Développement de nouveaux matériaux organométalliques pour des applications dans le domaine de la conversion d’énergie solaire

Dans un contexte où l’approvisionnement énergétique mondial du 21e siècle est un enjeu majeur, le développement de sources d’énergie renouvelables suscite l’attention croissante de la communauté scientifique et industrielle. L’énergie solaire est définitivement l’une des meilleures alternatives aux combustibles fossiles en tant que source d’énergie du monde de demain. Ce mémoire traite donc du développement de nouveaux matériaux organométalliques pour des applications de photorécoltage d’énergie en photovoltaïque et en production d’hydrogène. Le premier chapitre présente la synthèse assistée par microondes de quatre nouveaux complexes de Co(II), Ni(II), Cu(II) et Zn(II) basés sur le ligand tétra-p-méthoxyphényl-azadipyrrométhène (ADPM) avec des rendements variant de 89% à quantitatif. Ces complexes sont mis en relation avec d’autres complexes homoleptiques connus portant le tétraphényl-ADPM comme ligand ainsi qu’avec leurs chélates de BF2+ pour une meilleure compréhension des tendances engendrées par la substitution de l’agent coordonnant et/ou des substituants p-méthoxy. Pour ce faire, le comportement électrochimique et photophysique est présenté. De façon générale, la présence des quatre groupements p-méthoxy semble rendre les dérivés de cet ADPM plus susceptibles à la dégradation électrochimique en conditions d’oxydation et induire un déplacement bathochromique des propriétés optiques d’absorption et d’émission. Les structures rayons X du ligand tétra-p-méthoxyphényl-ADPM et de son complexe homoleptique de Co(II) sont aussi discutées. Cette étude a été effectuée dans l’espoir de fournir des informations utiles sur la stabilité des ADPM aux chercheurs du domaine photovoltaïque en quête de nouveaux chromophores dans le proche infrarouge (NIR). Le deuxième chapitre présente quant à lui les propriétés de senseur envers les anions F-, OAc- et H2PO4- de deux nouveaux complexes neutres de Re(I) de type mono- et dinucléaire basés sur une phénanthroline substituée en position 5 contenant un récepteur thio-urée. Ces composés ont été obtenus dans des rendements de 81% et 60%, respectivement. L’effet de la formation de ponts hydrogène lors de l’ajout d’anions versus la déprotonation du récepteur a été évalué par des titrations UV/Vis et RMN 1H et semble indiquer que la formation de la base conjuguée du récepteur est favorisée pour ce type de système. De plus, la structure rayons X d’un des précurseurs est présentée et permet une discussion sur la chiralité des complexes mono- et dinucléaire obtenus. L’obtention d’un complexe bimétallique par autoassemblage ouvre la voie à la préparation d’antennes moléculaires pour des systèmes de photosynthèse artificielle.

Architectures radiales hétéro-poly-métalliques pour la photosynthèse artificielle et le stockage de l'information

Par une approche supramoléculaire, des architectures radiales hétéro-poly-métalliques ont été réalisées pour des applications en photosynthèse artificielle et en magnétisme moléculaire. Dans une première partie, la synthèse et la caractérisation (spectroscopie UV-vis, émission, électrochimique, DRX) de complexes de ruthénium(II), possédant une gamme de ligands polypyridines, ont été réalisées. Les calculs théoriques ont été effectués afin de soutenir l’interprétation des propriétés photophysiques. Ces complexes, présentant un certain nombre de pyridines externes, ont servi de cœur à des architectures à base de rhénium tris-carbonyles (pour les effets d’antenne), et de cobaloximes (pour les propriétés catalytiques). Les nucléarités obtenues varient de 2 à 7 selon le cœur utilisé. Ces systèmes ont été engagés dans des cycles de photo-production de dihydrogène, démontrant une meilleure efficacité que la référence du domaine, le [Ru(bpy)3]2+. La seconde partie concerne l’étude de couples de métaux de transition, construits à partir de briques polycyanométallates, ou de lanthanides pontés par des ligands oxamides. Ces approches « complexes comme ligand » puis « assemblages comme ligand » permettent d’obtenir des systèmes de haute nucléarité, présentant des propriétés de molécule-aimant ou des effets magnéto-caloriques (à base de CrNi, GdCu, DyCu). Des propriétés photomagnétiques ont été observées sur les couples RuCu et MoCu, pouvant servir de commutateurs moléculaires dans des systèmes complexes. Enfin, une structure hétéro-tétra-métallique trifonctionnelle a été obtenue contenant à la fois un commutateur MoCu, une entité molécule-aimant CuTb et un complexe de ruthénium.

