对所配碱性K2S2O8溶液加微量HCl（1＋9）处理、延长消解时间至50min、消解完取出比色管后迅速冷却等方法也可适当降低空白吸光值,但不能确保在0．030以下。消解仪器与分光光度计的不同对分析结果无显著影响。     

不同深施肥方式对稻田氨挥发及水稻产量的影响

为探讨减少农田氨排放的方法,探究不同深施肥方式对稻田氨挥发损失、氮素利用率及水稻产量的影响,为水稻合理施肥提供理论依据,在湖南省长沙市金井镇长沙农业环境观测站布置盆栽试验,试验设7个处理,分别为：N₀（不施化肥）、S300（传统氮肥撒施）、S210（减氮30%+传统氮肥撒施）、R5（减氮30%+条施,深度为5 cm）、R10（减氮30%+条施,深度为10 cm）、B5（减氮30%+大颗粒球肥深施,深度为5 cm）、B10（减氮30%+大颗粒球肥深施,深度为10 cm）。施肥后第1 d进行氨挥发连续性监测,直至施肥处理氨排放量与不施肥处理无明显差异为止,并在水稻成熟期测定氮含量和产量。结果表明,深施处理可降低田面水铵态氮浓度,促进植株氮素吸收。与S300处理相比,氨挥发损失量降低了30.13%~47.85%。与S210处理相比,深施处理氮素回收率（NRE）提高了9.16%~29.44%;氮素农艺利用效率（NAE）增加了13.85%~32.14%;籽粒生产效率（NGPE）增加了12.18%~28.27%。在减氮30%的基础上,深施处理水稻产量较S210处理增加了12.79%~28.27%,其中B10处理显著减少氨挥发损失量并提高氮素利用率。这说明深施处理有效降低了稻田氨挥发损失,提高了氮素利用率,其中以B10处理（减氮30%+10 cm大颗粒球肥深施）效果最佳;同时深施肥的机械化需要进一步研发和推广。     

Simulations of Gas-Phase Chemical Reactions: Applications to SN2 Nucleophilic Substitution

Computer simulations and animations of the motion of atoms as a chemical reaction proceeds give a detailed picture of how the reaction occurs at a microscopic level. This information is particularly useful for testing the accuracy of statistical models, which are used to calculate various attributes of chemical reactions. Such simulations and animations, in concert with experimental and ab initio studies, have begun to provide a microscopic picture of the intimate details of a particular class of gas-phase ion-molecule bimolecular reactions known as S(N)2 nucleophilic substitution. In these reactions, a nucleophile is displaced from a molecule by another nucleophile. The dynamical model of S(N)2 reactions that emerges from the computer studies, and its relation to statistical theories, is discussed here.