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1.
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.  相似文献   

2.
Platinum catalysts are reported for the direct, low-temperature, oxidative conversion of methane to a methanol derivative at greater than 70 percent one-pass yield based on methane. The catalysts are platinum complexes derived from the bidiazine ligand family that are stable, active, and selective for the oxidation of a carbon-hydrogen bond of methane to produce methyl esters. Mechanistic studies show that platinum(II) is the most active oxidation state of platinum for reaction with methane, and are consistent with reaction proceeding through carbon-hydrogen bond activation of methane to generate a platinum-methyl intermediate that is oxidized to generate the methyl ester product.  相似文献   

3.
Agriculture plays a major role in the global fluxes of the greenhouse gases carbon dioxide, nitrous oxide, and methane. From 1991 to 1999, we measured gas fluxes and other sources of global warming potential (GWP) in cropped and nearby unmanaged ecosystems. Net GWP (grams of carbon dioxide equivalents per square meter per year) ranged from 110 in our conventional tillage systems to -211 in early successional communities. None of the annual cropping systems provided net mitigation, although soil carbon accumulation in no-till systems came closest to mitigating all other sources of GWP. In all but one ecosystem, nitrous oxide production was the single greatest source of GWP. In the late successional system, GWP was neutral because of significant methane oxidation. These results suggest additional opportunities for lessening the GWP of agronomic systems.  相似文献   

4.
用三角锥形四齿配体三［（Ｎ 甲基 ２ 苯并咪唑）甲基］胺为配体，合成了甲烷单加氧酶的活性组分—羟基化酶的模型化合物。用叔丁基过氧化氢作氧化剂，研究了单加氧酶模型化合物对低碳烷烃和烯烃在温和条件下氧化的催化活性。实验结果表明，该模型化合物具有较高的催化活性。  相似文献   

5.
将四(5,6-二氢-1,4-二噻英)四氮杂卟啉(FePz(dtn)4)通过电沉积的方式固载在玻碳电极上,该电极在抗坏血酸(AA)和尿酸(UA)等干扰物存在下,可选择性地检测多巴胺(DA).对比裸电极,在循环伏安测量中修饰过后的电极在氧化电位处对DA表现出良好的电催化活性.并且出现一对可逆的氧化还原峰,阳极和阴极的电位值分别为0.182V和0.142V.在电解质溶液中氧化峰电流随着DA的浓度线性增加.两个线性范围分别是1～10和10～200μg/mL,相关系数分别为0.996 7和0.998 8.检出限为0.3μg/mL.  相似文献   

6.
[目的]探究AAPH诱导的槲皮素氧化产物对Hep G2细胞氧化还原状态的影响。[方法]用紫外-可见波长扫描、HPLC-MS方法分析AAPH和槲皮素在37℃下反应12 h生成的产物结构;以槲皮素-AAPH反应产物处理Hep G2细胞24 h,测定其对细胞存活率、ROS水平及细胞总抗氧化能力(T-AOC)、谷胱甘肽过氧化物酶(GSH-Px)活性、超氧化物歧化酶(SOD)活性、GSH/GSSG比值及丙二醛(MDA)含量的影响,并测定Nrf2、Keap1、NQO1、Prdx1相关抗氧化基因的mRNA表达。[结果]AAPH与槲皮素体系在反应12 h后于294 nm波长处有特征吸收,LC-MS解析结果表明该体系反应生成了含4种主要氧化产物的混合物。与空白组相比,槲皮素与AAPH氧化产物孵育显著降低了细胞存活率,同时细胞内ROS水平和MDA含量升高,细胞内T-AOC水平、GSH-Px及SOD活性显著降低,并显著下调Nrf2、NQO1、Prdx1 mRNA表达,上调Keap1 mRNA表达。[结论]槲皮素氧化产物可造成Hep G2细胞出现氧化应激。  相似文献   

