Selective bond dissociation and rearrangement with optimally tailored, strong-field laser pulses

We used strong-field laser pulses that were tailored with closed-loop optimal control to govern specified chemical dissociation and reactivity channels in a series of organic molecules. Selective cleavage and rearrangement of chemical bonds having dissociation energies up to approximately 100 kilocalories per mole (about 4 electron volts) are reported for polyatomic molecules, including (CH3)2CO (acetone), CH3COCF3 (trifluoroacetone), and C6H5COCH3 (acetophenone). Control over the formation of CH(3)CO from (CH3)2CO, CF3 (or CH3) from CH3COCF3, and C6H5CH3 (toluene) from C6H5COCH3 was observed with high selectivity. Strong-field control appears to have generic applicability for manipulating molecular reactivity because the tailored intense laser fields (about 10(13) watts per square centimeter) can dynamically Stark shift many excited states into resonance, and consequently, the method is not confined by resonant spectral restrictions found in the perturbative (weak-field) regime.     

Growth of SiO2 at room temperature with the use of catalyzed sequential half-reactions

Films of silicon dioxide (SiO2) were deposited at room temperature by means of catalyzed binary reaction sequence chemistry. The binary reaction SiCl4 + 2H2O --> SiO2 + 4HCl was separated into SiCl4 and H2O half-reactions, and the half-reactions were then performed in an ABAB ellipsis sequence and catalyzed with pyridine. The pyridine catalyst lowered the deposition temperature from >600 to 300 kelvin and reduced the reactant flux required for complete reactions from approximately 10(9) to approximately 10(4) Langmuirs. Growth rates of approximately 2.1 angstroms per AB reaction cycle were obtained at room temperature for reactant pressures of 15 millitorr and 60-second exposure times with 200 millitorr of pyridine. This catalytic technique may be general and should facilitate the chemical vapor deposition of other oxide and nitride materials.     

The hydroperoxyl radical in atmospheric chemical dynamics: reaction with carbon monoxide

From measurements of the photochemical rate of production of CO(2)(16,18) and CO(2)(16,16), produced from the low intensity photolysis of mixtures of CO, H(2)O, Ar, and O(2)(18,18), the rate constant for the reaction HO(2) + CO --> CO(2) + OH has been determined at 300 degrees K to be less than or equal to 10(-20) cubic centimeter per molecule per second. These measurements indicate that the reaction of thermalized HO(2) is of negligible importance as a sink mechanism for converting CO to CO(2) in either the troposphere or the stratosphere.     

Mass-independent oxygen isotope fractionation in atmospheric CO as a result of the reaction CO + OH

Atmospheric carbon monoxide (CO) exhibits mass-independent fractionation in the oxygen isotopes. An 17O excess up to 7.5 per mil was observed in summer at high northern latitudes. The major source of this puzzling fractionation in this important trace gas is its dominant atmospheric removal reaction, CO + OH --> CO2 + H, in which the surviving CO gains excess 17O. The occurrence of mass-independent fractionation in the reaction of CO with OH raises fundamental questions about kinetic processes. At the same time the effect is a useful marker for the degree to which CO in the atmosphere has been reacting with OH.     

Carbon monoxide and nitric oxide consumption in polluted air: the carbon monoxide-hydroperoxyl reaction

A recent laboratory measurement of the ratio of the rate constant for the reaction CO + HO (2) --> C0(2) + OH relative to that for H + HO(2) --> 2OH indicates that the former reaction is probably faster than CO + OH --> CO(2) + H. On this basis a simple analysis is given showing that the calculated lifetime of nitric oxide in polluted atmospheres would be appreciably longer than that estimated on the assumption that the carbon monoxide-hydroperoxyl reaction may be neglected. A fast carbon monoxide-hydroperoxyl reaction implies that the cyclic consumption of carbon monoxide (an atmospheric sink) could occur even with no nitric oxide present.     

