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Dissertations / Theses on the topic 'Gelsemium'

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1

Wilkinson, Mark C. "A [4+3] cycloaddition strategy for the synthesis of gelsemine." Thesis, University of Nottingham, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.342482.

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2

Kuzmich, Daniel. "Gelsemium alkaloids : a total synthesis of dl-21-oxogelsemine /." The Ohio State University, 1995. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487864485228496.

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3

Venard, Christine. "Régulation de la neurostéroïdogenèse dans la moëlle épinière et le système limbique par la gelsémine er Gelsemium sempervirens : Analyse cellulaire et implications neurophysiologiques." Université Louis Pasteur (Strasbourg) (1971-2008), 2008. https://publication-theses.unistra.fr/public/theses_doctorat/2008/VENARD_Christine_2008.pdf.

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La gelsémine synthétique, principe actif majoritaire de Gelsemium sempervirens, et la glycine stimulent la biosynthèse d’alloprégnanolone dans la moelle épinière (ME) de rat. De même, les dilutions homéopathiques de gelsémine et de Gelsemium sempervirens augmentent la production d’alloprégnanolone dans la ME et le système limbique. La strychnine, qui n’induit d’elle-même aucune modification de la neurostéroïdogenèse, bloque totalement les effets stimulateurs de ces substances démontrant l’implication des récepteurs glycinergiques dans les mécanismes d’action de ces composés. Ces résultats obtenus in vitro ont été corrélés à des analyses in vivo mettant en relation l’activité de la 3a-hydroxystéroïde oxydo-réductase dans la ME avec les variations des seuils de sensibilité à la douleur. Des stratégies thérapeutiques efficaces avec les dilutions homéopathiques de gelsémine et de Gelsemium sempervirens peuvent ainsi être développées dans le cadre du contrôle de la douleur et de l’anxiété
Synthetic gelsemine, the major active principle in Gelsemium sempervirens composition, and glycine stimulated allopregnanolone biosynthesis in the rat spinal crod (SC). Similarly, homeopathic dilutions of gelsemine and Gelsemium sempervirens strongly increased allopregnanolone production in the SC and limbic system. Strychnine, which did not modify by itself neurosteroid formation, completely blocked the stimulatory effects induced by these substances, indicating that glycinergic receptors are involved in the action mechanisms of these compounds. These results obtained in vitro were correlated with in vivo analyses by linking the 3a-hydroxysteroid oxido-reductase in the SC with changes in thermal and mechanical nociceptive thresholds. Altogether, the data open new possibilities for the development of therapeutic strategies with homeopathic dilutions of gelsemine and Gelsemium sempervirens in the control of pain and anxiety
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4

Bainbridge, Jeremy D. E. "Synthetic studies towards gelsemine." Thesis, University of East Anglia, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.389255.

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5

Fraser, Rebecca Jane. "Synthetic studies towards gelsemine." Thesis, University of Nottingham, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.403697.

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6

Aponte, Jennifer. "Towards the total synthesis of gelsemine." Thesis, University of Birmingham, 2014. http://etheses.bham.ac.uk//id/eprint/4816/.

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Discovered in 1870, in the roots of Gelsemium sempervirens, gelsemine has attracted the attention of numerous research groups over the years. Chapter 1 discusses the isolation and structure elucidation of this cage-like alkaloid, along with the synthetic strategies developed to assemble the densely functionalised hexacyclic skeleton. An overview of the project and optimisation of the synthetic route to the gelsemine core structure are presented in Chapter 2. This sequence involves a 4+3 cycloaddition, a novel access to \(\alpha\) \(\beta\)-unsaturated esters and an elimination - Michael addition step. Finally, a shortened access to the gelsemine core structure from the key step is presented yielding sufficient material for further functionalisation studies. Chapter 3 discusses two novel strategies towards the construction of the gelsemine spiro-oxindole from a key tricyclic ketone. A series of attempts at -arylation of ketones using haloacetanilide derivatives are described, culminating an unexpected one-pot indole synthesis. A spiro-oxindole synthesis is presented using a metal catalysed free-radical CH activation. Progress towards implementing this strategy on the gelsemine core structure is discussed. In Chapter 4 the functionalisation of the bicyclo3.2.1octane core structure is discussed. Selective reduction of the tricyclic ketone gives an axial alcohol that cyclises to afford a lactone as the precursor of the tetrahydropyran ring.
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7

Berber, Karatepe Gulen. "Model studies towards the synthesis of gelsemine." Thesis, University of East Anglia, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.302082.

