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1.
The nature of chain folding in polymers and the determination of the chain length at which folding occurs have been central questions in polymer science. The study of the formation of lamellar polymer crystals through chain folding has received a new impetus as a result of the recent synthesis of normal alkanes of strictly uniform chain lengths up to C(390) H(782). Chain folding is found in all such paraffins starting with C(150)H(302). As with polyethylenes obtained by conventional polymerization, the fold length in the normal alkanes varies with crystallization temperature, but it is always an integral reciprocal of the full chain length. This behavior indicates that the methyl end groups are located at the lamellar surface and that the fold itself must be sharp and adjacently reentrant.  相似文献   

2.
Liquid alkanes with the number of carbon atoms ranging from C7 to C15 were selectively produced from biomass-derived carbohydrates by acid-catalyzed dehydration, which was followed by aldol condensation over solid base catalysts to form large organic compounds. These molecules were then converted into alkanes by dehydration/hydrogenation over bifunctional catalysts that contained acid and metal sites in a four-phase reactor, in which the aqueous organic reactant becomes more hydrophobic and a hexadecane alkane stream removes hydrophobic species from the catalyst before they go on further to form coke. These liquid alkanes are of the appropriate molecular weight to be used as transportation fuel components, and they contain 90% of the energy of the carbohydrate and H2 feeds.  相似文献   

3.
A 50-gram sample of lunar fines was subjected to stepwise extraction in a mixture of benzene and methanol while intact, after being pulverized, and after being digested in hydrofluoric acid. None of these three extracts contained detectable quantities of C(15) to C(30) alkanes. No C(15) to C(30) alkane was present in this lunar sample at a concentration exceeding I part per billion by weight.  相似文献   

4.
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).  相似文献   

5.
The silica-supported transition metal hydrides (=Si-O-Si=)(=Si-O-)2Ta-H and (=Si-O-)xM-H (M, chromium or tungsten) catalyze the metathesis reaction of linear or branched alkanes into the next higher and lower alkanes at moderate temperature (25degrees to 200degreesC). With (=Si-O-Si=)(=Si-O-)2Ta-H, ethane was transformed at room temperature into an equimolar mixture of propane and methane. Higher and lower homologs were obtained from propane, butane, and pentane as well as from branched alkanes such as isobutane and isopentane. The mechanism of the step leading to carbon-carbon bond cleavage and formation likely involves a four-centered transition state between a tantalum-alkyl intermediate and a carbon-carbon final sigma-bond of a second molecule of alkane.  相似文献   

6.
用链烷烃作为内源指示剂测定绵羊的消化率   总被引:3,自引:1,他引:3  
6只阉公绵羊喂给再生长3周的黑麦草450kg,用全收粪法测得的干物质消化率为80.5%,用31碳(C31)和33碳(C33)的链烷烃作为内源指示剂估测的干物质消化率分别为81.5%和79.6%。用C1估测的消化率高于C33(P=0.031),但用该两种链烷烃估测的消化率与用全收粪法测得的消化率无显著差异(P>0.05)。  相似文献   

