Vibrational promotion of electron transfer

By using laser methods to prepare specific quantum states of gas-phase nitric oxide molecules, we examined the role of vibrational motion in electron transfer to a molecule from a metal surface free from the complicating influence of solvation effects. The signature of the electron transfer process is a highly efficient multiquantum vibrational relaxation event, where the nitrogen oxide loses hundreds of kilojoules per mole of energy on a subpicosecond time scale. These results cannot be explained simply on the basis of Franck-Condon factors. The large-amplitude vibrational motion associated with molecules in high vibrational states strongly modulates the energetic driving force of the electron transfer reaction. These results show the importance of molecular vibration in promoting electron transfer reactions, a class of chemistry important to molecular electronics devices, solar energy conversion, and many biological processes.     

Reaction product imaging: the h + d2 reaction

The differential cross section for the H + D(2) --> HD + D reaction has been measured using a technique called reaction product imaging. In this experiment, a photolytically produced beam of hydrogen (H) atoms crossed a beam of cold deuterium (D(2)) molecules. Product D atoms were ionized at the intersection of the two particle beams and accelerated toward a position-sensitive detector. The ion images appearing on the detector are two-dimensional projections of the three-dimensional velocity distribution of the D atom products. The reaction was studied at nominal center-of-mass collision energies of 0.54 and 1.29 electron volts. At the lower collision energy, the measured differential cross section for D atom production, summed over all final states of the HD(v,J) product, is in good agreement with recent quasi-classical trajectory calculations. At the higher collision energy, the agreement between the theoretical predictions and experimental results is less favorable.     

Attosecond control and measurement: lightwave electronics

Electrons emit light, carry electric current, and bind atoms together to form molecules. Insight into and control of their atomic-scale motion are the key to understanding the functioning of biological systems, developing efficient sources of x-ray light, and speeding up electronics. Capturing and steering this electron motion require attosecond resolution and control, respectively (1 attosecond = 10(-18) seconds). A recent revolution in technology has afforded these capabilities: Controlled light waves can steer electrons inside and around atoms, marking the birth of lightwave electronics. Isolated attosecond pulses, well reproduced and fully characterized, demonstrate the power of the new technology. Controlled few-cycle light waves and synchronized attosecond pulses constitute its key tools. We review the current state of lightwave electronics and highlight some future directions.     

Electronically induced atom motion in engineered CoCun nanostructures

We have measured the quantum yield for exciting the motion of a single Co atom in CoCu(n) linear molecules constructed on a Cu(111) surface. The Co atom switched between two lattice positions during electron excitation from the tip of a scanning tunneling microscope. The tip location with highest probability for inducing motion was consistent with the position of an active state identified through electronic structure calculations. Atom motion within the molecule decreased with increased molecular length and reflected the corresponding variation in electronic structure.     

Ultrafast interfacial proton-coupled electron transfer

The coupling of electron and nuclear motions in ultrafast charge transfer at molecule-semiconductor interfaces is central to many phenomena, including catalysis, photocatalysis, and molecular electronics. By using femtosecond laser excitation, we transferred electrons from a rutile titanium dioxide (110) surface into a CH3OH overlayer state that is 2.3 +/- 0.2 electron volts above the Fermi level. The redistributed charge was stabilized within 30 femtoseconds by the inertial motion of substrate ions (polaron formation) and, more slowly, by adsorbate molecules (solvation). According to a pronounced deuterium isotope effect (CH3OD), this motion of heavy atoms transforms the reverse charge transfer from a purely electronic process (nonadiabatic) to a correlated response of electrons and protons.     

Time-resolved holography with photoelectrons

Ionization is the dominant response of atoms and molecules to intense laser fields and is at the basis of several important techniques, such as the generation of attosecond pulses that allow the measurement of electron motion in real time. We present experiments in which metastable xenon atoms were ionized with intense 7-micrometer laser pulses from a free-electron laser. Holographic structures were observed that record underlying electron dynamics on a sublaser-cycle time scale, enabling photoelectron spectroscopy with a time resolution of almost two orders of magnitude higher than the duration of the ionizing pulse.     