La terre de personne : [le Madrid]

Jérémie et Liliane n’ont pas terminé leurs grilled cheese, et leurs Tetra Pak de jus de pomme sont vides. Charles a déjà réglé l’addition. Devant la porte du restaurant, un homme tend un sac de voyage à une femme. Ils se regardent sans parler. Un petit garçon est plaqué contre la femme, la tête pressée contre sa hanche, le pouce dans la bouche. Charles consulte sa montre. Son ex-femme devait arriver il y a trente minutes. Il s’en veut d’avoir rangé les cahiers à colorier au fond des sacs. Les enfants fixent un des téléviseurs de la salle à manger. Leurs traits sont tirés. Chez lui, ils dorment mal, trop de bruit, trop peu d’espace. Charles aurait mieux fait de passer son tour cette fin de semaine. La grippe qu’il garde à distance depuis vendredi est en train d’éclore. Scusez… J’prendrais un p’tit refill de café. En ce milieu de dimanche après-midi, la salle à manger du Madrid ressemble à une zone de transit. La plupart des tables sont occupées par des pères divorcés et leurs enfants. Même s’il figure parmi les nouveaux venus, Charles reconnaît quelques visages.

Studies on the Flammability of Short Kevlar Fiber-Thermoplastic Polyurethane Composite

The flammability of short Kevlar aramide fiber-thermoplastic polyurethane (TPU) has been investigated with respect to fiber loading and various flame retardant additives such as halogen containing polymers, antimony oxide/chlorine donor combination, zinc borate, and aluminum hydroxide. Smoke generation was reduced drastically, while the oxygen index was reduced marginally in the presence of short fibers. The best improvement in the oxygen index was obtained with antimony oxide/chlorinated paraffin wax combination, in the weight ratio 1:6. A 70 phr loading of aluminum hydroxide improved LOI and reduced smoke generation.

OFFLINE AND ONLINE SOLID PHASE EXTRACTION/PRECONCENTRATION OF INORGANICS

Solid phase extraction (SPE) is a powerful technique for preconcentration/removal or separation of trace and ultra trace amounts of toxic and nutrient elements. SPE effectively simplifies the labour intensive sample preparation, increase its reliability and eliminate the clean up step by using more selective extraction procedures. The synthesis of sorbents with a simplified procedure and diminution of the risks of errors shows the interest in the areas of environmental monitoring, geochemical exploration, food, agricultural, pharmaceutical, biochemical industry and high purity metal designing, etc. There is no universal SPE method because the sample pretreatment depends strongly on the analytical demand. But there is always an increasing demand for more sensitive, selective, rapid and reliable analytical procedures. Among the various materials, chelate modified naphthalene, activated carbon and chelate functionalized highly cross linked polymers are most important. In the biological and environmental field, large numbers of samples are to be analysed within a short span of time. Hence, online flow injection methods are preferred as they allow extraction, separation, identification and quantification of many numbers of analytes. The flow injection online preconcentration flame AAS procedure developed allows the determination of as low as 0.1 µg/l of nickel in soil and cobalt in human hair samples. The developed procedure is precise and rapid and allows the analysis of 30 samples per hour with a loading time of 60 s. The online FI manifold used in the present study permits high sampling, loading rates and thus resulting in higher preconcentration/enrichment factors of -725 and 600 for cobalt and nickel respectively with a 1 min preconcentration time compared to conventional FAAS signal. These enrichment factors are far superior to hitherto developed on line preconcentration procedures for inorganics. The instrumentation adopted in the present study allows much simpler equipment and low maintenance costs compared to costlier ICP-AES or ICP-MS instruments.

