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Flux Measurements of Volatile Organic Compounds from an Urban Tower PlatformPark, Chang Hyoun 2010 May 1900 (has links)
A tall tower flux measurement setup was established in metropolitan Houston, Texas, to
measure trace gas fluxes from both anthropogenic and biogenic emission sources in the
urban surface layer. We describe a new relaxed eddy accumulation system combined
with a dual-channel gas chromatography - flame ionization detection used for volatile
organic compound (VOC) flux measurements in the urban area, focusing on the results
of selected anthropogenic VOCs, including benzene, toluene, ethylbenzene and xylenes
(BTEX), and biogenic VOCs including isoprene and its oxidation products, methacrolein
(MACR) and methyl vinyl ketone (MVK). We present diurnal variations of
concentrations and fluxes of BTEX, and isoprene and its oxidation products during
summer time (May 22 - July 22, 2008) and winter time (January 1 - February 28). The
measured BTEX values exhibited diurnal cycles with a morning peak during weekdays
related to rush-hour traffic and additional workday daytime flux maxima for toluene and
xylenes in summer time. However, in winter time there was no additional workday
daytime peaks due mainly to the different flux footprints between the two seasons. A comparison with different EPA National Emission Inventories (NEI) with our summer
time flux data suggests potential underestimates in the NEI by a factor of 3 to 5.
The mixing ratios and fluxes of isoprene, MACR and MVK were measured during the
same time period in summer 2008. The presented results show that the isoprene was
affected by both tail-pipe emission sources during the morning rush hours and biogenic
emission sources in daytime. The observed daytime mixing ratios of isoprene were much
lower than over forested areas, caused by a comparatively low density of isoprene
emitters in the tower's footprint area. The average daytime isoprene flux agreed well
with emission rates predicted by a temperature and light only emission model (Guenther
et al., 1993). Our investigation of isoprene's oxidation products MACR and MVK
showed that both anthropogenic and biogenic emission sources exist for MACR, while
MVK was strongly dominated by a biogenic source, likely the isoprene oxidation
between the emission and sampling points.
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Le risque de découverte des prix sur les marchés boursiers : aspects théoriques et empiriques / The equity market and its price discovery riskLigot, Stephanie 20 October 2017 (has links)
La thèse se concentre sur l’étude des impacts de la directive européenne concernant les Marchés d’Instruments Financiers (MIF) et de sa révision (MIF II et MiFIR) sur le processus de découverte des prix. Selon Schreiber et Schwartz (1986), celui-ci est défini comme l´incorporation de l´information nouvelle dans le prix des actifs et la recherche de l´équilibre par le marché. Cette directive clé a pour objectif d´augmenter la concurrence et l´efficience au niveau des marchés européens tout en assurant la protection des investisseurs, ceci via une augmentation de la transparence et une exigence de politique de meilleure exécution des ordres de la part des firmes d´investissement. Plus particulièrement, l´étude se focalise sur les actions françaises du CAC40 qui peuvent désormais être échangées en dehors du marché national réglementé, Euronext Paris. Les plateformes multilatérales de trading, les internalisateurs systématiques et les dark pools sont des alternatives qui ont été introduites par la directive. En l´absence de consolidation du marché européen dans son ensemble et en présence d’une fragmentation spatiale des ordres de bourse, le risque est que certaines places d´échanges reçoivent plus d´ordres d´achat et d´autres, plus d´ordres de vente. Certains pensent que la technologie devrait lier des marchés spatialement fragmentés. Cependant, si suffisamment de flux d´ordres est retiré du marché réglementé et transparent, ce dernier pourrait ne plus assurer la découverte des prix car les prix et les quantités d´équilibre n´auraient pas été découverts par le marché dans son ensemble. De plus, même en présence d´un marché consolidé au niveau spatial, une fragmentation temporelle peut subsister. Elle correspond à la fracturation du flux d’ordres dans le temps, rendant la rencontre des ordres d´achat et de vente plus compliquée. […] La thèse apporte tout d’abord un éclairage sur les enjeux et les implications de la directive sur l’efficience des marchés européens. Dans le premier chapitre, nous proposons un cadre d´évaluation de la directive. Une sélection des principaux travaux académiques est réalisée dans le domaine de la microstructure des marchés afin d´identifier les problématiques restant sans réponse et les enjeux pour sa révision en cours (MIF II). Ensuite, une revue de la littérature sur le processus de découverte des prix du marché est opérée par la mise en lumière des principaux travaux théoriques, méthodologiques et empiriques. Les deux principales fonctions d´un marché sont de fournir de la liquidité et de permettre la découverte des prix. Cependant, la fonction de découverte des prix a souvent été un objectif de régulation négligé par rapport