High-selectivity, high-flux silica membranes for gas separation

Process improvements in silica membrane fabrication, especially the use of clean-room techniques, resulted in silica membranes without detectable mesoscopic defects, resulting in significantly improved transport properties. Supported membranes calcined at 400 degreesC were 30 nanometers in thickness, showed a H2 permeance at 200 degreesC of 2 x 10(-6) moles per square meter per second per Pascal (mol m-2 s-1 Pa-1), and had a CH4 permeance more than 500 times smaller. Molecules larger than CH4 were completely blocked. Silica membranes calcined at 600 degreesC showed no detectable CH4 flux, with a H2 permeance of 5 x 10(-7) (mol m-2 s-1 Pa-1) at 200 degreesC. These results signify an important step toward the industrial application of these membranes such as purification of H2 and natural gas as well as the selective removal of CO2.     

An Inorganic Double Helix: Hydrothermal Synthesis, Structure, and Magnetism of Chiral [(CH3)2NH2]K4[V10O10(H2O)2(OH)4(PO4)7]{middle dot}4H2O

Very complicated inorganic solids can be self-assembled from structurally simple precursors as illustrated by the hydrothermal synthesis of the vanadium phosphate, [(CH(3))(2)NH(2)]K(4)[V(10)O(10)(H(2)O)(2)(OH)(4)(PO(4))(7)].4H(2)O, 1, which contains chiral double helices formed from interpenetrating spirals of vanadium oxo pentamers bonded together by P(5+). These double helices are in turn intertwined with each other in a manner that generates unusual tunnels and cavities that are filled with (CH(3))(2)NH(2)(+) and K(+) cations, respectively. The unit cell contents of dark blue phosphate 1, which crystallizes in the enantiomorphic space group P4(3) with lattice constants a = 12.130 and c = 30.555 angstroms, are chiral; only one enantiomorph is present in a given crystal. Magnetization measurements show that 1 is paramagnetic with ten unpaired electrons per formula unit at higher temperatures and that antiferromagnetic interactions develop at lower temperatures.     

A mercury-catalyzed, high-yield system for the oxidation of methane to methanol

A homogeneous system for the selective, catalytic oxidation of methane to methanol via methyl bisulfate is reported. The net reaction catalyzed by mercuric ions, Hg(II), is the oxidation of methane by concentrated sulfuric acid to produce methyl bisulfate, water, and sulfur dioxide. The reaction is efficient. At a methane conversion of 50 percent, 85 percent selectivity to methyl bisulfate ( approximately 43 percent yield; the major side product is carbon dioxide) was achieved at a molar productivity of 10(-7) mole per cubic centimeter per second and Hg(II) turnover frequency of 10(-3) per second. Separate hydrolysis of methyl bisulfate and reoxidation of the sulfur dioxide with air provides a potentially practical scheme for the oxidation of methane to methanol with molecular oxygen. The primary steps of the Hg(II)-catalyzed reaction were individually examined and the essential elements of the mechanism were identified. The Hg(II) ion reacts with methane by an electrophilic displacement mechanism to produce an observable species, CH(3)HgOSO(3)H, 1. Under the reaction conditions, 1 readily decomposes to CH(3)OSO(3)H and the reduced mercurous species, Hg(2)(2+) The catalytic cycle is completed by the reoxidation of Hg(2)(2+) with H(2)SO(4) to regenerate Hg(II) and byproducts SO(2) and H(2)O. Thallium(III), palladium(II), and the cations of platinum and gold also oxidize methane to methyl bisulfate in sulfuric acid.     

Water, hydrogen, deuterium, carbon, carbon-13, and oxygen-18 content of selected lunar material

The water content of the breccia is 150 to 455 ppm, with a deltaD from-580 to -870 per mil. Hydrogen gas content is 40 to 53 ppm with a deltaD of -830 to -970 per mil. The CO(2) is 290 to 418 ppm with delta (13)C = + 2.3 to + 5.1 per mil and delta(18)O = 14.2 to 19.1 per mil. Non-CO(2) carbon is 22 to 100 ppm, delta(13)C = -6.4 to -23.2 per mil. Lunar dust is 810 ppm H(2)O (D = 80 ppm) and 188 ppm total carbon(delta(13)C = -17.6 per mil). The (18)O analyses of whole rocks range from 5.8 to 6.2 per mil. The temperature of crystallization of type B rocks is 1100 degrees to 1300 degrees C, based on the oxygen isotope fractionation between coexisting plagioclase and ilmenite.     

