Supramolecular chemistry: receptors, catalysts, and carriers

Supramolecular chemistry is the study of the structures and functions of the supermolecules that result from binding substrates to molecular receptors. Macropolycyclic receptors and coreceptors have been designed that form cryptate inclusion complexes and display molecular recognition towards spherical, tetrahedral, and linear substrates of various kinds (metal cations, inorganic anions, and organic or biological cations or anions). Anion binding has led to the development of anion coordination chemistry. Metalloreceptors simultaneously bind organic molecules and metal ions; speleands combine polar and nonpolar binding subunits. Receptors bearing reactive functional groups may act as molecular reagents or catalysts, performing a chemical transformation on the bound substrates (by such reactions as hydrogen transfer, ester cleavage, and protoadenosinetriphosphatase and protokinase activities). Receptors fitted with lipophilic groups can operate as molecular carriers, translocating bound species through a membrane; this transport can be coupled to chemical potentials (proton and redox gradients).     

Ionosphere of venus: first observations of the dayside ion composition near dawn and dusk

The first in situ measurements of the composition of the ionosphere of Venus are provided by independent Bennett radio-frequency ion mass spectrometers on the Pioneer Venus bits and orbiter spacecraft, exploring the dawn and duskside regions, respectively. An extensive composition of ion species, rich in oxygen, nitrogen, and carbon chemistry is idenitified. The dominant topside ion is O(+), with C(+), N(+), H(+), and He(+) as prominent secondary ions. In the lower ionosphere, the ionzization peak or F(1) layer near 150 kilometers reaches a concentration of about 5 x l0(3) ions per cubic centimeter, and is composed of the dominant molecular ion, O(2)(+), with NO(+), CO(+), and CO(2)(+), constituting less than 10 percent of the total. Below the O(+) peak near 200 kilometers, the ions exhibit scale heights consistent with a neutral gas temperature of about 180 K near the terminator. In the upper ionosphere, scale heights of all species reflect the effects of plasma transport, which lifts the composition upward to the often abrupt ionopause, or thermal ion boundary, which is observed to vary in height between 250 to 1800 kilometers, in response to solar wind dynamics.     

Protonated Ozone: Experimental Detection of O3H+ and Evaluation of the Proton Affinity of Ozone

The elusive protonated ozone ion (O(3)H(+)) has been long postulated as a reactive intermediate but never experimentally observed. This ion has been detected here in mass spectrometric experiments with the use of Fourier transform ion cyclotron resonance. In these experiments, ozone (O(3)) was protonated by strong acids-for example, H(3)(+), KrH(+), XeH(+), and CH(5)(+). The hitherto experimentally unknown proton affinity of O(3) was evaluated by a "bracketing" technique and determined to be 148 -/+ 3 kilocalories mole(-1) at 298 kelvin, in excellent agreement with a value determined in a recent theoretical study of the O(3)/O(3)H(+) system, which was 148 kilocalories mole(-1) at zero temperature ( approximately 149.5 kilocalories mole(-1) at 298 kelvin).     

Gas-phase ion chemistry

Progress has been made in the understanding of potential energy surfaces for unimolecular ion dissociations and ion-molecule reactions. With recent advances in instrumentation, many new techniques have been developed to generate and study ions, ion-molecule complexes, and large ionic clusters. Developments in ion spectroscopy have enabled considerable advances to be made in the determination of ion structures.     

Comparison of calculated and measured ion densities on the dayside of venus

Datafrom the Pioneer Venus ion mass spectrometers are compared with model calculations of the ion density distributions appropriate for daytime conditions. The model assumes diffusive equilibrium upper boundary conditions for the major ions (O(2)(+), O(+), CO(2)(+), He(+), and H(+)); the agreement between the calculated and measured gross behavior of these ions is reasonably good except for H(+), which may be influenced strongly by convective transport processes. The distributions of five minor ions (C(+), N(+), NO(+), CO(+), and N(2)(+)) are also calculated for the chemically controlled region ( less, similar 200 kilometers); the agreements are, in general, poor, an indication that our present understanding of the Venus minor ion chemistry is still incomplete.     

Studies of unusual simple molecules by neutralization-reionization mass spectrometry

Reactive or unstable molecules are key intermediates in many important reactions, but can be difficult to prepare for experimental studies. Species with missing (:CH-OH) or extra (H3) substituents can often be formed conveniently in the gas phase by neutralizing a beam of a more stable ionic counterpart (CH = O+H, H3+). Reionization of the neutral after approximately 10(-6) seconds tests its stability, whereas its unimolecular chemistry can be probed by preparing it with different amounts of internal energy. The resulting neutral products are reionized and mass analyzed. Isomers are then characterized by ion dissociation and a third mass-analysis step. Many unusual molecules have been characterized with this technique, which can also be used to probe complex unimolecular chemistry, such as that of cyclobutadiene and ethylene oxide.     