aux objectifs de transparence et de concurrence. […] / The thesis focusses on the impacts of the European Markets in Financial Instruments Directive (MiFID) and its revisions (the MiFID II and the MiFIR) on the price discovery process. According to Schreiber and Schwartz (1986), the price discovery process is defined as the incorporation of new information into the prices of assets and the search for an equilibrium by the market participants. This key directive aims to increase competition and efficiency at the European level without neglecting investor protection by increasing transparency and by requiring a best execution policy for the execution of client orders from investment firms.The study specifically highlights the CAC40 stocks, which, with the implementation of the MiFID, can be exchanged outside the regulated domestic market (Euronext Paris). The directive has introduced Multilateral Trading Facilities (MTFs), Systematic Internalisers (SI) and Dark Pools as alternative trading venues.In absence of an overall consolidation of the European market and in presence of a spatial fragmentation of orders, there is a risk that some exchange places may receive more buy orders and others more sell orders. Technology should bind spatially fragmented markets; however, if enough of the order flow were removed from the regulated and transparent market, it would be unable to ensure the price discovery because the equilibrium prices and quantities would not befound by the overall market. In addition, even in the presence of a consolidated market at the spatial level, temporal fragmentation may still exist. […]The first chapter studies the challenges and the implications of the MiFID on the efficiency of the European financial markets. This research proposes a regulatory framework to assess the directive. A selection of the principal academic work in the microstructure research area has been carried out in order to identify the remaining unanswered issues and challenges for the current revision of the MIF. The second chapter proposes a literature review of the concept of price discovery by highlighting the principal theoretical, methodological and empirical academic research. The two main functions of a market are to provide liquidity and to allow price discovery. However, the price discovery function has often been a neglected regulatory objective in comparison to transparency and competition objectives. It is important to assess the impacts of fragmentation on the quality of the market after the implementation of the MiFID. The object of study is the price discovery accuracy in the post-crisis context of more high-frequency and algorithmic trading. At this level, the thesis first offers a quantification of the degree of spatial and temporal fragmentation of CAC40 shares in the post-MiFID context. This study shows an increase in fragmentation. Furthermore, the quality of the market is evaluated from a price discovery perspective through the study of an indicator developed by Ozenbas et al. (2002, 2011) called the normalised volatility ratio. The study confirms the existence of a price discovery risk at the opening of the market before and after the implementation of MiFID. The potential causes of price discovery accuracy have been studied using three types of variables that characterise each transaction. The number of ransactions and the proportion of high-frequency traders on the buy side for the first half-hour of the day are significant variables for price discovery accuracy. In the post-MiFID scenario, spatial fragmentation does not significantly affect the market quality of CAC40 shares. At this level, temporal fragmentation seems to be a greater determinant. […]
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Studium extrakce biologicky aktivních látek do tukového základu / Study of extraction of biologically active substances into fatty baseKomárek, Šimon January 2020 (has links)
This diploma thesis deals with macerates of comfrey (Symphytum officinale) in selected fats (food lard, cosmetic lard and almond oil). Selected fats were first characterized by dry matter content, saponification, acid, iodine number, peroxide value. At the same time, total and free fatty acids were determined using GC-FID. Macerates were prepared by extraction of comfrey roots with selected fats. In prepared macerates the change in acid and peroxide value was monitored, as well as the content of selected bioactive compounds. The content of total phytosterol and total carotenoid content was determined by UV-VIS spectrometry, phytosterols and carotenoids were also analysed using HPLC-DAD. Total phenolic content was measured using Folin-Ciocalteu reagent and antioxidant activity by ABTS assay. The measured properties were then compared with industrially produced comfrey ointment. In macerated fats the increase in acid and peroxide value was determined. Furthermore, an increase in the content of total phytosterols and total carotenoids was observed. Using HPLC-DAD the content of -sitosterol and stigmasterol was determined, but carotenoids were not detected. Of the tocopherols, only DL--tocopherol acetate was detected. During maceration, the content of total phenolic compound in fat increased, which caused a change in antioxidant activity.