Bioactivity Profile of Polyunsaturated Fattyacid extracts from Sardinella longiceps and Sardinella fimbriata – A comparative study

The oceans have proved to be an interminable source of new and effective drugs. Innumerable studies have proved that specific compounds isolated from marine organisms have great nutritional and pharmaceutical value. Polyunsaturated fattyacids (PUFA) in general are known for their dietary benefits in preventing and curing several critical ailments including Coronary heart disease (CHD) and cancers of various kinds. Eicosapentaenoic Acid (EPA) and Docosahexaenoic Acid (DHA) are two PUFA which are entirely marine in origin – and small Clupeoid fishes like sardines are known to be excellent sources of these two compounds. In this study, we selected two widely available Sardine species in the west coast, Sardinella longiceps and Sardinella fimbriata, for a comparative analysis of their bioactive properties. Both these sardines are known to be rich in EPA and DHA, however considerable seasonal variation in its PUFA content was expected and these variations studied. An extraction procedure to isolate PUFA at high purity levels was identified and the extracts obtained thus were studied for anti-bacterial, anti-diabetic and anti-cancerous properties.Samples of both the sardines were collected from landing centre, measured and their gut content analysed in four different months of the year – viz. June, September, December and March. The fish samples were analyzed for fattyacid using FAME method using gas chromatography to identify the full range of fattyacids and their respective concentration in each of the samples. The fattyacids were expressed in mg/g meat and later converted to percentage values against total fatty acids and total PUFA content. Fattyacids during winter season (Dec-Mar) were found to be generally higher than spawning season (June-Sept). PUFA dominated the profiles of both species and average PUFA content was also higher during winter. However, it was found that S. longiceps had proportionately higher EPA as compared to S. fimbriata which was DHA rich. Percentage of EPA and DHA also varied across months for both species – the spawning season seemed to show higher EPA content in S. longiceps and higher DHA content in S. fimbriata. Gut content analysis indicate that adult S. fimbriata is partial to zooplanktons which are DHA rich while adult S. longiceps feed mainly on EPA rich phytoplankton. Juveniles of both species, found mainly in winter, had a gut content showing more mixed diet. This difference in the feeding pattern reflect clearly in their PUFA profile – adult S. longiceps, which dominate the catch during the spawn season, feeding mostly on phytoplankton is concentrated with EPA while the juveniles which are found mostly in the winter season has slightly less EPA proportion as compared to adults. The same is true for S. fimbriata adults that are caught mostly in the spawning season; being rich in DHA as they feed mainly on zooplankton while the juveniles caught during winter season has a relatively lower concentration of DHA in their total PUFA.Various extraction procedures are known to obtain PUFA from fish oil. However, most of them do not give high purity and do not use materials indicated as safe. PUFA extracts have to be edible and should not have harmful substances for applying on mice and human subjects. Some PUFA extraction procedures, though pure and non-toxic, might induce cis-trans conversions during the extraction process. This conversion destroys the benefits of PUFA and at times is harmful to human body. A method free from these limitations has been standardized for this study. Gas Chromatography was performed on the extracts thus made to ensure that it is substantially pure. EPA: DHA ratios for both samples were derived - for S. longiceps this ratio was 3:2, while it was 3:8 for S. fimbriata.Eight common strains of gram positive and gram negative bacterial strains were subjected to the PUFA extracts from both species dissolved in acetone solution using Agar Well Diffusion method. The activity was studied against an acetone control. At the end of incubation period, zones of inhibition were measured to estimate the activity. Minimum inhibitory concentration for each of the active combinations was calculated by keeping p < 0.01 as significant. Four of the bacteria including multi-resistant Staphylococcus aureus were shown to be inhibited by the fish extracts. It was also found that the extracts from S. fimbriata were better than the one from S. longiceps in annihilating harmful bacteria.Four groups of mice subjects were studied to evaluate the antidiabetic properties of the PUFA extracts. Three groups were induced diabetes by administration of alloxan tetra hydrate. One group without diabetes was kept as control and another with diabetes was kept as diabetic control. For two diabetic groups, a prescribed amount of fish extracts were fed from each of the extracts. The biochemical parameters like serum glucose, total cholesterol, LDL & HDL cholesterol, triglycerides, urea and creatinine were sampled from all four groups at regular intervals of 7 days for a period of 28 days. It was found that groups fed with fish extracts had marked improvement in the levels of total LDL & HDL cholesterol, triglycerides and creatinine. Groups fed with extracts from S. fimbriata seem to have fared better as compared to S. longiceps. However, both groups did not show any marked improvement in blood glucose levels or levels of urea.Cell lines of MCF-7 (Breast Cancer) and DU-145 (Prostate Cancer) were used to analyse the cytotoxicity of the PUFA extracts. Both cell lines were subjected to MTT Assay and later the plates were read using an ELISA reader at a wavelength of 570nm. It was found that both extracts had significant cytotoxic effects against both cell lines and a peak cytotoxicity of 85-90% was apparent. IC50 values were calculated from the graphs and it was found that S. longiceps extracts had a slightly lower IC50 value indicating that it is toxic even at a lower concentration as compared to extracts from S. fimbriata.This study summarizes the bioactivity profile of PUFA extracts and provides recommendation for dietary intake; fish based nutritional industry and indigenous pharmaceutical industry. Possible future directions of this study are also elaborated.

