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比较研究了以C2O42-为共反应物时5个结构相关的Ru(II)配合物[Ru(bpy)2L1]2+, [Ru(bpy)2L2]2+, [Ru(bpy)2L3]2+, [Ru(phen)2L1]2+和[Ru(phen)2L2]2+(其中bpy=2,2′-联吡啶, phen=1,10-邻菲啰啉, L1=4-羧基苯基咪唑[4,5-f][1,10]邻菲啰啉, L2=3-羧基-4-羟基苯基咪唑[4,5-f][1,10]邻菲啰啉, L3=3,4-二羟基苯基咪唑[4,5-f][1,10]邻菲啰啉)的电致化学发光(ECL)性质. 结果表明, 酚羟基的存在能有效地淬灭Ru(II)配合物[Ru(bpy)2L2]2+, [Ru(bpy)2L3]2+和[Ru(phen)2L2]2+的ECL, 其它Ru(II)配合物的ECL量子效率与[Ru(bpy)3]2+相差不大. 相似文献
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为了探索侧链R基团对碱金属离子与多肽复合物气相裂解反应的影响, 采用电喷雾电离质谱法研究了碱金属离子Li+, Na+和K+分别与甘氨酸三肽(GGG)、 甘氨酰-苯丙氨酰-甘氨酸三肽(GFG)和甘氨酰-甘氨酰-苯丙氨酸三肽(GGF)形成的复合物的气相裂解反应. 质谱定性实验结果表明, Li+, Na+和K+与GGG, GFG或GGF在气相中可以形成稳定的复合物, 配合比为1∶1或2∶1. 竞争反应质谱图显示, GGG, GFG或GGF与碱金属离子形成的复合物的质谱峰丰度按Li+, Na+, K+顺序依次下降, 表明随着碱金属离子半径的增加, 它们与三肽的结合强度依次减弱. 碰撞诱导解离显示, 母体离子[GGG+Na]+, [GGF+Na]+和[GFG+Na]+ 的质心碰撞能量E(CM)50数值分别为1.94, 1.76和1.63 eV. 通过质谱滴定法测得[GGG+Na]+, [GFG+ Na]+和[GGF+Na]+ 的结合常数lg 分别为5.30, 5.25和5.17. 质谱法定量结果进一步确认复合物的稳定性顺序为[GGG+Na]+>[GGF+Na]+>[GFG+Na]+, 表明由于空间位阻的影响, 侧链R基团含有苄基的GFG或 GGF与Na+的键合强度要小于侧链R全部为H的GGG. 串级质谱分析结果显示, 碱金属化的GGG断裂位点较多, 可解离出丰富的金属化a2, b和y型碎片离子, 而碱金属化的GGF和GFG解离出的金属化y型离子较多, b型离子其次, 金属化a型离子几乎没有. 此外, 双碱金属化的GGF可解离出较多金属化y型离子. 复合物[GGF+Na]+的裂解曲线显示, 当碰撞能量为25 eV时, [y2+Na-H]+ 和[b2+Na+OH]+为主要碎片离子, 当碰撞能量>40 eV时, 只有[b2+Na+OH]+ 碎片离子占有优势数量. 根据质子化三肽裂解机理可以推测, 钠化GFG裂解后生成含噁唑酮的[b2+Na]+离子, 该离子经过一系列过渡态生成[a2+Na]+(2-苄基-4-咪唑酮), 而不是常见的亚胺离子. 相似文献
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碳苷研究(Ⅵ)——1-芳基-D-吡喃葡萄糖碳苷的快原子轰击质谱 总被引:1,自引:0,他引:1
快原子轰击质谱(FAB-MS)是近几年发展起来的一种质谱新技术[1],特别适于极性大、不易挥发和对热不稳定的化合物,已用于多肽[2]、核酸[3]及苷[4]的结构测定。 相似文献
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<正>甲醛是一种无色有刺激性气味的气体,被世界卫生组织(WHO)定为致畸和致癌的物质之一[1]。我国规定室内空气甲醛的限值为0.10 mg·m-3[2]。目前监测环境中甲醛的国家标准测定方法很多[3],常用的有4-氨基-3-联氨-5-巯基-1,2,4-三氮杂茂(Ⅰ)(AHMT)分光光度法[4]、3-甲基-2-苯并噻唑啉酮腙盐酸盐水合物(MBTH)酚试剂分光光度法[5]、乙酰丙酮分光光度法[6]、气相色谱法(GC)[7]、 相似文献
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二苯并噻吩及其氧化物与离子液体相互作用的理论研究 《燃料化学学报》2012,40(12):1444-1453
采用密度泛函理论方法比较了DBT/DBTO2和[BMIM]+[PF6]-/[BMIM]+[BF4]-的相互作用。对最稳定的[BMIM]+[PF6]-、[BMIM]+[PF6]--DBT、[BMIM]+[PF6]--DBTO2、[BMIM]+[BF4]-、[BMIM]+[BF4]--DBT、[BMIM]+[BF4]--DBTO2进行了NBO和AIM分析。结果表明,DBT和[BMIM]+[PF6]-/[BMIM]+[BF4]-中的咪唑环彼此相互平行,NBO和AIM分析表明它们之间发生了π-π相互作用。H1'和H9'形成的F…H氢键有利于π-π堆积作用的形成。DBTO2倾向于趋近C2-H2和甲基基团形成O…H相互作用;DBTO2优先吸附在[BMIM]+[PF6]-/[BMIM]+[BF4]-。在模拟油中,[BMIM]+[PF6]-和[BMIM]+[BF4]-离子液体对DBTO2的萃取能力大于DBT,其原因是可能是DBTO2具有较大的极性和O…H与F…H的氢键作用。 相似文献
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近年来,离子选择性电极已应用于有机氯、溴[1-3]及碘[4]的微量分析。但在电位滴定中,水介质的终点不明显[5-6],非水介质用的乙酸[1,2]有刺激性,而1,4-二氧环[3]已烷则价太贵。 相似文献
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苯乙烯基吡啶化合物,由于它可能在医学方面[1]和光电子功能材料[2]方面有实际应用前景,已引起人们的兴趣。苯乙烯吡啶化合物的光化学性质类似于二苯乙烯化合物,在光照下可以发生顺-反异构反应[3]、加成反应和二聚反应[4]等不同的光化学反应。 相似文献
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动物油在不同催化剂上的转化 总被引:1,自引:0,他引:1
在固定床微反装置内,对动物油在USY,HZSM-5,ANA,Al2O3和SiO2催化剂上的反应行为进行了研究.结果表明,脂肪酸酯分子一般先发生脱羧和脱羰反应(主要是C-O键的断裂),初始裂化反应产生的大分子烃类及其含氧衍生物会在催化剂的酸性位上发生二次裂化和脱氧等反应.USY和HZSM-5分子筛的酸性强,有利于二次裂化,生成较多的液化气和汽油;在具有弱酸位、大孔的Al2O3催化剂上,发生温和的二次裂化反应,转化率略低;而在非酸性的大孔SiO2催化剂及无孔的ANA分子筛上,二次裂化反应被显著抑制,转化率更低,产物中存在大量的含氧衍生物.热裂化反应会产生较多的CO2,而催化裂化反应会产生相对较多的CO. 相似文献