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Radiofrekvenční metoda detekce výbušnin a drog - NQR / RF detection method of explosives and drugs - NQRMotyčka, Lukáš January 2013 (has links)
The thesis deals with RF spectroscopic methods, which are applicable for the detection of hazardous substances such as explosives or drugs. Particular attention is focused on promising method of nuclear quadrupole resonance. Abroad this method has recently been applied in the detection of energetic materials in hazardous locations. The cornerstone of the nuclear quadrupole resonance is to evaluate the interaction between electromagnetic radiation, in the range of medium to very short waves, and the researched substance. Observed parameter are the resonant frequencies of the substance. Spectral analysis of signal is used for their evaluation. Resonant frequencies are always typical for the crystalline structure, therefore every explosive or drug is clearly identifiable by this method.
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Development of a GC Method for the Quantification of Short Chain Carboxylic Acids in Aqueous SolutionÅkervall, Anton January 2020 (has links)
Petroleum powered vehicles emit volatile organic compounds (VOCs) through combustion that contributes to the pollution of the environment. A technique in the 1970s was developed to decrease these emissions, especially for nitrogen oxides (NOx) and sulphuric oxides (SOx) which is called exhaust gas recirculation (EGR). The technique works by recirculating a portion of the combusted gas back into the engine, this limits the NOx and SOx emissions because of lower temperatures and less available oxygen. The problems that follow these effects is the formation and condensation of acids that corrode the material of the EGR system, which are created by many different reactions. It is of importance to understand how the compounds in the EGR system behaves through analysis of authentic and simulated condensates, which is why a quantitative method for these compounds are of interest. The aim of the project was to develop a simple quantitative analysis method for formic acid, acetic acid, and lactic acid in aqueous solution, which was done at Gränges Sweden AB. The technique used for detection and quantification was gas chromatography (GC) coupled to a flame ionization detector (FID) and a water compatible polyethylene glycol (PEG) column. Fractional factorial design (FFD) was used for determination of adequate operating parameters of the GC method and the sample preparation. Sample preparation only required filtration and pH adjustment prior to direct aqueous injection (DAI) to the chromatographic instrument. Detection of the analytes was very difficult because of non-compatibility with the FID, and quantification of asymmetric peak shapes made this problem worse, omitting lactic acid from further analysis. Limit of detection (LOD) and limit of quantification (LOQ) was 490 and 1640 ppm for formic acid and 120 and 400 ppm for acetic acid, with an injection volume of 0.3 μL and split ratio 10:1. Limits were too high for every EGR sample leaving no peaks detected for the sample preparation used. Further development should be done with complementary techniques and sample reprocessing in order to quantify the compounds.
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Development of selected sulphur compounds and oxygenated volatile organic compounds reference gas mixtures for air quality monitoringLeshabane, Nompumelelo 05 1900 (has links)
Highly accurate analysis for the quantification of sulphur compounds and
oxygenated volatile organic compounds are crucial for the adherence of the
legislation in different environmental sectors. The sulphur compounds and
oxygenated volatile organic compounds measurements are challenging, due to
various factors such as molecules being adsorbed on the inner surfaces of
cylinders. It is therefore important to produce accurate and reliable reference gas
mixtures with mole fraction at ambient levels for the air quality monitoring and field
of gas sensing in South Africa. The challenges in producing sulphur compounds
and oxygenated volatile organic compounds reference gas mixtures are that the
overall process from gravimetric preparation steps until the comparison analysis
process and the stability of mixture in the gas cylinder, results in the large
measurement uncertainties. In order to produce reference gas mixtures of the
highest level, three important steps are followed: purity assessment of starting
material, gravimetric preparation, and verification/validation of prepared gas
mixtures. The purity analysis of high purity starting materials was determined using
gas chromatography coupled with various detectors and Karl Fischer for
determination of moisture content in high purity chemicals.
