Self-Assembly of n-Alkyl Thiols as Disulfides on Au(111)

A grazing incidence x-ray diffraction study of CH(3)(CH(2))(9)SH self-assembled on the (111) surface of gold revealed a disulfide head group structure, which provides a context in which to understand the structure and self-assembly process of this widely studied system. The structure consists of a nearly hexagonal two-dimensional arrangement of the hydrocarbon chains with a dimerization of the sulfur head groups (accommodated through a gauche bond), resulting in a S-S spacing of 2.2 angstroms. These results demonstrate the importance of internal molecular degrees of freedom in the templating of "soft" organic materials on inorganic substrates.     

Recent changes in atmospheric carbon monoxide

Measurements of carbon monoxide (CO) in air samples collected from 27 locations between 71 degrees N and 41 degrees S show that atmospheric levels of this gas have decreased worldwide over the past 2 to 5 years. During this period, CO decreased at nearly a constant rate in the high northern latitudes. In contrast, in the tropics an abrupt decrease occurred beginning at the end of 1991. In the Northern Hemisphere, CO decreased at a spatially and temporally averaged rate of 7.3 (+/-0.9) parts per billion per year (6.1 percent per year) from June 1990 to June 1993, whereas in the Southern Hemisphere, CO decreased 4.2 (+/-0.5) parts per billion per year (7.0 percent per year). This recent change is opposite a long-term trend of a 1 to 2 percent per year increase inferred from measurements made in the Northern Hemisphere during the past 30 years.     

Ultrafast carbon-carbon single-bond rotational isomerization in room-temperature solution

Generally, rotational isomerization about the carbon-carbon single bond in simple ethane derivatives in room-temperature solution under thermal equilibrium conditions has been too fast to measure. We achieved this goal using two-dimensional infrared vibrational echo spectroscopy to observe isomerization between the gauche and trans conformations of an ethane derivative, 1-fluoro-2-isocyanato-ethane (1), in a CCl4 solution at room temperature. The isomerization time constant is 43 picoseconds (ps, 10(-12) s). Based on this value and on density functional theory calculations of the barrier heights of 1, n-butane, and ethane, the time constants for n-butane and ethane internal rotation under the same conditions are approximately 40 and approximately 12 ps, respectively.     

A Net Sink for Atmospheric CH3Br in the East Pacific Ocean

Surface waters along a cruise track in the East Pacific Ocean were undersaturated in methyl bromide (CH(3)Br) in most areas except for coastal and upwelling regions, with saturation anomalies ranging from + 100 percent in coastal waters to -50 percent in open ocean areas, representing a regionally weighted mean of -16 (-13 to -20) percent. The partial lifetime of atmospheric CH(3)Br with respect to calculated oceanic degradation along this cruise track is 3.0 (2.9 to 3.6) years. The global, mean dry mole fraction of CH3Br in the atmosphere was 9.8 +/- 0.6 parts per trillion, with an interhemispheric ratio of 1.31 +/- 0.08. These data indicate that approximately 8 percent (0.2 parts per trillion) of the observed interhemispheric difference in atmospheric CH3Br could be attributed to an uneven global distribution of oceanic sources and sinks.     

球磨杠柳木质素化学结构特性

对球磨的杠柳(Periploca sepium)采用含有0.05mol/L HCl的80%液体二氧六环在85℃处理4h、二甲基亚砜在85℃处理4h,以及8% NaOH在50℃处理3h,得到86%的原本木质素.采用FTIR、UV、液态1H和13C-NMR研究了酸性二氧六环、二甲基亚砜和碱溶性木质素组分的结构特征.结果表明:温和条件下,球磨与酸水解对分离的木质素大分子结构破坏不大.其中,温和酸水解使半纤维素和木质素之间醚键发生显著断裂,并使半纤维素发生部分降解.由于酸性二氧六环溶解的木质素主要来自初生壁,而碱溶性木质素主要来自次生壁,导致酸性二氧六环溶解的木质素与二甲基亚砜和碱溶性木质素结构不同.     

Giant electrostriction and relaxor ferroelectric behavior in electron-irradiated poly(vinylidene fluoride-trifluoroethylene) copolymer

An exceptionally high electrostrictive response ( approximately 4 percent) was observed in electron-irradiated poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] copolymer. The material exhibits typical relaxor ferroelectric behavior, suggesting that the electron irradiation breaks up the coherent polarization domain (all-trans chains) in normal ferroelectric P(VDF-TrFE) copolymer into nanopolar regions (nanometer-size, all-trans chains interrupted by trans and gauche bonds) that transform the material into a relaxor ferroelectric. The expanding and contracting of these polar regions under external fields, coupled with a large difference in the lattice strain between the polar and nonpolar phases, generate an ultrahigh strain response.     