7.
Previous studies of anaerobic biocorrosion have suggested that microbial sulfur and phosphorus products as well as cathodic hydrogen consumption may accelerate anaerobic metal oxidation. Methanogenic bacteria, which normally use molecular hydrogen (H(2)) and carbon dioxide (CO(2)) to produce methane (CH(4)) and which are major inhabitants of most anaerobic ecosystems, use either pure elemental iron (Fe(0)) or iron in mild steel as a source of electrons in the reduction of CO(2) to CH(4). These bacteria use Fe(0) oxidation for energy generation and growth. The mechanism of Fe(0) oxidation is cathodic depolarization, in which electrons from Fe(0) and H(+) from water produce H(2), which is then released for use by the methanogens; thermodynamic calculations show that significant Fe(0) oxidation will not occur in the absence of H(2) consumption by the methanogens. The data suggest that methanogens can be significant contributors to the corrosion of iron-containing materials in anaerobic environments.  相似文献   

8.
为了探究施铁对普通野生稻田甲烷的减排效果，对1个根表铁膜形成能力较强的普通野生稻居群进行了水泥池小区对比试验，观测了施铁处理和对照的CH4排放速率、土壤孔隙水Fe2+浓度和根表铁膜。结果表明:施铁导致CH4总排放量减少了29.51%，在普通野生稻生长前期CH4减排效应尤为明显。移栽后第19 天，施铁小区的土壤孔隙水Fe2+浓度为0.57 mmol·L?1 ，显著大于对照小区。根生物量和单株根表铁膜数量在施铁处理和对照之间的差异随植株年龄增大而增大。因此，施铁措施对具有厚铁膜潜力的普通野生稻居群的CH4减排能起到明显的促进作用。  相似文献   

9.
Lazaroff N 《Science (New York, N.Y.)》1983,222(4630):1331-1334
Infrared spectra demonstrate that neither FeSO(4) . 7H(2)O nor its bacterial or abiotic hydrated oxidation products incorporate deuterium in acid D(2)O solutions. Deuterium exchange occurred as bridging OD when bacterially oxidized iron was precipitated from D(2)O solutions as ferric hydroxysulfates. The exclusion of deuterium depended upon the stabilization of aquated Fe(II) and Fe(III) complexes by sulfate ions in outer-sphere coordination and is consistent with the requirement and postulated role of sulfate in iron oxidation by Thiobacillus ferrooxidans.  相似文献   

10.
亚铁厌氧微生物氧化及其在环境污染修复中的作用机制   总被引：1，自引：0，他引：1  
亚铁厌氧微生物氧化是一种新发现的微生物代谢形式.本文介绍了已发现的亚铁厌氧微生物氧化类型:不产氧光合亚铁厌氧微生物氧化、氯酸盐还原型亚铁厌氧微生物氧化、硝酸盐还原型亚铁厌氧微生物氧化,分析了其主要的环境影响因素,重点探讨了亚铁厌氧微生物氧化对污染物迁移、转化及降解过程的影响,并在此基础上提出了进一步的研究方向.  相似文献   

11.
Lower Cretaceous cold-seep fossil assemblages have been found in the Canadian Arctic Archipelago. Serpulid worm tubes and bivalves are most abundant in these communities; in contrast, fossils are scarce in the surrounding strata. The fossils are contained in an isotopically light (delta(13)C = -25 to -50 per mil) carbonate rock groundmass that is interpreted to have formed from bacterial oxidation of methane. The rocks were deposited at intermediate depth (相似文献   