Synthesis and Photochemistry of a few Olefin appended Dibenzobarrelenes and Bisdibenzobarrelenes

The thesis entitled: ‘Synthesis and Photochemistry of a few Olefin appended Dibenzobarrelenes and Bisdibenzobarrelenes’ is divided into 5 chapters.In Chapter 1, the fundamental concepts of Diels-Alder reaction, di-r:methane rearrangement and energy transfer process in organic photochemistry is discussed.Chapter 2 presents the synthesis of 9-olefin appended anthracenes and bisanthracenes. The target of synthesising various bridgehead olefin appended dibenzobarrelenes and some novel bisdibenzobarrelenes, led us to the synthesis of the appropriate alkenylanthracenes and bisanthracenes as precursor molecules. Diels-Alder reaction was the synthetic tool for the preparation of the target olefin appended dibenzobarrelenes and bisdibenzobarrelenes. This chapter attempts to throw light on our endeavours in synthesising the various 9-alkenylanthracenes and bisanthracenes.Chapter 3 deals with the synthesis of olefin appended dibenzobarrelenes and bisdibenzobarrelenes. Ever since the discovery of di-It-methane rearrangement dibenzobarrelenes, tailored with dijferent substituents at various positions have always been a tool to photochemists in unravelling the mechanisms of light induced reactions. Our intention of analysing the role of a It-moiety at the bridgehead position of the dibenzobarrelene, was synthetically envisaged via the Diels-Alder reaction. Bisdibenzobarrelenes were synthesised through tandem Diels-Alder reaction. Various alkenylanthracenes and bisanthracenes were employed as dienes and the dienophiles used were dimethyl acetylenedicarboxylate and dibenzoylacetylene. In this chapter, we report our venture in synthesising the various olefin appended dibenzobarrelenes and bisdibenzobarrelenes. Chapter 4 describes the preliminary time-resolved fluorescence studies of some olefin appended dibenzobarrelenes and bisdibenzobarrelenes.To understand the primary and secondary physicochemical processes in a photochemical reaction it is necessary to characterise the excited states and the transient intermediates during their short lifetime. A number of methods developed on the basis of the physical properties of the transient species are available for their detection. Time-correlated single-photon counting technique has been utilised in the present study of the excited states of olefin appended dibenzobarrelenes and bisdibenzobarrelenes. To understand the primary and secondary physicochemical processes in a photochemical reaction it is necessary to characterise the excited states and the transient intermediates during their short lifetime. A number of methods developed on the basis of the physical properties of the transient species are available for their detection. Time-correlated single-photon counting technique has been utilised in the present study of the excited states of olefin appended dibenzobarrelenes and bisdibenzobarrelenes.Chapter 5 portrays the photochemistry of olefin appended dibenzobarrelenes and bisdibenzobarrelenes. Dibenzocyclooctatetraene and dibenzosemibullvalene are the photoproducts obtained respectively through the singlet excited state and the triplet excited state of dibenzobarrelenes. Chemical literature shows evidences of the photoreactivity of dibenzobarrelenes generating both the singlet and triplet mediated photoproducts, in a single photoreaction. Our research target in synthesising various bridgehead olefin appended dibenzobarrelenes and bisdibenzobarrelenes, was based on the perception that olefins are eflicient triplet quenchers, thereby quenching intramolecularly the triplet excited state of the barrelenes. A It-moiety at the bridgehead position of the dibenzobarrelene, creates a tetra tr-methane system, which similar to a 6li—7l' or tri-tr-methane systems, could be the fertile ground for interesting photochemical rearrangements. Our attempts in deciphering the photochemistry of the olefin appended dibenzobarrelenes and bisdibenzobarrelenes is the substance of this chapter.

