Solar chemistry of metal complexes

Electronic excited states of certain transition metal complexes undergo oxidation-reduction reactions that store chemical energy. Such reactions have been extensively explored for mononuclear complexes. Two classes of polynuclear species exhibit similar properties, and these complexes are now being studied as possible homogeneous sensitizer-catalysts for hydrogen production from aqueous solutions.     

Chiral metal complexes as discriminating molecular catalysts

As molecular recognition continues to gain importance in the biological and physical sciences as well as in the technologies of molecular electronics and optics, so has the need for efficient syntheses of chiral molecules. Chemists are fulfilling this need through use of chiral organometallic molecules. These chiral metal complexes precisely discriminate between enantiotopic atoms, groups, or faces in achiral molecules and catalyze production of a broad array of natural or unnatural substances of excellent enantiomeric purity. Because of their ability to efficiently multiply chirality, even on an industrial level, these catalysts promise to exert a general impact on molecular science and engineering.     

Activation of alkanes with organotransition metal complexes

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.     

Accelerated electron transfer between metal complexes mediated by DNA

DNA-mediated long-range electron transfer from photoexcited 1,10-phenanthroline complexes of ruthenium, Ru(phen)2(3)+, to isostructural complexes of cobalt(III), rhodium(III), and chromium(III) bound along the helical strand. The efficiency of transfer depended upon binding mode and driving force. For a given donor-acceptor pair, surface-bound complexes showed greater rate enhancements than those that were intercalatively bound. Even in rigid glycerol at 253 K, the rates for donor-acceptor pairs bound to DNA remained enhanced. For the series of acceptors, the greatest enhancement in electron-transfer rate was found with chromium, the acceptor of intermediate driving force. The DNA polymer appears to provide an efficient intervening medium to couple donor and acceptor metal complexes for electron transfer.     

麻疯树树皮的挥发性化学成分研究

采用乙醇加热回流法提取麻疯树树皮中的挥发性成分,利用气相色谱-质谱联用仪(GC-MS)及GC对其提取物化学成分进行了解析,分离鉴定化合物的组成及相对含量。从麻疯树树皮的挥发性物质中分离出56个色谱峰,鉴定出37种化合物。化合物类型包括醛、酮、酯、萜类化合物、甾醇类、脂肪酸、烷烃、烯烃、芳香族化合物等,实验证明乙醇加热回流提取是一种提取植物挥发性成分很有效的方法。麻疯树皮的提取物中发现了多种具有开发价值的三萜类和植物甾醇类物质,3个地点采集的麻疯树树皮的化合物组成和相对含量差异不明显,为了解麻疯树的化学物质基础和进一步开发研究提供了理论依据。     

麻疯树的挥发性化学成分

利用气相色谱—质谱联用技术,研究了采自云南省建水县、石屏县和元阳县的麻疯树叶、树皮及种子的挥发性成分,共分离鉴定出66种挥发性化合物,其中树叶39种,树皮35种,种子30种,化合物类型包括醛、酮、酯、萜类化合物、甾醇类、脂肪酸、烷烃、烯烃、芳香族化合物等。5-羟甲基康醛、蒽、棕榈酸、棕榈酸乙酯、亚油酸、亚油酸乙酯、亚油酸甘油酯、角鲨烯和β-豆甾醇等8种化合物为麻疯树叶、树皮及种子共有的挥发性成分。在麻疯树叶、皮及种子的提取物中发现了多种具有开发利用价值的三萜类和植物甾醇类物质和天然维生素E,同时发现相同海拔和生境的麻疯树样品的挥发性化学成分组成较相似,为了解麻疯树各部位的化学物质基础和进一步开发研究提供了理论依据。     

挥发性有机废气的生物处理

挥发性有机化合物(VOCs)具有沸点低、常温常压下易挥发、在大气中持久、不易降解等特征,是仅次于颗粒污染物的又一大类污染物。我国环境监测总站提出了反映我国环境特征的中国环境优先污染物,共有14类68种,其中有机物12类58种,VOCs占有机物总数的50%。挥发性有机化合物包括低浓度的苯、甲苯、苯乙烯、多环芳烃等,这类挥发性有机化合物会对人体健康和生态环境造成危害,治理VOCs污染是大气污染治理的重要部分。本文主要介绍生物洗涤塔的工艺流程特点、生物反应器中填料和微生物的特点。     

蒙古栎叶挥发性成分的分析

用水蒸馏法提取了两个不同树龄(16年生、55年生)的蒙古栎叶样品中的挥发性成分,采用气相色谱—质谱(GC/MS)技术和标准图谱检索对照的方法分别分离和鉴定了两个样品中的挥发油成分,并用离子流色谱峰面积归一化法计算了各组分的相对含量。从两样品中都分离出了31种化合物,并分别鉴定出了其中的28种(16年生的蒙古栎叶样品)和27种(55年生的蒙古栎叶样品)化合物。结果表明,两样品中都含有烷烃、醇、酯、酮、酸、酚和烯,主要成分都有二十三烷、二十五烷和二十七烷。同时,比较了两样品中挥发油成分的差异。     