12.
Lunar rock 66095 contains a hydrated iron oxide and has an unusual amount of water for a lunar rock (140 to 750 parts per million), 90 percent of which is released below 690 degrees C. The deltaof water released at these low temperatures varies from -75 to -140 per mil relative to standard mean ocean water (SMOW). The small amount of water released between 690 degrees and 1300 degrees C has a delta of about -175 +/-25 per mil SMOW. These delta values are not unusual for terrestrial water. The delta(18)O of water extracted from 110 degrees to 400 degrees C has a value of +5+/- I per mil SMOW, similar to the value for lunar silicates from rock 66095 and different from the value of -4 to -22 per mil found for samples of terrestrial rust including samples of rusted meteoritic iron. The amount of carbon varies from 11 to 59 parts per million with a delta(13)C from -20 to -30 per mil relative to Pee Dee belemnite. Only very small amounts of reduced species (such as hydrogen, carbon monoxide, and methane) were found, in contrast to the analyses of other lunar rocks. Although it is possible that most of the water in the iron oxide (goethite) may be terrestrial in origin or may have exchanged with terrestrial water during sample return and handling, evidence presented herein suggests that this did not happen and that some lunar water may have a deltaD that is indistinguishable from that of terrestrial water.  相似文献   

13.
Despite being implicated as important intermediates, iron(V) compounds have proven very challenging to isolate and characterize. Here, we report the preparation of the iron(V) nitrido complex, [PhB((t)BuIm)(3)Fe(V)≡N]BAr(F24) (PhB((t)BuIm)(3)(-) = phenyltris(3-tert-butylimidazol-2-ylidene)borato, BAr(F24) = B(3,5-(CF(3))(2)C(6)H(3))(4)(-)), by one electron oxidation of the iron(IV) nitrido precursor. Single-crystal x-ray diffraction of the iron(V) complex reveals a four-coordinate metal ion with a terminal nitrido ligand. M??bauer and electron paramagnetic resonance spectroscopic characterization, supported by electronic structure calculations, provide evidence for a d(3) iron(V) metal center in a low spin (S = 1/2) electron configuration. Low-temperature reaction of the iron(V) nitrido complex with water under reducing conditions leads to high yields of ammonia with concomitant formation of an iron(II) species.  相似文献   

14.
Massive microbial mats covering up to 4-meter-high carbonate buildups prosper at methane seeps in anoxic waters of the northwestern Black Sea shelf. Strong 13C depletions indicate an incorporation of methane carbon into carbonates, bulk biomass, and specific lipids. The mats mainly consist of densely aggregated archaea (phylogenetic ANME-1 cluster) and sulfate-reducing bacteria (Desulfosarcina/Desulfococcus group). If incubated in vitro, these mats perform anaerobic oxidation of methane coupled to sulfate reduction. Obviously, anaerobic microbial consortia can generate both carbonate precipitation and substantial biomass accumulation, which has implications for our understanding of carbon cycling during earlier periods of Earth's history.  相似文献   

15.
设施栽培土壤甲烷氧化的研究   总被引：3，自引：0，他引：3       下载免费PDF全文
研究了设施栽培土壤的甲烷氧化.结果表明,不同土壤对甲烷的氧化能力各异,可能与土壤的理化性质有关;土壤微生物是甲烷氧化的主要生物类群:土壤含水量对甲烷氧化有明显影响,含水量过高或过低对甲烷氧化均具有抑制作用;氮源(包括有机和无机氮源)对甲烷氧化均有抑制作用;不同碳源对甲烷氧化的影响各异,纤维素对甲烷氧化抑制作用最小,而高浓度的甲醇、葡萄糖则对甲烷氧化具有强烈的抑制作用;在甲烷氧化过程中加入葡萄糖能迅速抑制甲烷氧化;在加入葡萄糖的同时保持瓶中充足的氧气,则这种抑制作用可以在5.5 d后得到解除.此外,还研究了从土壤中分离的甲烷氧化菌对碳源的利用情况,表明在甲烷释放极少的设施栽培土壤中,兼性营养的甲烷氧化菌可能在甲烷氧化中占据主要的地位.  相似文献   

16.
The iron isotope composition of sedimentary pyrite has been proposed as a potential proxy to trace microbial metabolism and the redox evolution of the oceans. We demonstrate that Fe isotope fractionation accompanies abiotic pyrite formation in the absence of Fe(II) redox change. Combined fractionation factors between Fe(II)(aq), mackinawite, and pyrite permit the generation of pyrite with Fe isotope signatures that nearly encapsulate the full range of sedimentary δ(56)Fe(pyrite) recorded in Archean to modern sediments. We propose that Archean negative Fe isotope excursions reflect partial Fe(II)(aq) utilization during abiotic pyrite formation rather than microbial dissimilatory Fe(III) reduction. Late Proterozoic to modern sediments may reflect greater Fe(II)(aq) utilization and variations in source composition.  相似文献   