A Comparative Study Of Tensile And Microstructural Characteristics Of Friction Welded Joints And Conventionally Welded Joints Of Aluminium Alloy 6061

Welding of high strength and low weight materials like Aluminium Alloys without any defects by conventional welding techniques is a major challenge in industries. Hence research on solid state welding techniques like Friction stir welding and Friction welding techniques have got much importance in joining of Aluminium alloys. However most of the industries are not changing conventional techniques as skilled workers are available on that area. Most common conventional welding techniques used for joining of Aluminium alloys are Gas welding and Arc welding. Friction welding is a solid-state welding process that generates heat through mechanical friction between a moving and a stationary component with the addition of a lateral force called “upset” to plast ically displace and fuse the materials. In this work, experimental study on tensile and micro structural characteristics of welded joints formed from conventional welding techniques and Rotary friction welding(suitable for weld specimens with circular cross section) has been carried out and the same were compared. The process parameters for arc welding used was 50-70 Amp reverse polarity DC and electrodes of 2.3mm diameter. In Gas welding, the parameters were oxy acetylene neural flame at 3200°C and 3mm electrodes . In the case of friction welding an axial pressure loading of 3Mpa with 5 MPa as upsetting pressure and 500 rpm were used to obtain good welded joints. Tensile characteristic studies of Arc welded joints and Gas welded joints showed 48% and 60 % variations respectively from the maximum load bearing characteristics of parent metal. In the case of friction welded joint, the variation was found to 46%. Micro structural evaluation of conventionally welded joints exhibited clear distinct zones of various weld regions. In the case of friction welded joint micro structural photographs showed comparable features both in parent metal and welded region. Thus the tensile characteristic study and microstructure evaluations proved that friction welded joints are good in both aspects compared to conventionally welded joints.

Characterization and applications of two protease enzymes obtained by culture dependent and independent approaches from mangrove sediments

Soil community genomics or metagenomics is employed in this study to analyze the evolutionary related - ness of mangrove microbial community. The metagenomic DNA was isolated from mangrove sediment and 16SrDNA was amplified using universal primers. The amplicons were ligated into pTZ57R/T cloning vector and transformed onto E. coli JM109 host cells. The recombinant plasmids were isolated from positive clones and the insert was confirmed by its reamplification. The amplicons were subjected to Amplified Ribosomal DNA Restriction Analysis (ARDRA) using three different tetra cutter restriction enzymes namely Sau3A1, Hha1 and HpaII. The 16SrDNA insert were sequenced and their identity was determined. The sequences were submitted to NCBI database and accession numbers obtained. The phylo - genetic tree was constructed based on Neighbor-Joining technique. Clones belonged to two major phyla of the bacterial domain, namely Firmicutes and Proteobacteria, with members of Firmicutes predominating. The microbial diversity of the mangrove sediment was explored in this manner.

Organic field-effect transistors and phototransistors based on amorphous materials

A comparison between the charge transport properties in low molecular amorphous thin films of spiro-linked compound and their corresponding parent compound has been demonstrated. The field-effect transistor method is used for extracting physical parameters such as field-effect mobility of charge carriers, ON/OFF ratios, and stability. In addition, phototransistors have been fabricated and demonstrated for the first time by using organic materials. In this case, asymmetrically spiro-linked compounds are used as active materials. The active materials used in this study can be divided into three classes, namely Spiro-linked compounds (symmetrically spiro-linked compounds), the corresponding parent-compounds, and photosensitive spiro-linked compounds (asymmetrically spiro-linked com-pounds). Some of symmetrically spiro-linked compounds used in this study were 2,2',7,7'-Tetrakis-(di-phenylamino)-9,9'-spirobifluorene (Spiro-TAD),2,2',7,7'-Tetrakis-(N,N'-di-p-methylphenylamino)-9,9'-spirobifluorene (Spiro-TTB), 2,2',7,7'-Tetra-(m-tolyl-phenylamino)-9,9'-spirobifluorene (Spiro-TPD), and 2,2Ž,7,7Ž-Tetra-(N-phenyl-1-naphtylamine)-9,9Ž-spirobifluorene (Spiro alpha-NPB). Related parent compounds of the symmetrically spiro-linked compound used in this study were N,N,N',N'-Tetraphenylbenzidine (TAD), N,N,N',N'-Tetrakis(4-methylphenyl)benzidine (TTB), N,N'-Bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), and N,N'-Diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (alpha-NPB). The photosensitive asymmetrically spiro-linked compounds used in this study were 2,7-bis-(N,N'-diphenylamino)-2',7'-bis(biphenyl-4-yl)-9,9'-spirobifluorene (Spiro-DPSP), and 2,7-bis-(N,N'-diphenylamino)-2',7'-bis(spirobifluorene-2-yl)-9,9'-spirobifluorene (Spiro-DPSP^2). It was found that the field-effect mobilities of charge carriers in thin films of symmetrically spiro-linked compounds and their corresponding parent compounds are in the same order of magnitude (~10^-5 cm^2/Vs). However, the thin films of the parent compounds were easily crystallized after the samples have been exposed in ambient atmosphere and at room temperature for three days. In contrast, the thin films and the transistor characteristics of symmetrically spiro-linked compound did not change significantly after the samples have been stored in ambient atmosphere and at room temperature for several months. Furthermore, temperature dependence of the mobility was analyzed in two models, namely the Arrhenius model and the Gaussian Disorder model. The Arrhenius model tends to give a high value of the prefactor mobility. However, it is difficult to distinguish whether the temperature behaviors of the material under consideration follows the Arrhenius model or the Gaussian Disorder model due to the narrow accessible range of the temperatures. For the first time, phototransistors have been fabricated and demonstrated by using organic materials. In this case, asymmetrically spiro-linked compounds are used as active materials. Intramolecular charge transfer between a bis(diphenylamino)biphenyl unit and a sexiphenyl unit leads to an increase in charge carrier density, providing the amplification effect. The operational responsivity of better than 1 A/W can be obtained for ultraviolet light at 370 nm, making the device interesting for sensor applications. This result offers a new potential application of organic thin film phototransistors as low-light level and low-cost visible blind ultraviolet photodetectors.