Quantum theory of chemical reaction dynamics

It is now possible to use rigorous quantum scattering theory to perform accurate calculations on the detailed state-to-state dynamics of chemical reactions in the gas phase. Calculations on simple reactions, such as H + D2 --> HD + D and F + H2 --> HF + H, compete with experiment in their accuracy. Recent advances in theory promise to extend such accurate predictions to more complicated reactions, such as OH + H2 --> H2O + H, and even to reactions of molecules on solid surfaces. New experimental techniques for probing reaction transition states, such as negative-ion photodetachment spectroscopy and pump-probe femtosecond spectroscopy, are stimulating the development of new theories.     

Cell type-specific loss of BDNF signaling mimics optogenetic control of cocaine reward

The nucleus accumbens is a key mediator of cocaine reward, but the distinct roles of the two subpopulations of nucleus accumbens projection neurons, those expressing dopamine D1 versus D2 receptors, are poorly understood. We show that deletion of TrkB, the brain-derived neurotrophic factor (BDNF) receptor, selectively from D1+ or D2+ neurons oppositely affects cocaine reward. Because loss of TrkB in D2+ neurons increases their neuronal excitability, we next used optogenetic tools to control selectively the firing rate of D1+ and D2+ nucleus accumbens neurons and studied consequent effects on cocaine reward. Activation of D2+ neurons, mimicking the loss of TrkB, suppresses cocaine reward, with opposite effects induced by activation of D1+ neurons. These results provide insight into the molecular control of D1+ and D2+ neuronal activity as well as the circuit-level contribution of these cell types to cocaine reward.     

Imaging of single organic molecules in motion

High-resolution transmission electron microscopy revealed nearly atomically precise images of stepping conformational change and translational motion of single hydrocarbon molecules confined in carbon nanotubes. One or two C12 or C22 alkyl chains were tethered to a carborane end group and then embedded in the nanotubes. Images of the hydrocarbon chains interacting with each other and with a graphitic surface provide information on three-dimensional structures and dynamic molecular interactions that cannot be obtained by other analytical methods.     

The future of attosecond spectroscopy

Attoscience is the study of physical processes that occur in less than a fraction of a cycle of visible light, in times less than a quadrillionth of a second. The motion of electrons inside atoms and molecules that are undergoing photoionization or chemical change falls within this time scale, as does the plasma motion that causes the reflectivity of metals. The techniques to study motion on this scale are based on careful control of strong-field laser-atom interactions. These techniques and new research opportunities in attosecond spectroscopy are reviewed.     

多菌种联合发酵饲料对肉鸡抗沙门氏菌感染能力的影响

旨在探明发酵饲料对肉鸡抗沙门氏菌感染的影响。将50只1日龄中速黄羽肉鸡随机分为5个处理组,对照组、模型对照组饲喂基础饲粮(基础日粮+10%未发酵饲料),抗生素对照组在基础饲粮中添加20 mg·kg^-1硫酸粘杆菌素,5%发酵组、10%发酵组分别用5%、10%发酵饲料替代基础饲粮中的未发酵饲料。肉鸡13日龄时,对照组连续2 d口腔灌服400 μL无菌水,其他组连续2 d口腔灌服400 μL沙门氏菌液(1×10⁹ CFU·mL^-1)。肉鸡15日龄时进行屠宰,取血清测定促炎因子(IL-1β、IL-6、TNF-α)、内毒素(LPS)、D-乳酸(D-LA)水平,取结肠进行HE染色观察结肠形态,取结肠黏膜测定TLR4路径关键信号分子的基因表达量。结果表明,沙门氏菌感染导致肉鸡血清促炎因子(IL-1β、IL-6、TNF-α)水平显著上升,TLR4信号通路中的关键信号分子(TLR4、MyD88、TRAF6、NF-κB)mRNA相对表达量显著上升,血清LPS、D-LA水平显著上升,而抗生素组、5%发酵组、10%发酵组的这些指标均有不同程度的改善,表明多菌种联合发酵饲料能够改善沙门氏菌感染导致的炎症反应和肠道屏障受损,效果接近20 mg·kg^-1硫酸粘杆菌素。     