Detection of SO in Io's exosphere

The Galileo orbiter's close pass by Io in 1995 produced evidence for extensive mass loading of the plasma torus through the ionization of SO2. On 11 October 1999, Galileo passed even closer to Io, this time across the upstream side relative to the flow of magnetospheric plasma that corotates with Jupiter. On the first flyby, ion cyclotron waves gave direct evidence for the production of SO2+ ions. On the second flyby, ion cyclotron waves associated with SO+ were stronger and more persistent. Moreover, SO+ emissions were seen closer to Io than SO2+ emissions, suggesting that the exosphere was spatially inhomogeneous. The location of the waves suggests a fan-shaped region of ion pickup extending in the anti-Jupiter direction. Because the wave spectra were different even where the 1995 and 1999 trajectories crossed, we infer that Io's exosphere is temporally variable.     

Kinetic evidence for five-coordination in AlOH(aq)2+ ion

Trivalent aluminum ions are important in natural bodies of water, but the structure of their coordination shell is a complex unsolved problem. In strong acid (pH < 3.0), Al(III) exists almost entirely as the octahedral Al(H2O)6(3+) ion, whereas in basic conditions (pH > 7), a tetrahedral Al(OH)(4- structure prevails. In the biochemically and geochemically critical pH range of 4.3 to 7.0, the ion structures are less clear. Other hydrolytic species, such as AlOH(aq)2+, exist and are traditionally assumed to be hexacoordinate. We show, however, that the kinetics of proton and water exchange on aqueous Al(III), coupled with Car-Parrinello simulations, support a five-coordinate Al(H2O)4OH2+ ion as the predominant form of AlOH(aq)2+ under ambient conditions. This result contrasts Al(III) with other trivalent metal aqua ions, for which there is no evidence for stable pentacoordinate hydrolysis products.     

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.     

Chemical reactions of anions in the gas phase

Anions of many types, both organic and inorganic, farmiliar and exotic, can be generated in the gas phase by rational chemical synthesis in a flowing afterglow apparatus. Once formed, the rates, products, and mechanisms of their reactions with neutral species of all kinds can be studied, not only at room temperature but at higher energies in a drift field. These completely unsolvated ions undergo a large number of reactions that are analogous to those they undergo in solution, as well as some that are less familiar. New types of ions, for which there are no counterparts in solution, can be produced and their chemical reactions explored.     

Ionosphere of venus: first observations of day-night variations of the ion composition

The Bennett radio-frequency ion mass spectrometer on the Pioneer Venus orbiter is returning the first direct composition evidence of the processes responsible for the formation and maintenance of the nightside ionosphere. Early results from predusk through the nightside in the solar zenith angle range 63 degrees (dusk) to 120 degrees (dawn) reveal that, as on the dayside, the lower nightside ionosphere consists of F(1)and F(2) layers dominated by O(2)(+) and O(+), respectively. Also like the dayside, the nightside composition includes distributions of NO(+), C(+), N(+), H(+), He(+), CO(2)(+), and 28(+) (a combination of CO(+) and N(2)(+)). The surprising abundance of the nightside ionosphere appears to be maintained by the transport of O(+) from the dayside, leading also to the formation of O(2)(+) through charge exchange with CO(2). Above the exobase, the upper nightside ionosphere exhibits dramatic variability in apparent response to variations in the solar wind and interplanetary magnetic field, with the ionopause extending to several thousand kilometers on one orbit, followed by the complete rertnoval of thermal ions to altitudes below 200 kilometers on the succeeding orbit, 24 hours later. In the upper ionosphere, considerable structure is evident in many of the nightside ion profiles. Also evident are horizontal ion drifts with velocities up to the order of 1 kilometer per second. Whereas the duskside ionopause is dominated by O(+) H(+) dominates the topside on the dawnside of the antisolar point, indicating two separate regions for ion depletion in the magnetic tail regions.     

Search for interstellar superheavy hydrogen

Models for fundamental physical interactions allow for the existence of stable or nearly stable elementary particles much heavier than the proton. Stellar spectra were searched for a positively charged superheavy particle, X(+), which, with a bound electron, should appear as apparently superheavy neutral hydrogen in the interstellar medium. An upper limit for the abundance of X relative to normal hydrogen in the line of sight toward the bright star gamma Cassiopeiae is 2 x 10(-8).     

