Toward separation and purification of olefins using dithiolene complexes: an electrochemical approach

The complex Ni[S2C2(CF3)2]2 reacts with light olefins, including ethylene and propylene, selectively and reversibly. The reaction is not poisoned by hydrogen gas, carbon monoxide, acetylene, or hydrogen sulfide, which are commonly present in olefin streams, presumably because olefin binding occurs through the sulfur ligand rather than the metal center. The reversible reaction of olefins with Ni[S2C2(CN)2]2n (n = 0, -1, -2) can be controlled electrochemically, where the oxidation state-dependent binding and release of olefins are fast on the electrochemical time scale. The observed tolerance to poisons and controllable electrochemical reactivity present an alternative approach to the separation of olefins from complex streams.     

Conjugated polymer films for gas separations

Permeabilities for a series of gases through free-standing films of the conjugated polymer polyaniline are reported. A remarkable selectivity has been achieved for important gas pairs incuding hydrogen-nitrogen, oxygen-nitrogen, and carbon dioxide-methane. The selectivity values of 3590 for H(2)/N(2), 30 for O(2)/N(2), and 336 for CO(2)/CH(4) surpass the highest previously reported values of 313, 16, and 60 for the nonconjugated polymers poly(trifluorochloroethylene), cellulose nitrate, and a fluorinated polyimide, respectively. The process for tailoring gas selectivity of a polyaniline membrane involves first enhancing the permeabilities of gases with small diameters [<3.5 angstroms (A)] by doping and undoping the polymer film with counterions of an appropriate size. High selectivities are then achieved by decreasing the permeabilities of larger gases (>3.5 A diameter) through controlled redoping of the polymer. The permanent morphological changes induced in this conjugated polymer system and others indicate the potential for development of universal membranes for gas separations.     

Methane to ethylene with 85 percent yield in a gas recycle electrocatalytic reactor-separator

Methane was oxidatively coupled to ethylene with an ethylene yield up to 85 percent and a total C(2) hydrocarbon yield up to 88 percent in a gas recycle high-temperature (800 degrees C) electrocatalytic or catalytic reactor where the recycled gas passes continuously through a molecular sieve trap in the recycle loop. Oxygen is supplied either electrocatalytically by means of the solid electrolyte support of the silver-based catalyst or in the gas phase. The C(2) products are obtained by subsequent heating of the molecular sieve trap. The selectivity to ethylene is up to 88 percent for methane conversion up to 97 percent.     

The 1979 nobel prize for chemistry

The 1979 Nobel Prize for Chemistry has been awarded jointly to Georg Wittig of the University of Heidelberg and Herbert C. Brown of Purdue University for their separate work in organic synthesis. Wittig's major achievement was the development of a highly specific method for the synthesis of olefins. Brown found major new routes to add substituents to olefins selectively. Both employed elements that had found little previous use in organic synthesis, and both prospered by following up on unexpected observations.     

酚醛树脂基炭膜的制备与性能研究

采用真空涂膜法,以一定浓度的商用酚醛树脂为前驱体在多孔陶瓷管上制备复合炭膜,并考察真空度对复合膜气体渗透性能的影响。结果表明,采用真空法可以在载体表面形成均匀的炭膜,而传统提拉法较难获得连续的炭膜,涂膜真空度为0.6MPa更利于高性能炭膜的制备。对真空法制备的炭膜进行单组份气体渗透测试,发现随着涂膜真空度的增加,复合膜的气体渗透速率显著减低,而理想选择性出现峰值。等摩尔CO2/CH4混合气的渗透测试发现:室温下炭膜的CO2渗透速率达到1.4×10-7mol.Pa-1.m-2.s-1,αCO2/CH4达到48.3,高于其努森值。扫描电镜测试表明,此复合膜表面均匀、连续,膜厚度大约4μm,与载体结合紧密。     

Seasonal variations in the stable carbon isotopic signature of biogenic methane in a coastal sediment

Systematic seasonal variations in the stable carbon isotopic signature of methane gas occur in the anoxic sediments of Cape Lookout Bight, a lagoonal basin on North Carolina's Outer Banks. Values for the carbon isotope ratio (delta 13C) of methane range from -57.3 per mil during summer to -68.5 per mil during winter in gas bubbles with an average methane content of 95%. The variations are hypothesized to result from changes in the pathways of microbial methane production and cycling of key substrates including acetate and hydrogen. The use of stable isotopic signatures to investigate the global methane cycle through mass balance calculations, involving various sediment and soil biogenic sources, appears to require seasonally averaged data from individual sites.     