Venting of carbon dioxide-rich fluid and hydrate formation in mid-okinawa trough backarc basin

Carbon dioxide-rich fluid bubbles, containing approximately 86 percent CO(2), 3 percent H(2)S, and 11 percent residual gas (CH(4) + H(2)), were observed to emerge from the sea floor at 1335- to 1550-m depth in the JADE hydrothermal field, mid-Okinawa Trough. Upon contact with seawater at 3.8 degrees C, gas hydrate immediately formed on the surface of the bubbles and these hydrates coalesced to form pipes standing on the sediments. Chemical composition and carbon, sulfur, and helium isotopic ratios indicate that the CO(2)-rich fluid was derived from the same magmatic source as dissolved gases in 320 degrees C hydrothermal solution emitted from a nearby black smoker chimney. The CO(2)-rich fluid phase may be separated by subsurface boiling of hydrothermal solutions or by leaching of CO(2)-rich fluid inclusion during posteruption interaction between pore water and volcanogenic sediments.     

A Synchrotron X-ray Study of a Solid-Solid Phase Transition in a Two-Dimensional Crystal

A measurement and interpretation on a molecular level of a phase transition in an ordered Langmuir monolayer is reported. The diagram of surface pressure (pi) versus molecular area of a monolayer of chiral (S)-[CF(3)-(CF(2))(9)-(CH(2))(2)-OCO-CH(2)-CH (NH(3)(+))CO(2)(-)] over water shows a change in slope at about pi(s)= 25 millinewtons per meter. Grazing-incidence x-ray diffraction and specular reflectivity measurements indicate a solid-solid phase transition at pi(s). The diffraction pattren at low pressures reveals two diffraction peaks of equal intensities, with lattice spacings d of 5.11 and 5.00 angstroms; these coalesce for pi >/=pi(s). Structural models that fit the diffraction data show that at pi> pi(s) the molecules pack in a two-dimensional crystal with the molecules aligned vertically. At pi < pi(s) there is a molecular tilt of 16 degrees +/- 7 degrees . Independent x-ray reflectivity data yield a tilt of 26 degrees +/- 7 degrees . Concomitant with the tilt, the diffraction data indicate a transition from a hexagonal to a distorted-hexagonal lattice. The hexagonal arrangement is favored because the -(CF(2))(9)CF(3) moiety adopts a helical conformation. Compression to 70 millinewtons per meter yields a unit cell with increased crystallinity and a coherence length exceeding 1000 angstroms.     

3-（5-芝麻酚）-3-羟基氧化吲哚拼接衍生物和芝麻酚并吡喃螺环氧化吲哚拼接衍生物的合成研究

以取代靛红作为起始原料,通过和芝麻酚在10 mol%DABCO催化剂和二氯甲烷溶剂条件下的Aldol反应,高效合成3个未见文献报道的3-（5-芝麻酚）-3-羟基氧化吲哚（2a～2c）,产率为85%-92%。以取代靛红作为起始原料,通过和芝麻酚以及丙二腈在10 mol%DABCO催化剂和二氯甲烷溶剂条件下的三组分Domino反应,高效合成5个未见文献报道的芝麻酚并吡喃螺环氧化吲哚（3a-3e）,产率为87%-94%。底物取代基结构经1H NMR,13C NMR和MS（ESI）表征。     

The effect of magmatic activity on hydrothermal venting along the superfast-spreading East pacific rise

A survey of hydrothermal activity along the superfast-spreading (approximately 150 millimeters per year) East Pacific Rise shows that hydrothermal plumes overlay approximately 60 percent of the ridge crest between 13 degrees 50' and 18 degrees 40'S, a plume abundance nearly twice that known from any other rige portion of comparable length. Plumes were most abundant where the axial cross section is inflated and an axial magma chamber is present. Plumes with high ratios of volatile ((3)He, CH(4), and H(2)S) to nonvolatile (Mn and Fe) species marked where hydrothermal circulation has been perturbed by recent magmatic activity. The high proportion of volatile-rich plumes observed implies that such episodes are more frequent here than on slower spreading ridges.     

Carbon-14 in methane sources and in atmospheric methane: the contribution from fossil carbon

Measurements of carbon-14 in small samples of methane from major biogenic sources, from biomass burning, and in "clean air" samples from both the Northern and Southern hemispheres reveal that methane from ruminants contains contemporary carbon, whereas that from wetlands, pat bogs, rice fields, and tundra is somewhat, depleted in carbon-14. Atmospheric (14)GH(4) seems to have increased from 1986 to 1987, and levels at the end of 1987 were 123.3 +/- 0.8 percent modern carbon (pMC) in the Northern Hemisphere and 120.0 +/- 0.7 pMC in the Southern Hemisphere. Model calculations of source partitioning based on the carbon-14 data, CH(4) concentrations, and delta(13)C in CH(4) indicate that 21 +/- 3% of atmospheric CH(4) was derived from fossil carbon at the end of 1987. The data also indicate that pressurized water reactors are an increasingly important source of (14)CH(4).     