Dual signaling regulated by calcyon, a D1 dopamine receptor interacting protein

The synergistic response of cells to the stimulation of multiple receptors has been ascribed to receptor cross talk; however, the specific molecules that mediate the resultant signal amplification have not been defined. Here a 24-kilodalton single transmembrane protein, designated calcyon, we functionally characterize that interacts with the D1 dopamine receptor. Calcyon localizes to dendritic spines of D1 receptor-expressing pyramidal cells in prefrontal cortex. These studies delineate a mechanism of Gq- and Gs-coupled heterotrimeric GTP-binding protein-coupled receptor cross talk by which D1 receptors can shift effector coupling to stimulate robust intracellular calcium (Ca2+i) release as a result of interaction with calcyon. The role of calcyon in potentiating Ca2+-dependent signaling should provide insight into the D1 receptor-modulated cognitive functions of prefrontal cortex.     

Partial control of an ion-molecule reaction by selection of the internal motion of the polyatomic reagent ion

The ion-molecule reaction NH(3)(+) + ND(3) has been studied at various collision energies (1 to 5 electron volts in the center of mass) with preparation of the NH(3)(+) reagent in two nearly isoenergetic vibrational states. One state corresponds to pure out-of-plane bending of the planar NH(3)(+) ion (0.60 electron volts), whereas the other state is a combination of in-plane and out-of-plane motion (0.63 electron volts). The product branching ratios differ markedly for these two vibrational-state preparations. The differences in reactivity suggest that the in-plane totally symmetric stretching mode is essentially inactive in controlling the branching ratio of this reaction.     

Observation of large water-cluster anions with surface-bound excess electrons

Anionic water clusters have long been studied to infer properties of the bulk hydrated electron. We used photoelectron imaging to characterize a class of (H2O)n- and (D2O)n- cluster anions (n 相似文献   

Electron solvation in finite systems: femtosecond dynamics of iodide. (Water)n anion clusters

Electron solvation dynamics in photoexcited anion clusters of I-(D2O)n=4-6 and I-(H2O)4-6 were probed by using femtosecond photoelectron spectroscopy (FPES). An ultrafast pump pulse excited the anion to the cluster analog of the charge-transfer-to-solvent state seen for I- in aqueous solution. Evolution of this state was monitored by time-resolved photoelectron spectroscopy using an ultrafast probe pulse. The excited n = 4 clusters showed simple population decay, but in the n = 5 and 6 clusters the solvent molecules rearranged to stabilize and localize the excess electron, showing characteristics associated with electron solvation dynamics in bulk water. Comparison of the FPES of I-(D2O)n with I-(H2O)n indicates more rapid solvation in the H2O clusters.     

