杉木人工林土壤中毒性化感物质的鉴定与来源

针对杉木化感物质种类的争论，我们以生测活性做导向，对杉木人工林土壤中毒性化感物质进行了分离，并通过质谱、核磁共振等仪器对化感物质的化学结构进行了鉴定，然后研究了其活性和来源，同时从土壤养分和化感作用两个方面对杉木火力楠混交林解决杉木连栽障碍的作用机制进行了研究。结果表明： (1) 虽然不同连栽代数土壤养分与杉木幼苗苗高存在正相关关系，即随着杉木连栽代数的增加，土壤养分含量逐渐降低，土壤处理的杉木幼苗苗高也逐渐降低，但是同一林分中，距杉木根系不同距离的土壤养分含量与杉木幼苗根长存在负相关关系。在一代和二代杉木林中，与杉木林地土相比，杉木根际土能够显著地抑制杉木幼苗根生长。单用土壤养分匮缺来解释连栽杉木生产力下降是不充分的，杉木化感作用也是连栽障碍的重要原因之一。 (2) 从杉木人工林土壤中检测到8种酚酸类物质：对羟基苯甲酸、香草酸、阿魏酸、苯甲酸、肉桂酸、香草醛、异香草醛和香豆素。自然浓度的酚类物质没有抑制杉木幼苗的生长，反而促进了杉木幼苗的生长。从连栽杉木林土壤分离到一种新环二肽(6-hydroxy-1,3-dimethyl-8-nonadecyl-[1,4]-diazocane-2,5-diketone)，它在自然浓度条件下能够显著地抑制杉木幼苗的生长。而且当浓度达到40nmol•ml-1时，环二肽对杉木幼苗根生长的抑制率接近50%，显示其具有较高的化感活性。因此，引起连栽杉木生产力下降的化感物质不是对羟基苯甲酸等酚酸类物质，而是从杉木林土壤中分离得到的环二肽。 (3) 杉木各组织中环二肽含量最多的为叶凋落物，而且用杉木叶凋落物处理的土壤中环二肽含量显著增加，这说明杉木叶凋落物是环二肽的重要来源之一。杉木根系分泌物中含有环二肽，而且随着连栽代数的增加，杉木根系分泌环二肽的速率也增加，这说明杉木根系分泌物也是环二肽的重要来源之一。杉木成熟林每年每公顷凋落的叶凋落物中含有约0.173~0.418 mol的环二肽，而每年每公顷杉木根系分泌的环二肽可达1.289~1.362 mol，显著高于前者。因此，杉木根系分泌物是杉木化感物质环二肽最重要的来源。 (4) 杉木火力楠混交林能够提高土壤有机质、全氮等养分含量，增加土壤微生物数量及土壤蔗糖酶、脲酶和磷酸酶等土壤酶活性，从而提高了混交林土壤熟化程度，加速了土壤有机质的转化速率，增强了土壤养分的供应能力，改善了土壤养分匮缺的状况。与二代杉木林相比，杉木火力楠混交林中杉木根系分泌环二肽的速率降低了33.2%，杉木火力楠混交林能减少环二肽的释放量，从而降低土壤中化感物质的含量，减弱林地土壤对杉木幼苗生长的抑制作用，缓解了连栽杉木自毒作用。因此，杉木火力楠混交林是一种高生产力和生态协调的造林模式。

Synthèse et étude de nouvelles molécules potentiellement polymérisables pour la fabrication de matériaux électroluminescents : analogues du 1,3,5 benzènetripyrrole, méthyle 3,5-bipyrrolebenzoate et 6,12-diméthyle-1,5-dipyrrolediazocane

Pyrroles are found in various natural products and in the chemical composition of certain drugs because of their interesting biological properties. Lipitor, Tolmetin and Amtolmetin are examples of drugs with 1,2,5-substituted pyrroles in their composition, in which biological activities have been certified. Moreover, pyrroles are used as precursors of semiconductor polymers, oligomers and dendrimers useful for the synthesis of electroluminescent materials used in devices, such as organic light-emitting diodes, field-effect transistors, solar and organic photovoltaic cells. We are interested in conjugated polymers based on pyrrole due to their optical properties, electrochemical and the conductivity produced by electron delocalization along their carbon chains. The overall objective of the work presented in this thesis is the synthesis of new molecules based on pyrrole for studying their electronic and electrochemical properties as well for the synthesis of conjugated polymers. Initially, we performed the synthesis of 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes, which may serve as precursors for the synthesis of conjugated dendrimers. Their synthesis was made in three steps starting from trimethyl 1,3,5-benzene-tricarboxylate which was converted to 1,3,5-tri-(pent-4-enoyl)benzene using vinylmagnesium bromide in a Grignard reaction catalyzed by copper cyanide. The olefins of 1,3,5-tri-(pent-4-enoyl)benzene were oxidized to produce 1,3,5-tri-(4-oxopentanoyl)benzene using a modified protocol of the Tsuji-Wacker reaction. Subsequent, Paal-Knorr condensation reactions on 1,3,5-tri-(4-oxopentanoyl)benzene with different amines were used to synthesize 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes with different N-substituents in yields between 44 and 60%. Incomplete reaction of vinylmagnesium bromide with trimethyl 1,3,5-benzenetricarboxylate gave the methyl-3,5-di(pent-4-enoyl)benzoate, which was converted to methyl-3,5-dipyrrolylbenzoate following the reaction of Tsuji- Wacker and Paal-Knorr with yields between 30 and 60%. The photochemical and electrochemical properties of the 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes and methyl-3,5-dipyrrolylbenzoates were studied in collaboration with the research group of professor William Skene. The results have shown that both types of pyrrole have potential for the synthesis of conjugated polymers and dendrimers used in the manufacture of electroluminescent materials. Following these encouraging results, we performed the synthesis of 6,12-dimethyl-1,5-dipyrrolediazocane. Methyl N-(Boc)-β-alaninate was converted to its corresponding homoallylic ketone, which was oxidized to N-(Boc)aminoheptan-3,6-dione. The Paal-Knorr condensation between N-(Boc)aminoheptan-3,6-dione and aminoheptan-3,6-dione hydrochloride gave 6,12-dimethyl-1,5-dipyrrolediazocane in 17% yield. In sum, we have synthesized and characterized seven new molecules, six of them having photochemical and electrochemical properties interesting for the synthesis of conjugated polymers and dendrimers. The latter offering potential as precursor for the conception of compounds of therapeutic interest.