Comet encke: meteor metallic ion identification by mass spectrometer

Metal ions including 23(+) (Na(+)), 24(+) (Mg(+)) 28(+) (Si(+)), 39(+) (K(+)), 40(+) (Ca(+)), 45(+) (Sc(+)), 52(+) Cr(+)). 56(+) (Fe(+)), and 58(+) (Ni(+)) have been detected in the upper atmosphere during the period of the Beta Taurids meteor shower. The abundances of these ions relative to Si(+) show, agreement in most instances with abundances in chondrites. A notable exception is 45(+), which, if it is Sc(+), is 100 times more abundant than neutral scandium found in chondrites.     

植物液泡膜H+-ATPase和H+-PPase研究进展

植物液泡膜 ATP 酶（H+-ATPase）和液泡膜焦磷酸酶（H+-PPase）是液泡膜上两个含量丰富的蛋白,其功能的正常发挥在植物生长发育过程中扮演着重要角色。液泡膜 H+-ATPase 和 H+-PPase 水解底物释放能量,同时产生大量 H+由胞质泵入液泡内,形成细胞质与液泡间的 H+ 电化学势梯度,为多种溶质分子的跨膜主动运输提供驱动力,维持细胞内的离子稳态和渗透平衡,为细胞内各种生理生化反应的正常运行提供保障。此外,液泡作为植物细胞离子养分的储存库,其膜上 H+-ATPase 和 H+-PPase 能够通过改变其活性来调控硝酸盐在胞质和液泡间的分配比例,进而影响植物的氮素利用效率。在逆境胁迫条件下,提高液泡膜 H+-ATPase 和 H+-PPase 的活性有利于提高植株对逆境的适应能力,从而减少逆境胁迫对植株生长发育造成的不利影响。介绍了植物液泡膜 H+-ATPase 和 H+-PPase 的结构特征及其在植物生长发育过程中的生理功能,并对其在植物抵御非生物逆境胁迫过程中发挥的重要作用进行阐述,为进一步提高作物的氮素利用率及逆境适应能力提供方向。     

Laser resonance ionization mass spectrometry

The analysis of inorganic atomic species is greatly facilitated by the coupling of lasers with mass spectrometers. A tunable dye laser, alone or in combination with a pump laser, ionizes atoms by resonant excitation processes; the ions are then analyzed in the mass spectrometer. The laser-mass spectrometer system promises to overcome traditional limits of sensitivity and selectivity and to have diverse applications in analytical chemistry.     

MESSENGER observations of the composition of Mercury's ionized exosphere and plasma environment

The region around Mercury is filled with ions that originate from interactions of the solar wind with Mercury's space environment and through ionization of its exosphere. The MESSENGER spacecraft's observations of Mercury's ionized exosphere during its first flyby yielded Na+, O+, and K+ abundances, consistent with expectations from observations of neutral species. There are increases in ions at a mass per charge (m/q) = 32 to 35, which we interpret to be S+ and H2S+, with (S+ + H2S+)/(Na+ + Mg+) = 0.67 +/- 0.06, and from water-group ions around m/q = 18, at an abundance of 0.20 +/- 0.03 relative to Na+ plus Mg+. The fluxes of Na+, O+, and heavier ions are largest near the planet, but these Mercury-derived ions fill the magnetosphere. Doubly ionized ions originating from Mercury imply that electrons with energies less than 1 kiloelectron volt are substantially energized in Mercury's magnetosphere.     

Ion composition results during the international cometary explorer encounter with giacobini-zinner

The International Cometary Explorer spacecraft passed through the coma of comet Giacobini-Zinner about 7800 kilometers antisunward of the nucleus on 11 September 1985. The ion composition instrument was sensitive to ambient ions with mass-to-charge ratios in the ranges 1.4 to 3 atomic mass units per electron charge (amu e(-1)) and 14 to 33 amu e(-1). Initial interpretation of the measurements indicates the presence of H(2)O(+), H(3)O(+), probably CO(+) and HCO(+), and ions in the mass range 23 to 24; possible candidates are Na(+) and Mg(+). In addition to these heavy ions, measured over the velocity range 80 to 223 kilometers per second, the instrument measured He(2+) of solar wind origin over the range 237 to 463 kilometers per second. The heavy ions have a velocity distribution which indicates that they have been picked up by the motional electric field, whereas the light ions are steadily decelerated as the comet tail axis is approached. These results are in agreement with the picture of a comet primarily consisting of water ice, together with other material, that sublimes, streams away from the nucleus, becomes ionized, and interacts with the solar wind. K. W. Ogilvie, NASA/Goddard Space Flight Center, Code 692, Greenbelt, MD 20771.     

Proton magnetic resonance spectrum of polywater

With the aid of a time average computer, the proton magnetic resonance spectrum of anomalous water (polywater) is obtained. The spectrum conisists of a single broad resonance shifted approximately 300 hertz downfield from the resonance of ordinary water.