7.
三种类型柑橘成熟果实表面蜡质分析   总被引:3,自引:1,他引:2  
【目的】分析中国主栽柑橘类型(‘鄂柑一号’椪柑(Citrus reticulata Blanco cv.Ponkan)、尤力克柠檬(C. limon cv Eureka cv. Lemon)和沙田柚(C. grandis Osbeck cv. Shatian Yu)成熟期果实表面蜡质,建立中国柑橘果实蜡质基础数据,为科学指导柑橘采后生产提供依据。【方法】以3种类型柑橘的成熟果实为材料,采用扫描电镜观察果实表面蜡质晶体结构;用GC-MS测定果实表面蜡质成分及含量;用定量PCR检测蜡质相关基因在不同类型柑橘果皮表达特性。【结果】扫描电镜结果显示沙田柚蜡质晶体呈较大的倒伏片状,椪柑片状晶体较小,柠檬介于上述两者之间。GC-MS分析表明,3种类型柑橘果实表面外蜡中脂肪族物质主要组成成分相同,分别为:脂肪醛、饱和游离脂肪酸、饱和正链烷烃和伯醇,但品种之间各组分比例及碳原子分布有一定差异。椪柑、柠檬以及沙田柚外蜡含量分别为1.1、2.2和9.3 μg·cm-2。椪柑外蜡中醛、脂肪酸、烷烃和伯醇所占比例为50%、16%、28%和6%;柠檬中各个成分比例分别为42%、30%、18%和11%;沙田柚中则分别为50%、31%、12%和7%。椪柑中26醛和28醛含量最高;柠檬中碳原子数分配比较均匀,没有绝对占主导的成分;沙田柚脂肪族物质中高碳原子数所占比例比其他柑橘类型果实蜡质中高,尤其是32酸、31和33烷烃含量很高。椪柑和柠檬总蜡含量分别为4.3和4.6 μg·cm-2。椪柑总蜡中醛、脂肪酸、烷烃和伯醇与外蜡各成分所占比例相似,分别为57%、14%、23%和4%;柠檬总蜡各成分所占比例则分别为53%、15%、19%和8%。总蜡不同种类脂肪族物质碳原子数分配与外蜡基本相同。萜类物质种类和含量在不同品种类型之间存在较大差异:柠檬中主要的三萜类成分是软木三帖酮(friedelin)、羽扇豆醇(lupeol)、α-香树精(α-amyrin)和β-香树精(β-amyrin);椪柑中主要含有后3种,没有检测到软木三帖酮;角鲨烯和法尼醇为紧皮柑橘(柚和柠檬)特有。定量表达分析表明,超长链脂肪酸辅酶A合成酶KCS6在不同柑橘类型之间的表达趋势与其对应的物质含量比较吻合,推测该基因造成了这些柑橘类型蜡质含量的差异。酰基转移酶CER2在沙田柚中表达量最高,推测该基因则导致了沙田柚中大于30碳原子数的蜡质成分在不同柑橘类型中占据最高比例。3种类型柑橘果实表面总蜡和外蜡中脂肪族物质均以醛为主,烷烃或酸次之,伯醇最少。总蜡和外蜡物质分配存在差异,其中伯醇和超长链脂肪酸在外蜡中占据比例更高,烷烃则是在外蜡中占据比例较低。萜类物质中三萜类和淄醇仅在总蜡中可以测定出,而角鲨烯和法尼醇则在外蜡和总蜡中都含有。【结论】蜡质成分在柑橘果实中受遗传背景和果皮结构共同影响。宽皮柑橘与紧皮柑橘具有不同的蜡质特征,本研究结果对宽皮柑橘和紧皮柑橘品种特异性的果蜡配方研发具有重要参考价值。  相似文献   

8.
The formation of a single product from terminal functionalization of linear alkanes from a transition metal-catalyzed reaction is reported. The rhodium complex Cp*Rh(eta(4)-C(6)Me(6)) (Cp*, C(5)Me(5); Me, methyl) catalyzes the high-yield formation of linear alkylboranes from commercially available borane reagents under thermal conditions. These reactions now allow catalytic, regiospecific functionalization of alkanes under thermal conditions. The organoborane products are among the most versatile synthetic intermediates in chemistry and serve as convenient precursors to alcohols, amines, and other common classes of functionalized molecules.  相似文献   

9.
Anesthesia cutoff phenomenon: interfacial hydrogen bonding   总被引:6,自引:0,他引:6  
Anesthesia "cutoff" refers to the phenomenon of loss of anesthetic potency in a homologous series of alkanes and their derivatives when their sizes become too large. In this study, hydrogen bonding of 1-alkanol series (ethanol to eicosanol) to dipalmitoyl-L-alpha-phosphatidylcholine (DPPC) was studied by Fourier transform infrared spectroscopy (FTIR) in DPPC-D2O-in-CCl4 reversed micelles. The alkanols formed hydrogen bonds with the phosphate moiety of DPPC and released the DPPC-bound deuterated water, evidenced by increases in the bound O-H stretching signal of the alkanol-DPPC complex and also in the free O-D stretching band of unbound D2O. These effects increased according to the elongation of the carbon chain of 1-alkanols from ethanol (C2) to 1-decanol (C10), but suddenly almost disappeared at 1-tetradecanol (C14). Anesthetic potencies of these alkanols, estimated by the activity of brine shrimps, were linearly related to hydrogen bond-breaking activities below C10 and agreed with the FTIR data in the cutoff at C10.  相似文献   

10.
Water pollution: organic compounds in the Charles River, Boston   总被引:3,自引:0,他引:3  
The major lipophilic organic compounds present in water collected during November and December 1971 from the Charles River Basin (Boston) are as follows: normal alkanes (C(15) to C(31)), alkyl naphthalenes, alkyl anthracenes or phenanthrenes, pyrene, fluoranthene, dibutyl phthalate, and di(2-ethylhexyl) phthalate. The concentration of the naphthalenes (determined by liquid chromatography) correlates with the effective storm-water runoff content of the river. These data suggest a multiplicity of sources ranging from indigenous biological materials to automobile exhaust condensate.  相似文献   