Escape of hydrogen from venus

Recombination of O(2)(+) represents a source of fast oxygen atoms in Venus' exosphere, and subsequent collisions of oxygen atoms with hydrogen atoms lead to escape of about 10(7) hydrogen atoms per square centimeter per second. Escape of deuterium atoms is negligible, and the ratio of deuterium to hydrogen should increase with time. It is suggested that the mass-2 ion observed by Pioneer Venus is D(+), which implies a ratio of deuterium to hydrogen in the contemporary atmosphere of about 10(-2), an initial ratio of 5 x 10(-5) and an original H(2)O abundance not less than 800 grams per square centimeter.     

Hydrogen radicals, nitrogen radicals, and the production of O3 in the upper troposphere

The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3 in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HOx required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of O3 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day. This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more O3 than expected.     

不同施肥类型对北方稻田土壤温室气体排放的影响

利用静态暗箱-气相色谱法研究了吉林省延边地区不同施肥类型对水稻土壤CO2、CH4和N2O排放通量的影响。结果表明,稻田3种温室气体的排放存在明显的季节特征,CO2排放主要集中于8~10月,而CH4排放以7、8月为主,水稻生育盛期时N2O表现出明显的负排放特征,净排放发生于移栽期及秋季晒田期;有机肥与化肥配施促进了水稻生育盛期CO2和CH4的排放,导致生长季CO2和CH4排放总量显著高于单施化肥和单施有机肥处理,而单施化肥处理促进了生长季N2O净排放。水稻植株促进了水稻生育期6~8月稻田CO2和CH4的排放,与无植株相比,月均通量分别增加了42.9%~226.1%和146.6%~418.9%。生长季土壤温度对稻田CH4排放具有显著影响,但对CO2和N2O排放影响不显著。     

除草剂对土壤温室气体排放的影响

试验设对照、尿素、尿素+草甘膦和尿素+丁草胺4个处理,尿素氮用量为200mg·kg-1干土,除草剂用量为10mg有效成分·kg-1干土。在实验室恒温培养条件下,研究除草剂对菜田土壤温室气体排放的影响。结果表明,菜田土壤中施用氮肥显著增加了温室气体N2O、CO2和CH4的排放。尿素氮肥中添加草甘膦显著抑制N2O、CO2的排放,分别比尿素处理降低48.4%和20.2%;添加丁草胺显著抑制N2O排放,比尿素处理降低23.2%,对CO2排放略有减少但不显著;草甘膦和丁草胺对CH4排放都无明显影响。这说明除草剂对土壤温室气体的排放具有显著影响,但不同除草剂品种的效应也存在明显差异。因此,在农田温室气体排放估算时应考虑除草剂的施用对温室气体减排所产生的效果。     

Carbon Dioxide Transport by Ocean Currents at 25{degrees}N Latitude in the Atlantic Ocean

Measured concentrations of CO(2), O(2), and related chemical species in a section across the Florida Straits and in the open Atlantic Ocean at approximately 25 degrees N, have been combined with estimates of oceanic mass transport to estimate both the gross transport of CO(2) by the ocean at this latitude and the net CO(2) flux from exchange with the atmosphere. The northward flux was 63.9 x 10(6) moles per second(mol/s); the southward flux was 64.6 x 10(6) mol/s. These values yield a net CO(2) flux of 0.7 x 10(6) mol/s (0.26 +/- 0.03 gigaton of C per year) southward. The North Atlantic Ocean has been considered to be a strong sink for atmospheric CO(2), yet these results show that the net flux in 1988 across 25 degrees N was small. For O(2) the equivalent signal is 4.89 x 10(6) mol/s northward and 6.97 x 10(6) mol/s southward, and the net transport is 2.08 x 10(6) mol/s or three times the net CO(2) flux. These data suggest that the North Atlantic Ocean is today a relatively small sink for atmospheric CO(2), in spite of its large heat loss, but a larger sink for O(2) because of the additive effects of chemical and thermal pumping on the CO(2) cycle but their near equal and opposite effects on the CO(2) cycle.     