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N. A. S. Amin Sriraj Ammasi 《天然气化学杂志》2006,15(3):191-202
A dual-bed catalytic system is proposed for the direct conversion of methane to liquid hydrocarbons. In this system, methane is converted in the first stage to oxidative coupling of methane (OCM) products by selective catalytic oxidation with oxygen over La-supported MgO catalyst. The second bed, comprising of the HZSM-5 zeolite catalyst, is used for the oligomerization of OCM light hydrocarbon products to liquid hydrocarbons. The effects of temperature (650-800℃), methane to oxygen ratio (4 10), and SiO2/Al2O3 ratio of the HZSM-5 zeolite catalyst on the process are studied. At higher reaction temperatures, there is considerable dealumination of HZSM-5, and thus its catalytic performance is reduced. The acidity of HZSM-5 in the second bed is responsible for the oligomerization reaction that leads to the formation of liquid hydrocarbons. The activities of the oligomerization sites were unequivocally affected by the SiO2/Al2O3 ratio. The relation between the acidity and the activity of HZSM-5 is studied by means of TPD-NH:j techniques. The rise in oxygen concentration is not beneficial for the C5 selectivity, where the combustion reaction of intermediate hydrocarbon products that leads to the formation of carbon oxide (CO CO2) products is more dominant than the oligomerization reaction. The dual-bed catalytie system is highly potential for directly converting methane to liquid fuels. 相似文献
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Effects of ammonium exchange and Si/Al ratio on the conversion of methanol to propylene over a novel and large partical size ZSM-5 下载免费PDF全文
One type of ZSM-5 zeolite with large partical size was prepared and characterized by XRD, SEM, N2 adsorption-desorption, XRF, Py-IR and NH3-TPD techniques. Effects of ammonium exchange and SiO2/Al2O3 molar ratios on the reaction of methanol to propylene (MTP) over Na-ZSM-5 and H-ZSM-5 zeolites have been studied in a fixed-bed flow reactor under the operating conditions of T = 500 °C, P = 1 atm, and WHSV = 6 h-1. Ammonium exchange led to a rapid decrease in Na content for Na-ZSM-5 zeolite. The reaction results indicated that Na-ZSM-5 and H-ZSM-5 with different SiO2/Al2O3 molar ratios all exhibited high activity for methanol conversion. Ammonium exchange and the decreased SiO2/Al2O3 molar ratio of ZSM-5 zeolite led to an increase both in strong acid sites and weak acid sites. Na-ZSM-5 with high SiO2/Al2O3 molar ratio was favorable for the formation of propylene. The highest propylene selectivity (45.9%) was obtained over Na-ZSM-5 zeolite catalyst with SiO2/Al2O3 molar ratio of 220. 相似文献
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lntroductionThesmallolefinslikeethylene,propeneandbutenearethec0mmerciallydesirablepetrochemicalfeedstocksandarefoundincreasingusageinchemicalindustry.Theyareusuallyobtainedfromthepyrolysis0fpetroleumhydrocarb0nswithsteaInatveryhightemPeratUreandarealsoavailablefromFCCprocess.TheimProvedFCCcatalystforeIhancingtheolefinproducthasbeenreportedll].However,FCCisalrnostimPossiblefortheshortchainalkanefeedstockscutfrompetroleum0robtuinedfromrefinerygasornatUralgassincecrackingofhydrocarbonsbeco… 相似文献