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8

Wu, Shung C. "Approaches to a Total Synthesis of Gelsemine." The Ohio State University, 1991. http://rave.ohiolink.edu/etdc/view?acc_num=osu1391769463.

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9

Sims, Rupert Oliver. "A photochemical approach towards the synthesis of gelsemine." Thesis, University of Sussex, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.439622.

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10

Dutton, Jonathan Keith. "Approaches to the synthesis of gelsemine and related alkaloids." Thesis, University of Leeds, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.291086.

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11

Byrne, Paul. "A novel photochemical approach towards the synthesis of gelsemine." Thesis, University of Sussex, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.250186.

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12

Tercel, Moana. "New routes to spiro-oxindoles for the synthesis of gelsemine." Thesis, University of Cambridge, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.317870.

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13

Duff, Peter Thomas. "(A) Synthetic studies towards gelsemine : (B) A radical abstraction study." Thesis, University of Reading, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.359294.

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14

Ha, Deok-Chan. "Part I: Synthesis of carbapenems and aminosaccharides ; Part II: Studies toward a synthesis of gelsemine /." The Ohio State University, 1987. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487324944215364.

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15

Lee, Chih-Shone. "Part I. Studies toward a synthesis of gelsemine using free radical cyclization reactions ; Part II. Asymmetric synthesis of ?-lactams /." The Ohio State University, 1988. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487594970651228.

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16

Lam, Jonathan K. "Part I| Ring-Rearrangement Metathesis of Himbert Arene-Allene Cycloadducts for the Rapid, Modular Construction of Complex Molecular Scaffolds. Part II| Application of Zincke Aldehydes Toward the Synthesis of Gelsemine." Thesis, University of California, Irvine, 2014. http://pqdtopen.proquest.com/#viewpdf?dispub=3646740.

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Developing new synthetic methods and strategies is an important area of research in organic chemistry. Especially useful are transformations that rapidly and rationally generate complex molecular architectures, with multiple new bonds and new stereocenters, from simple, achiral and modular precursors. This dissertation discusses the synthetic investigation and exploitation of two such reactions.

In PART I, the intramolecular Diels–Alder (IMDA) reaction of aromatic dienes and allene dienophiles, utilized in conjunction with ring-rearrangement metathesis (RRM) to prepare angularly-fused polycyclic lactams, is discussed. The mechanism of the IMDA reaction was investigated with the aid of computational molecular modeling. The reaction was determined to proceed through a concerted mechanism; however, competing radical pathways accounted for stereochemical infidelity and fragmentation observed for some substrates.

An improved, modular synthesis of the precursors was developed to directly couple aromatic amines with the allene fragment precursor, which allowed for the preparation of a small library of heterocyclic compounds. This two-step protocol generates topologically interesting structures, containing two or more new rings, and two new sp3 stereocenters. Computational modeling also guided the development of the unknown analogous reaction for allenyl ketone substrates, which yield carbocyclic products.

Unexpected stereoselectivity and reactivity observations were made in the alkene metathesis reaction, which could not be readily explained. Computational studies were able to elucidate a subtle yet fundamental relationship between reaction mechanism and length of alkene tether in these types of substrates.

In PART II, efforts toward the synthesis of the alkaloid natural product gelsemine are discussed. The synthetic strategy employs a Zincke aldehyde rearrangement/IMDA cascade previously developed by the Vanderwal lab. Using 4-phenylpyridine as a model system, the expected transformation successfully gives an advanced synthetic intermediate lacking only the oxindole substructure, and the key C3–O4 and C5–C16 bonds present in the target. Elaboration of this intermediate toward the target is detailed.

A number of protected 4-(2-aminophenyl)pyridine analogues were prepared to facilitate oxindole formation and circumvent later stage complications that arose in the model system. These compounds all either failed to undergo Zincke salt formation, pyridinium ring-opening, or subsequent rearrangement/IMDA, thus delineating the synthetic boundaries of this type of chemistry.

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17

Mistry, Raakhee Gunvant. "The efficacy of a homoeopathic flu complex (arsenicum iodatum, gelsemium sempervirens, eupatorium perfoliatum and ferrum phosphoricum) in the treatment of influenza type syndrome." Thesis, 1999. http://hdl.handle.net/10321/2201.