东北季节性冻融农田土壤CO2、CH4、N2O通量特征研究

为了评估季节性冻融交替对土壤温室气体排放的影响,采用静态暗箱-气相色谱法,监测了东北松嫩平原两种典型农田生态系统(稻田和玉米田)非生长季土壤CO_2、CH_4和N_2O通量变化。研究表明:三种温室气体排放在土壤冻结期、覆雪期、融雪期和解冻期具有明显的季节动态特征。冻结期和融雪期对温室气体排放贡献最大,这两个时期内稻田和玉米田CO_2排放量分别占非生长季总累积排放量的74.9%和68.6%,稻田CH_4排放占非生长季总排放的95.7%,尽管玉米田土壤CH_4以吸收为主,但在融雪过程中存在明显释放峰,短暂的融雪期内N_2O呈集中爆发性释放,稻田和玉米田N_2O通量峰值分别是冻结前的40倍和99倍,排放量占到总累积排放量的73.9%和80.7%,覆雪期土壤CH_4和N_2O存在弱的吸收。另外,土壤温室气体排放存在土地利用方式间的差异,表现在稻田土壤比玉米田(非生长季)具有更高的温室气体排放潜力。稻田土壤CO_2、CH_4和N_2O累积排放量均高于玉米田,表现为净排放(源),而玉米田土壤CH_4通量表现为净吸收(汇);稻田土壤CO_2和CH_4平均排放速率显著高于玉米田;除覆雪期外,其他时期内三种温室气体平均通量在两类农田之间也存在显著差异。总之,在评价季节性冻土区温室气体排放时需要重视土壤冻结和融化过程,同时需要考虑不同土地利用方式间的差异。     

Dynamics of Saturn's magnetosphere from MIMI during Cassini's orbital insertion

The Magnetospheric Imaging Instrument (MIMI) onboard the Cassini spacecraft observed the saturnian magnetosphere from January 2004 until Saturn orbit insertion (SOI) on 1 July 2004. The MIMI sensors observed frequent energetic particle activity in interplanetary space for several months before SOI. When the imaging sensor was switched to its energetic neutral atom (ENA) operating mode on 20 February 2004, at approximately 10(3) times Saturn's radius RS (0.43 astronomical units), a weak but persistent signal was observed from the magnetosphere. About 10 days before SOI, the magnetosphere exhibited a day-night asymmetry that varied with an approximately 11-hour periodicity. Once Cassini entered the magnetosphere, in situ measurements showed high concentrations of H+, H2+, O+, OH+, and H2O+ and low concentrations of N+. The radial dependence of ion intensity profiles implies neutral gas densities sufficient to produce high loss rates of trapped ions from the middle and inner magnetosphere. ENA imaging has revealed a radiation belt that resides inward of the D ring and is probably the result of double charge exchange between the main radiation belt and the upper layers of Saturn's exosphere.     

Outgassing behavior and composition of comet C/1999 S4 (LINEAR) during its disruption

The gas activity of comet C/1999 S4 (LINEAR) was monitored at radio wavelengths during its disruption. A runaway fragmentation of the nucleus may have begun around 18 July 2000 and proceeded until 23 July. The mass in small icy debris (相似文献   