Redox reactions of group 5 elements, including element 105, in aqueous solutions

Standard redox potentials E^0(M^z+x/M^z+) in acidic solutions for group 5 elements including element 105 (Ha) and the actinide, Pa, have been estimated on the basis of the ionization potentials calculated via the multiconfiguration Dirac-Fock method. Stability of the pentavalent state was shown to increase along the group from V to Ha, while that of the tetra- and trivalent states decreases in this direction. Our estimates have shown no extra stability of the trivalent state of hahnium. Element 105 should form mixed-valence complexes by analogy with Nb due to the similar values of their potentials E^0(M^3+/M^2+). The stability of the maximumoxidation state of the elements decreases in the direction 103 > 104 > 105.

Synthesis and characterisation of novel nitrogen and fluorine containing spirobifluorene derivatives for electronic applications and crystal engineering

Among organic materials, spirobifluorene derivatives represent a very attractive class of materials for electronic devices. These compounds have high melting points, glass transitions temperatures and morphological stability, which makes these materials suitable for organic electronic applications. In addition, some of spirobifluorenes can form porous supramolecular associations with significant volumes available for the inclusion of guests. These molecular associations based on the spirobifluorenes are noteworthy because they are purely molecular analogues of zeolites and other microporous solids, with potential applications in separation, catalysis, sensing and other areas.

Phylogeographie und Populationsgenetik der Arten der Gattung Fosterella (Bromeliaceae) in den südamerikanischen Anden