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Dissertation submitted in partial compliance with the requirements for the Master's Degree in Technology: Homoeopathy in the Faculty of Health at Technikon Natal.
The purpose of this investigation was to evaluate the effect of a homoeopathic flu complex consisting of Arsenicum album, Gelsemium sempervirens, Eupertorium perfoliatum and Ferrum phosphoricum in the treatment of influenza type syndrome in terms of the patient's response to the treatment and the patient's oral temperature. It was hypothesised that the flu complex would reduce the severity and duration of symptoms in patients suffering from influenza type syndrome in terms of the patient's response to the treatment and the patient's temperature. This complex was formulated in the 30th potency by Dr Bloch and Dr Lewis of Cape Town, who have had much success using it in the treatment of influenza type syndrome, especially where no clear symptoms were present on which to prescribe. The remedies in the complex are often individually used to treat 'flu' ,with good results. This study was a double blind randomised, placebo-controlled investigation. Convenience sampling was used to select 30 patients of both sex and between the ages of 18 and 60 years, from the greater Johannesburg-Pretoria area. Patients had to have an oral temperature of 37.8\xB0C greater and had to experience influenza like symptoms of s 24 hour duration. 111ou
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18

Manson, Jessamyn. "The Ecological Consequences and Adaptive Function of Nectar Secondary Metabolites." Thesis, 2009. http://hdl.handle.net/1807/19290.

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Plants are under selection to simultaneously attract pollinators while deterring herbivores. This dilemma can lead to tradeoffs in floral traits, which are traditionally thought to be optimized for pollinators. My dissertation addresses the ecological costs and putative functional significance of nectar secondary metabolites, a paradoxical but widespread phenomenon in the angiosperms. I investigate this issue from the pollinator’s perspective using a series of controlled laboratory investigations focused primarily on the bumble bee Bombus impatiens and the nectar alkaloid gelsemine, from Gelsemium sempervirens. I begin by demonstrating that nectar enriched with the alkaloid gelsemine significantly deters visits from bumble bees at a range of natural alkaloid concentrations. However, this aversion can be mitigated by increasing the sucrose concentration such that the alkaloid-rich nectar is more rewarding than its alkaloid-free counterpart. I then demonstrate that the consumption of gelsemine-rich nectar can inhibit oocyte development and protein utilization in bees, but that this effect is limited to bees of suboptimal condition. Continuous consumption of the nectar alkaloid gelsemine also leads to a reduction in the pathogen load of bumble bees infected with Crithidia bombi, but direct interactions between the pathogen and the alkaloid have no impact on infection intensity. Gelsemine also fails to inhibit floral yeast growth, suggesting that nectar alkaloids may not be universally antimicrobial. Finally, I demonstrate that gross nectar cardenolides from the genus Asclepias are strongly correlated with gross leaf cardenolides and that the majority of individual cardenolides found in nectar are a subset of those identified in leaves. This pattern suggests that nectar cardenolides are a consequence of defense for Asclepias; however, they may not be a costly corollary because bumble bees show an overall preference for nectar cardenolides at mean concentrations. Altogether, my dissertation provides a new perspective on the role of chemical defenses against herbivores in plant-pollinator interactions.
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19

Liu, Gang. "Stereocontrolled total synthesis of (+/-)-gelsemine." Thesis, 1996. http://hdl.handle.net/1911/16928.

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Gelsemine (1) has been recognized as the major alkaloid component of Gelsemium sempervirens since 1870. It has attracted numerous synthetic efforts since the 1960s due to its unique rigid, hexacyclic cage structure. The first completely stereocontrolled total synthesis of gelsemine (1) via 21-oxogelsemine (3) is described herein. This synthesis features a stereospecific condensation between cyclopropyl carboxaldehyde (240) and 4-iodo-oxindole (259), facile construction of the tetracyclic intermediate (262) through a novel application of divinylcyclopropane-cycloheptadiene rearrangement, and an unprecedented silver-mediated cyclization between carbamoyl chloride and ene-carbamate.(UNFORMATTED TABLE OR EQUATION FOLLOWS)$$\vbox{\vskip108pt}$$(TABLE/EQUATION ENDS)
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20

JIAN, ZHENG-ZHENG, and 簡丞正. "Approaches towards gelsemine via organo-iron complexes I:addition of Cyanide." Thesis, 1991. http://ndltd.ncl.edu.tw/handle/06027499823809816755.

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