Surface-modified carbon nanotubes catalyze oxidative dehydrogenation of n-butane

Butenes and butadiene, which are useful intermediates for the synthesis of polymers and other compounds, are synthesized traditionally by oxidative dehydrogenation (ODH) of n-butane over complex metal oxides. Such catalysts require high O2/butane ratios to maintain the activity, which leads to unwanted product oxidation. We show that carbon nanotubes with modified surface functionality efficiently catalyze the oxidative dehydrogenation of n-butane to butenes, especially butadiene. For low O2/butane ratios, a high selectivity to alkenes was achieved for periods as long as 100 hours. This process is mildly catalyzed by ketonic CO groups and occurs via a combination of parallel and sequential oxidation steps. A small amount of phosphorus greatly improved the selectivity by suppressing the combustion of hydrocarbons.     

Annealing c60+: synthesis of fullerenes and large carbon rings

Laser vaporization of graphite generates C(60)(+) cluster ions that are fullerenes and a mixture of roughly planar polycyclic polyyne ring isomers. Experimental studies of the annealing of the non-fullerene C(60)(+) ions indicate that they can be converted (in the gas phase) into the fullerene and an isomer that appears to be a large monocyclic ring. Some fragmentation is associated with conversion to the fullerene geometry, but the majority of the non-fullerene C(60)(+) isomers are cleanly converted into an intact fullerene. The emergence of the monocyclic ring (as the clusters are annealed) suggests that this is a relatively stable non-spheroidal form of these all carbon molecules. The estimated activation energies for the observed structural interconversions are relatively low, suggesting that these processes may play an important role in the synthesis of spheroidal fullerenes.     

Efficient epoxidation of olefins with >/=99% selectivity and use of hydrogen peroxide

Epoxides are an important class of industrial chemicals that have been used as chemical intermediates. Catalytic epoxidation of olefins affords an interesting production technology. We found a widely usable green route to the production of epoxides: A silicotungstate compound, [gamma-SiW10O34(H2O)2]4-, is synthesized by protonation of a divacant, lacunary, Keggin-type polyoxometalate of [gamma-SiW10O36]8- and exhibits high catalytic performance for the epoxidation of various olefins, including propylene, with a hydrogen peroxide (H2O2) oxidant at 305 kelvin. The effectiveness of this catalyst is evidenced by >/=99% selectivity to epoxide, >/=99% efficiency of H2O2 utilization, high stereospecificity, and easy recovery of the catalyst from the homogeneous reaction mixture.     

Generation and migration of light hydrocarbons

Light hydrocarbons (containing from 1 to 14 carbon atoms) are formed from disseminated organic matter in sediments at the parts-per-billion level by biological and low-temperature (< 50 degrees C) chemical reactions and at the parts-permillion level by high-temperature (> 50 degrees C) cracking reactions. The cooler reactions produce mainly branched hydrocarbons, whereas the hotter reactions yield more straight chains. Hydrocarbon generation zones in the subsurface can be recognized on the basis of hydrocarbon distribution patterns. Hydrocarbons with tertiary carbon atoms form at lower temperatures than those with quaternary carbons. Methane and ethane migrate vertically through fine-grained shales by diffusion and solution, whereas many of the C(3+) hydrocarbons show little or no vertical migration. Concentrations of light hydrocarbons, including methane, in fine-grained source rocks decrease to low values in deep, high-temperature (>200 degrees C) sediments. This decrease may be one reason why no economic accumulation of gas has been found to date deeper than 8.2 kilometers (27,000 feet).     