Atmospheric trace gases in antarctica

Trace gases have been measured, by electron-capture gas chromatography and gas chromatography-mass spectrometry techniques, at the South Pole (SP) in Antarctica and in the U.S. Pacific Northwest (PNW) ( approximately 45 degrees N) during January of each year from 1975 to 1980. These measurements show that the concentrations of CCl(3)F, CCl(2)F(2), and CH(3)CCl(3) have increased exponentially at substantial rates. The concentration of CCl(3)F increased at 12 percent per year at the SP and at 8 percent per year in the PNW; CCl(2)F(2) increased at about 9 percent per year at both locations, and CH(3)CCl(3) increased at 17 percent per year at the SP and 11.6 percent per year at the PNW site. There is some evidence that CCl(4) ( approximately 3 percent per year) and N(2)O (0.1 to 0.5 percent per year) may also have increased. Concentrations of nine other trace gases of importance in atmospheric chemistry are also being measured at these two locations. Results of the measurements of CHClF(2)(F-22), C(2)Cl(3)F(3)(F-113), SF(6), C(2)-hydrocarbons, and CH(3)Cl are reported here.     

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.     

Decamethyldizincocene, a stable compound of Zn(I) with a Zn-Zn bond

Unlike mercury, which has an extensive +1 oxidation state chemistry, zinc usually adopts the +2 oxidation state. Decamethyldizincocene, Zn2(eta5-C5Me5)2, an organometallic compound of Zn(I) formally derived from the dimetallic [Zn-Zn]2+ unit, has been isolated from the low-temperature (-10 degrees C) reaction of Zn(C5Me5)2 and Zn(C2H5)2 in diethyl ether. X-ray studies show that it contains two eclipsed Zn(eta5-C5Me5) fragments with a Zn-Zn distance (+/- standard deviation) of 2.305(+/-3) angstroms, indicative of a metal-metal bonding interaction.     

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.     

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.     

Kaolinite Synthesis at 25{degrees}C

The addition of quercetin, an organic flavone (C(15)H(10)O(7)), to aqueous solutions containing silica and aluminum and adjusted to final pH's from 6.5 to 8.5 produced a 1 : 1 alumninosilicate precipitate which, after 6 to 16 months of aging in solution at 25 degrees C, contained as much as 5 percent well-formed kaolinite plates. Similar solutions containing no organic material produced relatively amorphous precipitates with the same composition and stability (standard free energy of formation = -897+/-1 kilocalories per mole) but with substantially smaller amounts of crystaline material even after 2 years of aging.     

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.     

Cell growth with trans fatty acids is affected by adenosine 3',5'-monophosphate and membrane fluidity

Two positional isomers (9 and 11) of trans octadecenoates did not support growth on glucose of an Escherichia coli mutant that requires unsaturated fatty acids. However, the trans fatty acids provided sufficient fluidity to produce much higher cell yields when the concentration of adenosine 3',5'-monophosphate was raised. The effectiveness of the trans acids rose from 0 to 1 cell per femtomole to 15 to 20 cells per femtomole as the concentration of adenosine 3',5'-monophosphate was increased. The corresponding cis positional isomers supported high yields (35 to 40 cells per femtomole) independent of supplementation. The enhanced growth with adenosine 3',5'-monophosphate supplementation is not due to an increased uptake and incorporation of the trans isomers relative to the cis isomers, since the 9-trans isomer was incorporated more rapidly than the 9-cis isomer into the membrane phospholipids under all growth conditions and represented 21 +/- 2 mole percent of the acids. The finding that cells growing with trans fatty acid isomers have a higher requirement for adenosine 3',5'-monophosphate may indicate that some fatty acids can alter the metabolic regulation normally exerted by the cyclic nucleotide.     

Brain and body temperatures in a panting lizard

Panting in Sauromalus obesus is effective enough to keep deep body temperature (T(C)) and brain temperature (T(B)) below an ambient temperature of 45 degrees C for extended periods of time and has a greater cooling effect on the brain than on the remainder of the body. Six animals maintained T(C) and T(B) 0.9 degrees C (+/- 0.08 standard error) and 2.7 degrees C (+/- 0.2 standard error) respectively lower than the ambient temperature of 45 degrees C. It is possible that intracranial vascular shunts play a role in cranial cooling during panting.