Die tropischen Anden sind eines der artenreichsten Gebiete der Erde. Fast die Hälfte der 45.000 in diesem Gebiet vorkommenden Gefäßpflanzenarten sind in den Anden endemisch (Myers et al. 2000). Die Gattung Fosterella (Bromeliaceae) ist eine den Anden zugeordnete Pflanzengruppe, denn die meisten ihrer 31 Arten kommen in den Anden vor. Achtzehn Arten sind kleinräumige Endemiten. Fosterella hat damit Modellcharakter für diese Region. In der vorliegenden Arbeit wurde die Evolution der Gattung in Raum und Zeit mithilfe der vergleichenden Sequenzierung von sechs plastidären Loci (atpB-rbcL, matK, psbB-psbH, rpl32-trnL, rps16-trnK, rps16-Intron) und einem nukleären Marker (PHYC) untersucht. Es wurden über 90 Akzessionen von 24 Fosterella-Arten untersucht. Mit 5,6 % informativer Merkmale innerhalb der Gattung war rpl32-trnL der informativste Chloroplastenmarker. Es wurden mit den kombinierten Sequenzdaten eine Maximum Parsimony-, eine Maximum Likelihood- und eine Bayes´sche Analyse berechnet. Weiterhin wurden biogeographische und ultrametrische Untersuchungen durchgeführt. Die 6-Locus-Phylogenie zeigt eine Aufteilung der monophyletischen Gattung Fosterella in sechs Gruppen, von denen vier – die penduliflora-, weddelliana-, weberbaueri- und micrantha-Gruppe - klar monophyletisch und gut gestützt sind. Die albicans- und die rusbyi-Gruppe bilden hingegen einen Komplex. Ultrametrische Analysen legen ein Alter der Gattung von ca. 9,6 Mio. Jahren nahe. Der geographische Ursprung von Fosterella befindet sich nach den vorliegenden biogeographischen Analysen in den Anden und nach der Biom-Analyse zu gleicher Wahrscheinlichkeit entweder in andinen Trockenwäldern (seasonally dry tropical forests, SDTFs) oder in azonalen Standorten des amazonischen Tieflands östlich der Anden. Es gab mehrere Ausbreitungsereignisse, von denen die beiden Fernausbreitungsereignisse nach Mittelamerika (F. micrantha) und in das zentrale Amazonasgebiet (F. batistana) die auffälligsten sind. Die feuchten Bergregenwälder (Yungas) der Anden wurden offenbar mehrfach unabhängig von Fosterella-Arten besiedelt. Insgesamt wurden elf nukleäre Marker (XDH, GS, RPB2, MS, ADH, MS, GLO/PI, CHS, FLO/LFY, NIAi3 und PHYC) auf ihre Anwendbarkeit für molekularsystematische Studien in Fosterella getestet. Davon konnten acht Marker erfolgreich mithilfe einer PCR amplifiziert werden. Die Fragmentgrößen lagen zwischen 350 bp und 1.500 bp. Nur für drei Loci (FLO/LFY, NIAi3 und PHYC) konnten lesbare DNA-Sequenzen in Fosterella erzeugt werden. FLO/LFY zeigte nur 1,5 % Variabilität innerhalb der Gattung. Der NIA-Locus erzeugte bei der Amplifikation mehrere Fragmente, die separat voneinander sequenziert wurden. Der Locus PHYC konnte hingegen aufgrund der guten Amplifizier- und Sequenzierbarkeit für das gesamte Probenset sequenziert werden. Dieser Marker zeigte eine Variabilität innerhalb der Gattung von 10,2 %, davon waren 6,8 % informativ. In der Phylogenie basierend auf PHYC ist Fosterella klar monophyletisch, innerhalb der Gattung zeigt sich jedoch an der Basis eine unaufgelöste Polytomie. Es lassen sich neun mehr oder weniger gut gestützte Artengruppen definieren – rusbyi-, villosula-, albicans-, weddelliana-, penduliflora-, weberbaueri-, micrantha-, robertreadii- und spectabilis-Gruppe - die sich in ihrer Zusammensetzung mit Ausnahme der weddelliana-Gruppe von den nach Chloroplastendaten definierten Gruppen unterscheiden. Viele Arten sind para- oder polyphyletisch, so z. B. F. albicans, F. penduliflora und F. rusbyi. Bei den beiden erstgenannten Arten weisen die unterschiedlichen Stellungen in Chloroplasten- und Kernphylogenie auf Hybridisierungsereignisse hin.

Efectos reglamentarios y jurisdiccionales del derecho comunitario Andino sobre el derecho administrativo colombiano

Este trabajo se soporta sobre una base conformada por dos conceptos, que constituyen el horizonte contextual de la investigación: Derecho Administrativo y Comunidad de integración. Es claro que al hablar de una Comunidad de integración específica como la Comunidad Andina (CAN), incide de forma directa en la actividad del derecho administrativo.Ha sido necesario que los países que conforman los grupos de integración económica cedan parte de sus competencias para crear un ordenamiento jurídico de orden supranacional, el cual modifica la dinámica social de las relaciones comerciales y afecta la estructura de la administración pública, haciendo que el derecho administrativo no se limite a interactuar solo con derecho nacional. Esta mutua dependencia de las políticas internas y las regionales se realiza, entonces, cada vez que existe participación y compromiso de los Estados frente a las decisiones, de carácter vinculante o no. En esa medida surge el problema de investigación tendiente a esclarecer cómo ha sido la adopción de las decisiones e interpretaciones, emanadas de los mecanismos oficiales del Derecho Comunitario Andino, en el ordenamiento jurídico colombiano. La existencia de varios puntos de vista con respecto a la obligatoriedad o no de dicha adopción, moldea un tema de suficiente amplitud y profundidad para ser estudiado en un trabajo de investigación.