Theoretical studies of the energetics and dynamics of chemical reactions

Computational studies of basic chemical processes not only provide numbers for comparison with experiment or for use in modeling complex chemical phenomena such as combustion, but also provide insight into the fundamental factors that govern molecular structure and change which cannot be obtained from experiment alone. We summarize the results of three case studies, on HCO, OH + H(2), and O + C(2)H(2), which illustrate the range of problems that can be addressed by using modern theoretical techniques. In all cases, the potential energy surfaces were characterized by using ab initio electronic structure methods. Collisions between molecules leading to reaction or energy transer were described with quantum dynamical methods (HCO), classical trajectory techniques (HCO and OH + H(2)), and statistical methods (HCO, OH + H(2), and O + C(2)H(2)). We can anticipate dramatic increases in the scope of this work as new generations of computers are introduced and as new chemistry software is developed to exploit these computers.     

Measurement of fast biochemical reactions

In the 4 years since Hammes (87) reviewed, in this journal, the application of flow and relaxation techniques to the study of primary processes in chemical reactions these methods have been applied to a wide range of biochemical problems. These applications have been facilitated by advances in stopped flow and temperature jump instrumentation, especially with respect to the range of physical properties that may be observed during a reaction, and the availability of instruments.     

Laser probing of chemical reaction dynamics

Lasers are used in increasingly sophisticated ways to carry out reactions between molecules in selected vibrational, rotational, and electronic states and to probe the product states of chemical reactions. Such investigations are providing unprecedented insights into chemical reaction dynamics, the study of the detailed motions that molecules undergo in simple chemical reactions. In many cases it is possible to describe the influence that specific types of molecular excitation have on reactive events. Experiments are also being carried out to leam about chemical reactivity as a function of the alignment of reagents. There is increasing excitement concerning the potential of laser methods to interrogate the transition states of molecular reactions.     

Gas-phase ionic reactions: dynamics and mechanism of nucleophilic displacements

Nucleophilic displacement reactions (the SN2 reaction) of ions in the gas phase are a prototypical reaction system that allows a study of dynamics, mechanisms, and structure-energy relations. This article reviews aspects of the kinetics (especially the applicability of statistical reaction rate theory), the relation of structure and reactivity, and the effects of small numbers of solvent molecules on the reaction and compares the behavior of the ionic reaction in the gas phase with that in solution.     

Photochemical reactions and the chemical evolution of purines and nicotinamide derivatives

The photochemical rearrangement of a tetramer of hydrogen cyanide to 4-aminoimidazole-5-carbonitrile, a critical step in the proposed prebiotic synthesis of purines, proceeds in high yield in the absence of oxygen without photodestruction of the reaction product. The mechanism of the rearrangement involves the conversion of the excited singlet of the hydrogen cyanide tetramer to 2-imino-3-cyano-4-aminoazetine, which then rearranges to the imidazole product. The photolysis of the vinylogous enaminonitrile 1,3-dicyano4-amino-1,3-butadiene yields 6-aminonicotinonitrile. The latter reaction affords an efficient route to a nicotinamide derivative from cyanoacetylene.     

某化工废水五日生化需氧量实验

采用水质指标评价法测定某化工厂废水的可生化性,其中COD_(Cr)测定采用在线监测,BOD_5测定采用稀释接种法。通过各构筑物的水样实验,得到结论:稀释接种法适用于该化工废水BOD_5的测定,可用水质指标法判定该废水的可生化性;采样及测定过程中产生的气泡对BOD_5的测定结果有影响,需对待测水样中的气泡进行处理后才能有效保证实验结果的准确性,否则会使BOD_5/COD_(Cr)偏大;当待测水样初始溶解氧浓度较低时,需要进行曝气处理,否则会使BOD_5/COD_(Cr)偏小,且最佳曝气时间为15 min。     

快速城市化地区景观生态安全时空演化过程分析——以东莞市为例

依托“压力-状态-响应”概念框架模型,建立景观生态安全评价指标体系,以东莞市为例,研究区域景观生态安全时空发展变化过程,揭示快速城市化地区生态安全发展变化的规律.结果表明:1988、1997和2005年东莞市的平均生态安全综合指数分别为0.497、0.436和0.395,区域总体生态安全从中高安全状态逐步降低到中低安全状态;生态中低安全的区域空间上从“市中心-镇中心”沿“市中心-镇中心-道路”不断扩张.采用以像元为中心的公里网格滑动模板的指标作为像元的评价指标,可以有效解决景观结构指数等指标的计算,在生态安全等级划分时边界过度很平滑,景观尺度的生态安全评价可以为生态可持续发展政策的制定提供科学依据.     

化学农药对家蚕生理生化影响的研究进展

家蚕是农业生态系统中重要的非靶标生物代表之一,同时也是重要的经济昆虫.本文综述了化学农药对家蚕生长发育、血淋巴中能源物质、血细胞、体内酶活及激素变化等主要生理生化指标的影响.     