丁香挥发油的研究进展

丁香挥发油是丁香中主要的抑菌成分,在食品和医药等方面有较大的发展潜力。为进一步开发利用丁香挥发油,对国内外丁香挥发油的应用研究现状进行了综述,介绍了丁香的种类和分布、丁香挥发油的提取方法及其利用价值,为进一步研究及开发利用丁香资源提供理论依据。     

烤烟红大品种总挥发酸和总挥发碱含量分析

[目的]测定并分析云南大理红大品种烤烟的总挥发酸和总挥发碱含量。[方法]以云南大理红大品种C3F等级烟叶为材料,采用连续流动法测定了108个烤烟样品中的总挥发酸和总挥发碱含量,并对不同品种、烟田类型、海拔、生态区域的烤烟总挥发酸和总挥发碱含量进行了比较分析。[结果]研究表明,云南大理红大品种烤烟总挥发酸含量平均为955.84μg/g,总挥发碱含量平均为1 098.23μg/g。红大品种的总挥发酸含量较高,总挥发碱含量较低。旱地种植的红大烤烟的总挥发酸含量显著高于水稻田;稻田种植的红大烤烟的总挥发碱含量高于旱地烟,但差异不显著。高海拔烟区红大烤烟的总挥发酸含量显著高于中、低海拔,低海拔烟区红大烤烟的总挥发碱含量显著高于高、中海拔。滨湖流域和红河源流域的红大烤烟总挥发碱含量显著高于澜沧江流域和金沙江流域。[结论]研究可为提高烤烟的香气质和香气量的理论研究和生产实践提供依据,也为大理红大烤烟在卷烟配方中的合理利用提供参考。     

Solar Energy Conversion by Water Photodissociation: Transition metal complexes can provide low-energy cyclic systems for catalytic photodissociation of water

The basic concepts for direct and catalyzed photodissociation of water have been summarized. Water dissociation in closed-cycle processes based on endothermic photochemical reactions offers a potential solution to the solar energy conversion problem. Transition metal complexes, whose excited state chemistry is extremely rich (23, 24) although mostly unexplored, are, in principle, suitable "catalysts" for cycles of this type. The most interesting cycles are those involving metal hydrido complexes or binuclear complexes in which the two metal atoms are bound into a macrocyclic ligand. Systematic investigations of the photochemistry of transition metal complexes with the aim of designing suitable systems for solar energy conversion have long-range promise and merit further consideration.     

迷迭香挥发油提取工艺优化及其化学成分分析

采用水蒸气蒸馏法提取迷迭香(Rosmarinus officindis L.)挥发油,运用正交设计优化提取工艺.结果表明,迷迭香挥发油最佳提取工艺条件为迷迭香剪成1 cm长的小段、料水质量比1∶15、浸泡时间3h、提取时间4h,此条件下挥发油的得率为1.870％.运用GC-MS技术分析并比较了迷迭香鲜样和干样挥发油的化学成分,结果表明二者化学成分基本相同,药材阴干后挥发油品质没有受到明显影响.     

2个莱檬品种果皮精油挥发性成分分析

利用气质联用技术(GC-MS),对云南德宏栽培的小菜檬、塔西提2个莱檬品种果皮精油挥发性成分进行研究.结果表明,小莱檬、塔西提莱檬果皮精油中分别检测到17种和24种挥发性成分,烯烃类物质是莱檬果皮精油挥发性的主要组分,其中特征香气成分D-柠檬烯含量最高,β-蒎烯、γ-萜品烯次之.塔西提莱檬特征香气成分物质种类和含量高于小菜檬.     

慢肝养阴胶囊挥发性成分的分析

分析慢肝养阴胶囊中挥发性成分。采用水蒸气蒸馏法提取挥发性成分并通过气相色谱-质谱联用技术进行分析。通过检索NIST08标准质谱图库鉴定出59种成分,占总量的83．16％。含量较多的3个化合物分别是8,9-去氢-9-甲酰基-环异长叶烯（7．0％）、棕榈酸乙酯（5．9％）和4,8,13-杜法三烯-1,3-二醇（5．7％）。慢肝养阴胶囊挥发性成分主要为萜类和酯类,占总成分的61．83％。     

紫丁香花挥发性物质定性分析

采用气相色谱-质谱、气相色谱-红外光谱的分析方法,并借鉴目前国内外研究气味物质的提取方法,对紫丁香花挥发性物质进行了定性分析,鉴定出了11种化合物。此外还发现丁香花花香浓郁绵长与高级烷烃的存在有关。     

植物挥发性有机物的研究进展

植物挥发物在生态系统中起着重要的作用,且与人们健康息息相关。在对大量国内外文献资料研究的基础上,从挥发性有机物的概念、合成代谢、影响因素和研究方法等方面,分别阐述了目前国内外研究进展,并在此基础上提出今后的研究方向。     

挥发性脂肪酸在动物体内的作用

挥发性脂肪酸不仅在反刍动物体内碳水化合物营养中占有重要地位，而且对动物体内代谢有调节作用，挥发性脂肪酸在体内产生的数量，比例受到诸多因素影响，现就此进行综述。