有机肥对日光温室生菜地土壤温室气体排放的影响

采用静态箱-气相色谱法研究日光温室生菜地不施肥(CK)、施用腐熟鸡粪(H)、羊粪(S)、鸡粪+秸秆(HSt)、羊粪+秸秆(SSt)、羊粪+鸡粪+秸秆(SHSt)等6种处理的温室气体排放通量及增温潜势(GWP)。结果表明:(1)H、S、HSt处理的N_2O排放通量在施肥前、中、后期呈近"V"型变化,CK、SSt、SHSt呈倒"V"型变化;S、SSt、SHSt处理的CH_4排放通量呈倒"V"型变化;CO_2排放通量均呈近"V"型变化(SSt除外);(2)施肥前期,HSt、S、H、SHSt、SSt处理的N_2O排放通量分别较CK显著增加2.89、2.32、1.48、1.17、0.95倍;S、H的CH_4排放通量显著高于CK处理1.91、1.11倍;H的CO_2排放通量显著低于CK处理3.88倍。施肥中期,HSt的N_2O排放通量显著低于CK处理1.93倍;SHSt的CH_4排放通量显著高于CK处理1.34倍;各施肥处理的CO_2排放通量与CK差异不显著。施肥后期,H的N_2O排放通量显著高于CK处理1.10倍;SHSt、SSt、S的CH_4排放通量显著低于CK处理3.76、5.25、5.58倍;HSt的CO_2排放通量显著高于CK处理8.61倍;(3)全球增温潜势(GWP)按照SSHStHStSStCKH依次减小,建议施用腐熟鸡粪、鸡粪加秸秆及羊粪加秸秆。     

秦岭火地塘林区不同海拔不同林型土壤CO_2、CH_4、N_2O通量研究

二氧化碳(CO_2)、甲烷(CH_4)、氧化亚氮(N_2O)是3种主要的温室气体,温带森林土壤是CO_2、N_2O重要的源,是CH_4重要的汇,以前的研究大部分都关注这3种温室气体在时间上的变化,而很少开展在空间变化上的研究。2014年10月至2015年10月,采用静态箱-气相色谱法对秦岭南坡火地塘林区不同海拔(海拔1 560、1 585、1 963、2 040、2 160m,分别为落叶阔叶林、温性针叶林、温性针叶林、寒温性针叶林、落叶阔叶林)森林土壤CO_2、CH_4和N_2O通量进行了为期1a的监测。结果表明,CO_2全年都为排放,季节波动较大,总体上随海拔增加排放量减少,海拔由低到高(包括3种林型)年排放量依次为:19.12、12.53、11.78、16.95、14.87t·hm^-2;CH_4全年主要为吸收,在非生长季出现排放,季节波动幅度较大,总体上随海拔增加吸收量增加,海拔由低到高年通量依次为:-2.57、-3.60、-5.94、-5.59、-3.92kg·hm^-2;N_2O全年以排放过程为主,存在吸收现象,季节波动幅度不大,海拔对其通量影响不明显,海拔由低到高年排放量依次为:0.23、0.62、0.63、0.60、0.95kg·hm^-2。土壤温度是影响CO_2、N_2O通量的关键因子。5个样地森林土壤CO_2通量与土壤铵态氮含量(20～40cm)显著相关(P<0.05)。高的土壤NH_4^+含量对CH_4的吸收有抑制作用。在冻融交替期,降雨对N_2O的通量有明显影响。海拔由低到高5个样地的GWP(全球增温潜势)分别为:119.13、12.65、11.85、17.02t·hm^-2和15.07t·hm^-2。     

Free energy and temperature dependence of electron transfer at the metal-electrolyte interface

The rate constant of the electron-transfer reaction between a gold electrode and an electroactive ferrocene group has been measured at a structurally well-defined metal-electrolyte interface at temperatures from 1 degrees to 47 degrees C and reaction free energies from -1.0 to +0.8 electron volts (eV). The ferrocene group was positioned a fixed distance from the gold surface by the self-assembly of a mixed thiol monolayer of (eta(5)C(5)H(5))Fe(eta(5)C(5)H(4))CO(2)(CH(2))(16)SH and CH(3)(CH(2))(15)SH. Rate constants from 1 per second (s(-1)) to 2 x 10(4) s(-1) in 1 molar HClO(4) are reasonably fit with a reorganization energy of 0.85 eV and a prefactor for electron tunneling of 7 x 10(4) s(-1) eV(-1). Such self-assembled monolayers can be used to systematically probe the dependence of electron-transfer rates on distance, medium, and spacer structure, and to provide an empirical basis for the construction of interfacial devices such as sensors and transducers that utilize macroscopically directional electron-transfer reactions.