Solubility in water of normal c9 and c10, alkane hydrocarbons

A new method for equilibrating water containing alkane hydrocarbons with a gas phase and analyzing the gas for hydrocarbon content by gas chromatography extends analytical sensitivity to better than 0.1 part per billion. The solubilities at 25 degrees C of the normal C(9) (220 parts per billion) and C(10) (52 parts per billion) alkanes decrease with increasing carbon number. A discontinuity occurs at the normal C(11), alkane, probably because of a change from true solubility (molecular dispersion) to accommodation (aggregation).     

Primary alcohols from terminal olefins: formal anti-Markovnikov hydration via triple relay catalysis

Alcohol synthesis is critical to the chemical and pharmaceutical industries. The addition of water across olefins to form primary alcohols (anti-Markovnikov olefin hydration) would be a broadly useful reaction but has largely proven elusive; an indirect hydroboration/oxidation sequence requiring stoichiometric borane and oxidant is currently the most practical methodology. Here, we report a more direct approach with the use of a triple relay catalysis system that couples palladium-catalyzed oxidation, acid-catalyzed hydrolysis, and ruthenium-catalyzed reduction cycles. Aryl-substituted terminal olefins are converted to primary alcohols by net reaction with water in good yield and excellent regioselectivity.     

Stable carbon isotopic evidence for carbon limitation in hydrothermal vent vestimentiferans

Stable carbon isotope composition (delta(13)C values) can be used to evaluate an animal's source of nutritional carbon. Most animals with chemoautotrophic endosymbionts have quite negative tissue delta(13)C values due to discrimination against (13)C associated with chemoautotrophic assimilation of inorganic carbon. However, the delta(13)C values of hydrothermal vent (HTV) vestimentiferans are significantly higher than the values reported for non-HTV vestimentiferans or other invertebrates with chemoautotrophic endosymbionts. Tissue delta(13)C values of two species of HTV vestimentiferans increase with increasing size of the animals. This relation supports the hypothesis that the relatively high delta(13)C values are the result of inorganic carbon limitation during carbon fixation. A more favorable relation between gas exchange and carbon fixation in the smaller individuals is expected, due to differences in the geometric scaling of gas-exchange surfaces and trophosome volume.     

Chiral-selective aminoacylation of an RNA minihelix

Amino acids in natural proteins have a chiral, asymmetric center at the alpha carbon that is of the L-configuration. The sugar backbone of natural RNAs are also homochiral, but of the D-configuration. Because protein synthesis requires the aminoacylation of RNA, it is this step that could have provided chiral selectivity. Here we show that an RNA minihelix was aminoacylated by an aminoacyl-phosphate-D-oligonucleotide with a clear preference for L- as opposed to D-amino acids. A mirror-image RNA system showed the opposite selectivity. These results suggest the possibility that the selection of L-amino acids for proteins was determined by the stereochemistry of RNA.     

All-Carbon Molecules: Evidence for the Generation of Cyclo[18]carbon from a Stable Organic Precursor

The unambiguous structural characterization of a single-sized all-carbon molecule requires its chemical synthesis. For cyclo[18]carbon, ab initio calculations predict a relatively stable, cyclic D9h ground state geometry with alternating C-C (1.36 angstroms) and C identical withC (1.20 angstroms) bonds. The synthesis and x-ray crystal structure of a direct precursor to C(18) are described. The analysis of laser flash heating experiments on this precursor by time-of-flight mass spectroscopy shows a sequence of retro-Diels-Alder reactions leading to C(18) as the predominant fragmentation pattern. Structural evidence is provided for the generation of an all-carbon molecule from a well-characterized organic precursor.     

Internal olefins to linear amines

The selective synthesis of linear amines from internal olefins or olefin mixtures was achieved through a catalytic one-pot reaction consisting of an initial olefin isomerization followed by hydroformylation and reductive amination. Key to the success is the use of specially designed phosphine ligands in the presence of rhodium catalysts. This reaction constitutes an economically attractive and environmentally favorable synthesis of linear aliphatic amines.     