11.
A sample of lunar dust was examined for organic compounds. Carbon detected in concentrations of 157 micrograms per gram had a delta(13)C per mil (PDB) value of + 20. Treatment with hydrochloric acid yielded hydrocarbons of low molecular weight, suggesting the presence of carbides. The gas chromatogram of the acylated and esterified derivatives of the hydrolyzate was similar to that obtained for the Pueblito de Allende meteorite. There were no detectable amounts of extractable high-molecular-weight alkanes, aromatic hydrocarbons, isoprenoid hydrocarbons, normal alkanes, fatty acids, amino acids, sugars, or nucleic acid bases. Traces of porphyrins were found, perhaps arising from rocket exhaust materials.  相似文献   

12.
Conversion of methane to higher hydrocarbons by its low-temperature activation without forming undesirable carbon oxides is of great scientific and practical importance. Methane can be highly activated, yielding high rates of conversion to higher hydrocarbons and aromatics (10 to 45 percent) at low temperatures (400° to 600°C), by its reaction over H-galloaluminosilicate ZSM-5 type (MFI) zeolite in the presence of alkenes or higher alkanes. The methane activation results from its hydrogen-transfer reaction with alkenes.  相似文献   

13.
Alkanes in fungal spores   总被引:1,自引:0,他引:1  
The chlamydospores of Ustilago maydis, U. nuda, and Sphacelotheca reiliana were analyzed by gas chromatography and mass spectrometry for their hydrocarbon contents. For the first time we observed that they contain paraffinic hydrocarbons; the average contents were 42, 58, and 146 parts per million, respectively. n-Alkanes having odd numbers of carbon atoms predom-inate, with carbon-chain lengths ranging from C(14) to C(37). The major alkanes are n-C(27) in U. maydis, n-C(27) and n-C(35) in U. nuda, and n-C(29) in S. reiliana. Each type of spore carried a distinctly characteristic population of hydrocarbons.  相似文献   

14.
施肥对苏丹草修复石油污染土壤的影响   总被引:2,自引:2,他引:0  
采用盆栽试验,研究了苏丹草修复石油污染土壤的效果,在有、无氮磷钾肥的条件下,对苏丹草的生长发育和石油的组分进行了分析。结果表明,经过90 d的修复,施肥处理的石油烃去除率比无施肥处理的对照高10.31%;苏丹草的株高、地上干重和地下干重也得到了显著提高,而叶绿素a/b和叶绿素a/类胡萝卜素均有所降低;芳烃(16种多环芳烃)的去除率和烷烃(C8~C40)的去除率分别提高了7.39%和6.44%。不论是对照还是施肥处理,烷烃的去除效果均优于芳烃。  相似文献   

15.
采前套袋对苹果梨表皮蜡质结构和化学组分的影响   总被引:5,自引:0,他引:5  
【目的】探讨采前套袋处理对苹果梨(Pyrus bretschneideri Rehd. cv. Pingguoli)果皮蜡质结构和化学组分的影响。【方法】在花后60 d对苹果梨果实进行双层套袋处理,通过扫描电镜观察和气相色谱-质谱联用(GC/MS)分析,了解套袋微域环境对果皮蜡质含量、结构和化学组分的影响。【结果】套袋处理苹果梨表皮蜡质含量与未套袋相比差异不显著;与未套袋相比,套袋果实表皮蜡质粗糙、蜡膜不均一、裂纹较多,且表面无蜡质结晶形成。对其蜡质组分分析表明,套袋与未套袋果实检出的蜡质组分数量与种类均存在差异;在含量上套袋果实烷烃较未套袋有所提高,链烷酸有所下降。同时采前套袋处理的果实蜡质组分中饱和链烷酸的碳数分布优势也发生了变化,未套袋果实以C28、C30和C26的相对丰度较大,而套袋果实仅以C26和C28的相对丰度较大,并未检测到C30饱和链烷酸。【结论】采前套袋处理对苹果梨表皮蜡质超微结构、化学组分种类和链长均具有明显的影响,但其影响机制尚需进一步研究。  相似文献   

16.
A species of the genus Bacillus, capable of growth on normal alkanes at 70 degrees C, was isolated by the method known as enrichment culture. Preliminary analyses of its amino acid composition indicate that it would be a good source of protein for human nutrition. Possible advantages of the use of such organisms for the production of single-cell protein include simplification of fermentor cooling and asepsis.  相似文献   

