Linear response breakdown in solvation dynamics induced by atomic electron-transfer reactions

The linear response (LR) approximation, which predicts identical relaxation rates from all nonequilibrium initial conditions that relax to the same equilibrium state, underlies dominant models of how solvation influences chemical reactivity. We experimentally tested the validity of LR for the solvation that accompanies partial electron transfer to and from a monatomic solute in solution. We photochemically prepared the species with stoichiometry Na0 in liquid tetrahydrofuran by both adding an electron to Na+ and removing an electron from Na-. Because atoms lack nuclear degrees of freedom, ultrafast changes in the Na0 absorption spectrum reflected the solvation that began from our two initial nonequilibrium conditions. We found that the solvation of Na0 occurs more rapidly from Na+ than Na-, constituting a breakdown of LR. This indicates that Marcus theory would fail to describe electron-transfer processes for this and related chemical systems.     

Steric effects and solvent effects in ionic reactions

Rates of SN2 reactions of chloride ion with methyl- and tert-butyl-substituted chloroacetonitrile were measured by using Fourier transform-ion cyclotron resonance spectrometry to follow the isotopic exchange reaction. Barrier heights for these reactions indicate that steric effects in the gas phase are diminished relative to apparent steric effects in solution. We attribute the increased barrier in solution to a solvation effect. Monte Carlo simulations done using statistical perturbation theory confirm that steric hindrance to solvation contributes to SN2 barriers in solution.     

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.     

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.     

Time-resolved photoacoustic calorimetry: probing the energetics and dynamics of fast chemical and biochemical reactions

Time-resolved photoacoustic calorimetry is a new experimental technique that measures the dynamics of enthalpy changes on the time scale of nanoseconds to microseconds for reactions initiated by absorption of light. When the reaction is carried out in water, it is also possible to obtain the dynamics of the corresponding volume changes. This method has been applied to a variety of biochemical, organic, and organometallic reactions.     

Polar coronal holes and cosmic-ray modulation

A comparison of the size of polar coronal holes with the cosmic-ray intensity observed during the most recent sunspot cycle shows close correspondence. This lends support to recent suggestions that the well-known sunspot-cycle modulation of cosmic rays is a three-dimensional effect, probably related to the global character of the interplanetary magnetic field.     

The nature of aqueous tunneling pathways between electron-transfer proteins

Structured water molecules near redox cofactors were found recently to accelerate electron-transfer (ET) kinetics in several systems. Theoretical study of interprotein electron transfer across an aqueous interface reveals three distinctive electronic coupling mechanisms that we describe here: (i) a protein-mediated regime when the two proteins are in van der Waals contact; (ii) a structured water-mediated regime featuring anomalously weak distance decay at relatively close protein-protein contact distances; and (iii) a bulk water-mediated regime at large distances. Our analysis explains a range of otherwise puzzling biological ET kinetic data and provides a framework for including explicit water-mediated tunneling effects on ET kinetics.     

Polar temperature of venus

The presence of substantial polar cooling of Venus, as derived from microwave interferometry at 10.6 cm wavelength, is shown to be open to doubt. Other microwave measurements give little evidence for significant pole-ward variation in temperature on the planet.     

Gaussian free-energy dependence of electron-transfer rates in iridium complexes

The kinetics of photoinduced electron-transfer (ET) reactions have been measured in a series of synthetic donor-acceptor complexes. The electron donors are singlet or triplet excited iridium(I) dimers (Ir(2)), and the acceptors are N-alkylpyridinium groups covalently bound to phosphinite ligands on the Ir(2) core. Rate constants for excited-state ET range from 3.5 x 10(6) to 1.1 x 10(11) per second, and thermal back ET (pyridinium radical to Ir(2)(+)) rates vary from 2.0 x 10(10) to 6.7 x 10(7) per second. The variation of these rates with driving force is in remarkably good agreement with the Marcus theory prediction of a Gaussian free-energy dependence.     

猪极体的保存研究

将从屠宰场采集的猪卵巢卵母细胞进行体外成熟培养和体外受精,得到猪第一极体和第二极体.通过形态学观察和台盼蓝染色,探讨不同保存温度(39 ℃、4 ℃、-20 ℃、-196 ℃)下猪第一极体和第二极体的存活情况.试验结果表明:随着保存温度的降低,猪第一极体和第二极体的存活率随之升高.第一、二极体在39 ℃条件下大都在几小时内发生退化;4 ℃条件下保存40 h存活率为70%～80%;-20 ℃保存7 d时存活率达90%以上;而在液氮中保存1个月时,第一极体和第二极体的存活率仍接近90%.     

Polar wandering on Mars?

Polar wandering during the past 10(8) years may be recorded by unique quasi-circular structures in the polar regions of Mars. Polar wandering on Mars is likely if deep convection is involved in the origin of the very large constructional volcanic features located near the equator. The magnitude of the nonhydrostatic low order components of the gravity field and their correlation with the equatorial volcanic features may be additional evidence of deep convection and associated polar wandering.     

Polar lightning and decadal-scale cloud variability on Jupiter

Although lightning has been seen on other planets, including Jupiter, polar lightning has been known only on Earth. Optical observations from the New Horizons spacecraft have identified lightning at high latitudes above Jupiter up to 80 degrees N and 74 degrees S. Lightning rates and optical powers were similar at each pole, and the mean optical flux is comparable to that at nonpolar latitudes, which is consistent with the notion that internal heat is the main driver of convection. Both near-infrared and ground-based 5-micrometer thermal imagery reveal that cloud cover has thinned substantially since the 2000 Cassini flyby, particularly in the turbulent wake of the Great Red Spot and in the southern half of the equatorial region, demonstrating that vertical dynamical processes are time-varying on seasonal scales at mid- and low latitudes on Jupiter.     

Polar lipids of archaebacteria in sediments and petroleums

Glycerol tetraethers with head-to-head isoprenoid 40-carbon chains that are typical of archaebacteria, in particular of methanogens, were identified in the polar lipids of sediments and petroleums. These structures are at least partially preserved in the subsurface beyond the stage of petroleum formation. Their identification provides further evidence that a significant part of geological organic matter derives from the lipids of membranes of microorganisms.     

土壤中含氧、含硫极性化合物预处理方法研究

甲醇作为抽提溶剂可以增加芳烃、非烃以及沥青质的抽提效率,对沥青质抽提效果尤为明显。采用二氯甲烷-甲醇(v/v,7∶1)作为土壤中含氧、含硫极性化合物预处理的抽提溶剂,并且在进行土壤有机抽提物族组分分离时,最后增加1ml甲酸淋滤,明显增加了酸性非烃化合物的回收量。利用层析柱进行族组分分离作为土壤样品有机物的预处理方法,具有较好的回收率,既不影响饱和烃组分和芳烃组分的检测,同时能对土壤中含氧、含硫极性化合物进行定性和定量分析。