17.
Magmatic differentiation helps produce the chemical and petrographic diversity of terrestrial rocks. The extent to which magmatic differentiation fractionates nonradiogenic isotopes is uncertain for some elements. We report analyses of iron isotopes in basalts from Kilauea Iki lava lake, Hawaii. The iron isotopic compositions (56Fe/54Fe) of late-stagemeltveins are 0.2 permil (per thousand) greater than values for olivine cumulates. Olivine phenocrysts are up to 1.2 per thousand lighter than those of whole rocks. These results demonstrate that iron isotopes fractionate during magmatic differentiation at both whole-rock and crystal scales. This characteristic of iron relative to the characteristics of magnesium and lithium, for which no fractionation has been found, may be related to its complex redox chemistry in magmatic systems and makes iron a potential tool for studying planetary differentiation.  相似文献   

18.
Three crystalline phases of xenon hexafluoride are based on tetrameric association of XeF(5)(+) and F(-) ions into eight-membered rings. Phase I (monoclinic, 8 XeF(6) units per cell) transforms at approximately 10 degrees C to phase II (orthorhombic, 16 XeF(6) units per cell), which in turn transforms at approximately -25 degrees C to phase 111 (monoclinic, 64 XeF(6) units per doubly primitive cell). The transformation from phase I to phase II requires gross reorientation of half of the tetramers in the structure. The transformation from phase II to phase III involves only an ordering of right-handed and left-handed configurations.  相似文献   

19.
目的 研究几种代表性商品化除草剂以及植物源除草化合物小檗碱及其类似物对拟南芥根尖细胞氧化还原电位的影响。方法 以靶向线粒体的氧化还原敏感绿色荧光蛋白（Mitochondria targeted redox-sensitive green fluorescent protein, mt-roGFP1）标记的拟南芥转基因植株为材料,采用不同质量浓度的化合物处理不同时间后,测定拟南芥根冠、分生区、过渡区和伸长区的细胞氧化还原电位的变化。结果 经几种商品化除草化合物处理后,拟南芥根部分生区的细胞氧化还原电位最小。从分生区到伸长区氧化还原电位逐渐增大,呈现逐渐被氧化的趋势。其中,光系统II抑制剂(莠去津和环嗪酮)的氧化还原电位变化规律最为明显,说明mt-roGFP1荧光探针能较好地响应光系统II抑制剂。氨基酸生物合成抑制剂草甘膦对拟南芥根尖细胞氧化还原的影响具有明显的剂量-效应关系,随着草甘膦质量浓度增加,氧化还原电位变化量也逐渐增大,呈正相关关系(R2 =0.9956)。小檗碱及其类似物处理后,大多数处理组的拟南芥根尖细胞的氧化还原电位在分生区达到最大还原值,并从分生区开始逐渐被氧化。结论 研究结果可以为应用roGFP荧光探针技术研究除草化合物对根系细胞线粒体的作用机制提供基础。  相似文献   

20.
Large (about 5 per mil) millennial-scale benthic foraminiferal carbon isotopic oscillations in the Santa Barbara Basin during the last 60,000 years reflect widespread shoaling of sedimentary methane gradients and increased outgassing from gas hydrate dissociation during interstadials. Furthermore, several large, brief, negative excursions (up to -6 per mil) coinciding with smaller shifts (up to -3 per mil) in depth-stratified planktonic foraminiferal species indicate massive releases of methane from basin sediments. Gas hydrate stability was modulated by intermediate-water temperature changes induced by switches in thermohaline circulation. These oscillations were likely widespread along the California margin and elsewhere, affecting gas hydrate instability and contributing to millennial-scale atmospheric methane oscillations.  相似文献   

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