17.
The gas-phase irradiation of CpRh(CO)(2) (Cp = eta(5)-C(5)H(5)) was examined in order to study the rates of reaction of the 16-electron intermediates presumed to be involved in the C-H oxidative addition of alkanes. "Naked" (unsolvated) CpRh(CO) was detected, and direct measurements of the rates of reaction of this very short-lived complex with alkane C-H bonds were made. Activation of C-H bonds occurs on almost every collision for alkanes of moderate size, and intermediates in which the alkanes are bound to the metal centers, without their C-H bonds being fully broken, are implicated as intermediates in the overall reaction.  相似文献   

18.
枯草芽孢杆菌BAB-1产脂肽类及挥发性物质的分离和鉴定   总被引:9,自引:1,他引:8  
【目的】对枯草芽孢杆菌Bacillus subtilis菌株BAB-1产生的脂肽类物质和挥发性物质进行分离鉴定和抑菌活性研究。【方法】采用HPLC和MALDI-TOF-MS对脂肽类物质进行分离纯化和鉴定;采用GC-MS对挥发性物质进行鉴定。【结果】HPLC分析表明,菌株BAB-1产生的脂肽类物质由LP-1、LP-2、LP-3三类组分组成,其中LP-2起主要抑菌作用。MALDI-TOF-MS质谱分析表明,LP-1为surfactin(C13—C15),LP-2为fengycin A(C14—C15)和fengycin B(C14—C18),LP-3成分未能确定。GC-MS结果表明,菌株BAB-1产生的挥发性物质由多种成分组成,主要为醇类、酮类、酸类、胺类和烷烃类等。【结论】枯草芽孢杆菌菌株BAB-1能够产生脂肽类物质和挥发性物质,并且这两类物质都具有较强的抑菌活性。  相似文献   

19.
采用索氏提取法和溶剂萃取法分别提取牛大力(Millettia speciosa Champ.)花苞、花朵和果荚的脂溶性成分,经GC-MS分析,从花苞脂溶性成分中鉴定出24个化合物,占总脂溶性成分的88.31%,主要为烷烃和烯烃类(52.00%)、醇类(17.46%)化合物;从花朵脂溶性成分中鉴定出29个化合物,占总脂溶性成分的91.38%,主要为烷烃和烯烃类(60.64%)、醇类(17.178%)化合物;从果荚脂溶性成分中鉴定出32个化合物,占总脂溶性成分的80.01%,主要为烷烃和烯烃类(32.56%)、苯基及其衍生物类(22.46%)、脂肪酸类(12.54%)化合物,其中6个化合物为共有成分。  相似文献   

20.
Alkanes, although plentiful enough to be considered for use as feedstocks in large-scale chemical processes, are so unreactive that relatively few chemical reagents have been developed to convert them to molecules having useful functional groups. However, a recently synthesized iridium (lr) complex successfully converts alkanes into hydridoalkylmetal complexes (M + R-H --> R-M-H). This is a dihydride having the formula Cp(*)(L)lrH(2), where Cp(*) and L are abbreviations for the ligands (CH(3))(5)C(5) and (CH(3))(3)P, respectively. Irradiation with ultraviolet light causes the dihydride to lose H(2), generating the reactive intermediate Cp(*)lrL. This intermediate reacts rapidly with C-H bonds in every molecule so far tested (including alkanes) and leads to hydridoalkyliridium complexes Cp(*)(L)lr(R)(H). Evidence has been obtained that this C-H insertion, or oxidative addition, reaction proceeds through a simple three-center transition state and does not involve organic free radicals as intermediates. Thus the intermediate Cp(*)lrL reacts most rapidly with C-H bonds having relatively high bond energies, such as those at primary carbon centers, in small organic rings, and in aromatic rings. This contrasts directly with the type of hydrogen-abstraction selectivity that is characteristic of organic radicals. The hydridoalkyliridium products of the insertion reactions can be converted into functionalized organic molecules-alkyl halides-by treatment with mercuric chloride followed by halogens. Expulsion (reductive elimination) of the hydrocarbon from the hydridoalkyliridium complexes can be induced by Lewis acids or heat, regenerating the reactive intermediate Cp(*)lrL. Oxidative addition of the corresponding rhodium complexes Cp(*)RhL to alkane C-H bonds has also been observed, although the products formed in this case are much less stable and undergo reductive elimination at -20 degrees C. These and other recent observations provide an incentive for reexamining the factors that have been assumed to control the rate of reaction of transition metal complexes with C-H bonds-notably the need for electron-rich metals and the proximity of reacting centers.  相似文献   

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