丙酸香叶酯的催化合成(英文)

[目的]进行丙酸香叶酯的合成并优化合成条件。[方法]在敞开体系中合成中孔分子筛Al-MCM-41。通过X射线衍射(XRD)、红外光谱(FT-IR)、NH3程序升温脱附(NH3-TPD)、N2吸附-脱附和气相色谱(GC)等方法对所合成样品的结构和催化性能进行表征分析。用其催化合成丙酸香叶酯,考察了反应时间、反应温度、催化剂用量、反应物配比及催化剂再生对香叶醇酯化反应结果的影响。[结果]合成的样品具有中孔分子筛的六方介孔结构以及良好的长程有序性和结晶度,属于典型的中孔材料,分子筛表面有弱酸中心。最佳的反应条件是n(香叶醇)/n(丙酸)=1.0∶1.5,反应温度为120℃,反应时间为8h,但香叶醇的转化率仅为40.01%,丙酸香叶酯的选择性为70.01%。催化剂使用到第5次时有失活现象,可通过焙烧除去掩盖酸中心的积碳,使催化剂的活性和选择性得到恢复。[结论]得到了丙酸香叶酯的合成优化条件,为进一步研究奠定基础。     

Synthesis gas: a raw material for industrial chemicals

Rapid increases in the price of imported crude oil have accelerated a shift in the raw material base for chemical feedstocks from natural gas to crude oil to coal. Widespread use of ethylene as a feedstock has depended on the availability at attractive prices of natural gas and petroleum. As the resource base shifts from natural gas and petroleum to coal, ethylene is being replaced by synthesis gas (a mixture of hydrogen and carbon monoxide of varying composition), which can be manufactured directly from any of these carbonaceous sources. This trend is expected to accelerate in the 1980's. Organics likely to be produced from synthesis gas include ethanol, ethylene glycol, and vinyl acetate.     

Systematic inflation of buckminsterfillerene c60: synthesis of diphenyl fulleroids c61 to c66

The synthesis of a new family of spheroidal carbon molecules derived from the fullerenes is described. The fulleroids are produced by incremental addition of a divalent carbon equivalent that has two phenyl (Ph) rings to fullerene C(60). The fulleroids Ph(2)C(61), Ph(4)C(62), Ph(6)C(63), Ph(8)C(64), Ph(10)C(65), and Ph(12)C(66) have been prepared and characterized.     

小麦籽粒氨基酸碳氮稳定同位素的测定与分析

 【目的】利用气相色谱-燃烧-同位素比值质谱仪（gas chromatography-combustion-isotope ratio mass spectrometry,GC-C-IRMS）测定小麦籽粒氨基酸碳氮稳定同位素组成。【方法】以小麦临汾50744为材料,水解得到其籽粒蛋白质氨基酸,将氨基酸标准样品以及小麦籽粒氨基酸衍生化为N-新戊酰基,O-异丙醇（N-pivaloyl-isopropyl,NPP）氨基酸酯,利用GC-C-IRMS测定其碳氮稳定同位素组成。【结果】氨基酸标准样品的碳氮同位素组成分析表明,NPP氨基酸酯的平均重现性δ13C为0.47‰,δ15N为0.28‰,并没有产生大的同位素分馏,因此δ13C和δ15N都能得到满意的测定结果。运用GC-C-IRMS测定了小麦临汾50744籽粒蛋白质氨基酸的稳定碳氮同位素的自然丰度,其中δ13C的变化范围在-28.7‰到-34.7‰,δ15N的变化范围为-6.2‰到9.5‰。采用系统聚类分析进行分类,根据δ13C可以将氨基酸分为两类;根据δ15N可以将氨基酸分为三类。【结论】运用GC-C-IRMS结合NPP氨基酸酯衍生物可以测定小麦籽粒氨基酸的稳定碳氮同位素,这对于揭示氨基酸代谢途径的差异以及逆境胁迫下氨基酸的合成差异具有重要的意义。