复合免疫增强剂对刺参生长和非特异性免疫酶活性的影响

为研究不同复合免疫增强剂对刺参Apostichopus japonicus非特异性免疫酶的影响,试验设置正常对照组(A组)、芽孢杆菌+壳寡糖+刺五加等中草药组(B组)、芽孢杆菌+壳寡糖+百合等中草药组(C组)、芽孢杆菌+壳寡糖+大黄等中草药组(D组)、芽孢杆菌+壳寡糖+黄芪等中草药组(E组)、芽孢杆菌+壳寡糖组(F组)、壳寡糖组(G组)和芽孢杆菌组(H组)8组,通过在饲料中添加中草药、芽孢杆菌和壳寡糖,研究了芽孢杆菌、壳寡糖和中草药对体质量为(3.87±0.54)g的刺参幼参生长及其酸性磷酸酶(ACP)、碱性磷酸酶(AKP)、溶菌酶(LZM)、超氧化物歧化酶(SOD)等非特异性免疫酶活力的影响。结果表明:投喂芽孢杆菌、壳寡糖和中草药制剂均促进了刺参的生长,各试验组刺参的增重率和特定生长率均显著高于对照组(P0.05),其中,D和E组均显著高于其他试验组(P0.05);在饲料中添加不同配伍的复合免疫增强剂对AKP活力无显著性影响(P0.05);投喂50 d后,C、D、E组ACP活力显著高于对照组(P0.05);投喂50 d后,除H组外,其他试验组SOD活力均显著高于对照组(P0.05),其中B、C和D组SOD活力较高;投喂50 d后,除G组外,其他试验组LZM活力均显著高于对照组(P0.05)。研究表明,饲料中共同添加芽孢杆菌、壳寡糖和中草药复合免疫增强剂能进一步提高刺参非特异性免疫酶活力,其中C、D和E试验组均能提高刺参的非特异性免疫力,且C组效果最好。     

4D visualization of transitional structures in phase transformations by electron diffraction

Complex systems in condensed phases involve a multidimensional energy landscape, and knowledge of transitional structures and separation of time scales for atomic movements is critical to understanding their dynamical behavior. Here, we report, using four-dimensional (4D) femtosecond electron diffraction, the visualization of transitional structures from the initial monoclinic to the final tetragonal phase in crystalline vanadium dioxide; the change was initiated by a near-infrared excitation. By revealing the spatiotemporal behavior from all observed Bragg diffractions in 3D, the femtosecond primary vanadium-vanadium bond dilation, the displacements of atoms in picoseconds, and the sound wave shear motion on hundreds of picoseconds were resolved, elucidating the nature of the structural pathways and the nonconcerted mechanism of the transformation.     

小豆生长发育规律的研究——Ⅷ 小豆短日处理的效应

研究表明:1)在(8L+16D)-(12L+12D)条件下的短日处理对小豆有抑制营养器官生长、促进生殖器官分化的作用,而且苗龄越大处理效果越显著;本试验结果表明,选用(10L+14D)处理诱导25天左右,可使晚熟生态类型小豆植株加快其生殖器官的分化,提早开花,又不致于植株过分早衰,进而提高杂交育种的工作效率.2)晚熟品种在(10L+14D)的短日诱导下,短日有效诱导周期最短为15-17天,最长为30-32天,短日处理停止后恢复自然日照(13小时以上),其植株又重新进入营养生长(称逆转),在南京地区8月下旬再一次进入生殖生长(即花芽分化).短日诱导时间愈长,其植株逆转愈加困难.     

Quantum criticality: competing ground states in low dimensions

Small changes in an external parameter can often lead to dramatic qualitative changes in the lowest energy quantum mechanical ground state of a correlated electron system. In anisotropic crystals, such as the high-temperature superconductors where electron motion occurs primarily on a two-dimensional square lattice, the quantum critical point between two such lowest energy states has nontrivial emergent excitations that control the physics over a significant portion of the phase diagram. Nonzero temperature dynamic properties near quantum critical points are described, using simple theoretical models. Possible quantum phases and transitions in the two-dimensional electron gas on a square lattice are discussed.     

Seemingly anomalous angular distributions in H + D₂ reactive scattering

When a hydrogen (H) atom approaches a deuterium (D(2)) molecule, the minimum-energy path is for the three nuclei to line up. Consequently, nearly collinear collisions cause HD reaction products to be backscattered with low rotational excitation, whereas more glancing collisions yield sideways-scattered HD products with higher rotational excitation. Here we report that measured cross sections for the H + D(2) → HD(v' = 4, j') + D reaction at a collision energy of 1.97 electron volts contradict this behavior. The anomalous angular distributions match closely fully quantum mechanical calculations, and for the most part quasiclassical trajectory calculations. As the energy available in product recoil is reduced, a rotational barrier to reaction cuts off contributions from glancing collisions, causing high-j' HD products to become backward scattered.