Geckos: adaptive significance and energetics of tail autotomy

Coleonyx variegatus is adapted to readily sacrifice its tail to predators. This adaptation is associated with characteristic tail behavior and rapid tail regeneration. There is no facultative metabolic increase associated with tail regeneration, and energy normally allocated to body growth and maintenance is diverted to tail regeneration. This supports the contention that tail behavior, autotomy, and rapid regeneration evolved as mechanisms promoting survival in terms of predator escape.     

Partitioning the energetics of walking and running: swinging the limbs is expensive

Explaining the energetics of walking and running has been difficult because the distribution of energy use among individual muscles has not been known. We estimated energy use by measuring blood flow to the hindlimb muscles in guinea fowl. Blood flow to skeletal muscles is controlled locally and varies directly with metabolic rate. We estimate that the swing-phase muscles consume 26% of the energy used by the limbs and the stance-phase muscles consume the remaining 74%, independent of speed. Thus, contrary to some previous suggestions, swinging the limbs requires an appreciable fraction of the energy used during terrestrial legged locomotion. Models integrating the energetics and mechanics of running will benefit from more detailed information on the distribution of energy use by the muscles.     

Diffusion of weak acids across lipid bilayer membranes: effects of chemical reactions in the unstirred layers

Chemical reactions in the aqueous unstirred layers of solution adjacent to a membrane can have dramatic effects on the diffusion of solutes across that membrane. This is demonstrated by the diffusion of labeled salicylate and salicylic acid across a phospholipid bilayer membrane. Two types of chemical reactions are considered. The first is an isotopic exchange reaction between the ionic and nonionic forms of a weak acid, HA + *A(-) [unknown] H*A + A(-). This reaction provides a way of estimating the true membrane permeability to a highly permeant weak acid and also a way of estimating the thickness of the unstirred layers. The second chemical reaction, the dissociation of a weak acid, HA [unknown] H(+) + A(-), can be used to show how the presence or absence of buffers in the unstirred layers controls the net transport of permeant weak acids across a membrane. In principle, the addition of appropriate "antacid" buffers to salicylates can increase their rate of absorption from the stomach.     

Probing chemical reactions: evidence for exploration of an excited potential energy surface at thermal energies

The reaction K + NaBr --> KBr + Na is probed during the reactive collision by a continuous wave laser tuned to frequencies not resonant with excitation in either reagents or products. Transient [K..Br..Na] absorbs a laser photon giving [K..Br..Na](*), which can decompose to Na(*) + KBr. Emission from excited Na(*) at the sodium D lines provides direct evidence of laser absorption during the reaction. Different excitation spectra were observed, depending on which sodium D line was monitored. This difference is explicable if, in the absence of the laser, the reaction flux partially bifurcates to a second potential energy surface during the reaction.     

豇豆荚螟在北京地区红小豆田为害消长规律及药剂防治

采用田间普查、定点调查和灯光诱集的方法明确了北京地区豇豆荚螟Marucavitrata发生特点及其在红小豆田的种群消长规律,采用田间药效试验筛选出防治该虫的有效药剂.结果表明,豇豆螟幼虫共有5个龄期,低龄幼虫喜食红小豆细嫩的花蕊,造成落花、落蕾.幼虫钻入豆荚时取食红小豆种子,有转荚为害习性.成虫对黑光灯和高压汞灯趋性不明显.北京地区豇豆荚螟发生为害开始于红小豆的始花期,集中在红小豆盛花期,豆花、豆荚上的幼虫数量在8月末达到高峰.田间药效筛选试验结果表明,当红小豆田中的豇豆荚螟幼虫数在防治指标（百花/荚虫数5～6头）以上时,稀释1000倍液的5％氯虫苯甲酰胺防治红小豆田豇豆荚螟幼虫效果明显优于常规药剂高氯甲维盐和阿维菌素,而且持效期在20d以上,具有明显的保花护荚作用.     

In vivo Ca2+ dynamics in a cricket auditory neuron: an example of chemical computation

Fura-2 calcium imaging in the cricket omega neuron revealed increased intracellular free calcium ion concentration in response to simulated cricket calling songs and other sound stimuli. The time course of the increase and decrease in intracellular calcium coincided with the time course of forward masking, a time-dependent modulation of auditory sensitivity. The buffering of calcium transients with high concentrations of a kinetically fast calcium buffer eliminated the post-stimulus hyperpolarization associated with forward masking, whereas the uncaging of calcium inside the neuron produced a hyperpolarization. The results suggest that sound-stimulated intracellular calcium accumulation acts by means of a calcium-activated hyperpolarizing current to produce forward masking. These findings underscore the importance of chemical dynamics in neural computation by demonstrating a behaviorally relevant role of calcium dynamics in vivo.