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Structural and mechanistic investigation of a phosphate-modified HZSM-5 catalyst for methanol conversion 总被引:1,自引:0,他引:1
Abubakar SM Marcus DM Lee JC Ehresmann JO Chen CY Kletnieks PW Guenther DR Hayman MJ Pavlova M Nicholas JB Haw JF 《Langmuir : the ACS journal of surfaces and colloids》2006,22(10):4846-4852
Phosphorus modification of a HZSM-5 (MFI) zeolite by wet impregnation has long been known to decrease aromatic formation in methanol conversion chemistry. We prepared and studied a catalyst modified by introducing trimethylphosphine under reaction conditions followed by oxidation. Magic-angle spinning (MAS) NMR shows that extensive dealumination occurs, resulting in a catalyst with a much higher framework SiO2/Al2O3 ratio, as well as extraframework aluminum and approximately 1.4 equiv of entrained phosphoric acid (under working conditions) per aluminum. Upon dehydration or regeneration, the phosphoric acid is converted, reversibly, to entrained P4O10. The aromatic selectivity of the modified catalyst is significantly lower than that of an unmodified zeolite with a similar, increased framework SiO2/Al2O3 ratio. By comparing the rates of H/D exchange in propene under conditions similar to those in methanol conversion chemistry, we determined that the acid site strength is indistinguishable on modified and unmodified zeolites, and this is consistent with theoretical modeling. On the phosphorus-modified zeolite, the rate of propene oligomerization is greatly suppressed, suggesting that entrained phosphate is an impediment to sterically demanding reactions. 相似文献
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含锆ZSM-5分子筛上丙烯齐聚反应的研究 总被引:3,自引:2,他引:3
以正丁胺(NBA)为模板剂,通过水热法直接合成了Zr/ZSM-5分子筛。XRD分析表明Zr/ZSM-5分子筛结晶度良好,但衍射峰的强度稍有差别。SEM显示样品分子筛表面规整,为3 μm~5 μm的棒状晶体。采用NH3-TPD法对分子筛进行了酸性测试,结果表明,在锆质量分数0.2%~1.2%,分子筛的中强酸和强酸量随锆质量分数的增加而增大,并向高温方向偏移。丙烯齐聚催化反应的活性评价结果显示,中强酸和强酸的量对Zr/HZSM-5催化性能有显著影响,在反应过程中对链的增长起促进作用。 相似文献
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High-resolution 17O/1H double resonance NMR spectra were obtained for two zeolites, one with a low Si/Al ratio (zeolite HY) and one with a high Si/Al ratio (HZSM-5), to investigate their local structure and Br?nsted acidity. Two different oxygen signals, corresponding to Br?nsted acid sites in supercages and sodalite cages of zeolite HY were readily resolved in the two-dimensional (2-D) 1H-17O heteronuclear correlation (HETCOR) NMR spectra allowing the 17O isotropic chemical shift (deltaCS) and quadrupolar coupling parameters (quadrupolar coupling constant, QCC, and asymmetry parameter, eta) for the two oxygen atoms to be extracted. Similar experiments for HZSM-5 showed that the sites in this system are associated with a much larger distribution in NMR parameters than found in HY. 17O-1H rotational echo double resonance (REDOR) NMR was applied to probe the O-H distances in zeolites HY and HZSM-5. Weaker 17O-1H dephasing was observed for zeolite HZSM-5 in comparison to that of HY, consistent with longer O-H bonds and/or increased proton mobility. 相似文献