The sulphur compounds and oxygenated volatile organic compounds to be
developed in this study were hydrogen sulphide, sulphur dioxide, acetone,
methanol, ethanol, isopropanol, and n-butanol. These components were produced
following the International Organisation for Standardisation documents at mole
fraction of 10 µmol/mol for sulphur compounds and 5 µmol/mol for oxygenated
volatile organic compounds. The preparation of sulphur compounds reference gas
mixtures was done with a static gravimetric method using a direct method where a
target component was transferred directly into the cylinder. The preparation of
oxygenated volatile organic compounds used an indirect method whereby a target
liquid component from high purity chemicals was transferred into a cylinder using a
gas-tight syringe.The comparison between the reference gas mixtures was
validated using Non-Dispersive Ultra-Violet analysers (NDUV), gas chromatograph
coupled with pulsed discharge helium ionisation detector (GC-PDHID, UV
fluorescence analysers for sulphur compounds and gas chromatograph coupled
with flame ionisation detector (GC-FID) for the oxygenated volatile organic compounds. A multi-point calibration method was used to analyse sulphur dioxide
and hydrogen sulphide on the NDUV analyser, and the single-point calibration
method was used for analysis on the gas chromatography and UV fluorescence
where a sample mixture is analysed against a reference mixture with a similar mole
fraction. The statistical data considered during analysis included calculation of the
instrument drift and percentage relative standard deviation to check measurements repeatability, reliability, and measurement uncertainty. The gravimetric results of
prepared sulphur compounds at 10 µmol/mol gave a percentage relative expanded
uncertainty of 0.041 % REU for hydrogen sulphide, 0.12 % REU for sulphur dioxide.
The gravimetric results of prepared oxygenated volatile organic compounds at 5
µmol/mol showed a percentage relative expanded uncertainty 0.068 to 0.35 % REU
for isopropanol and ethanol respectively and less than 2.4 % REU for multi component of oxygenated volatile organic compounds. Finally, the primary standard
gas mixtures of sulphur compounds and oxygenated volatile organic compounds
were developed with the highest metrological measurement uncertainty level of
(k=2). / Environmental Sciences / M. Sc. (Environmental Sciences)
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Volatile organic compounds(VOC's) analysis from Cape Town haze ll studyChiloane, Kgaugelo Euphinia 09 November 2006 (has links)
Student Number: 9503012G
Master of Science.
School of Geography, Archaeology and Environmental Studies / A brown haze which builds-up over Cape Town under calm and cold weather conditions causes public concern. The brown haze is thought to be due to the gaseous and particulate emissions from the city, industries, traffic and townships in the Cape Town region. Volatile organic carbon (VOCs) compounds are an important component of the haze layer particularly because of their reactivity. VOCs play an important role in the carbon budget and radiation balance, regional oxidant balance, and in the distribution of ozone and other reactive gases, both at the regional and global scale. In this study the variation in ambient VOC concentrations during brown and non-brown haze days over Cape Town during July and August 2003 were characterised. Ambient air samples were collected in evacuated stainless steel canistes from the South African Weather Service (SAWS) research aircraft (Aerocommander, ZS-JRB) and later analysed by gas chromotography equipped with a flame ionisation detector (GC-FID). Benzene, toluene, ethylbenzene and xylene (BTEX) were the specific VOCs targeted for this study. Comparable meteorology data was also collected to determine the effects of wind field and atmospheric stability on BTEX concentrations.
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Etude de la production et de l'émanation de composés volatils malodorants sur textile à usage sportif / Production and emission of human body odors from textile for sportsLéal, Françoise 04 November 2011 (has links)
Si la sueur fraîchement émise par le corps humain est inodore, la dégradation de celle-ci par la flore bactérienne cutanée produit des composés volatils malodorants, responsables des odeurs de transpiration. Les odeurs de transpiration apparaissent également sur les vêtements au cours de leur utilisation, particulièrement sur les textiles réalisés en fibres synthétiques. Ce travail a pour but d’améliorer la compréhension du phénomène d’émanation d’odeurs en étudiant l’effet du sujet testé, l’effet de la flore bactérienne et l’effet du textile sur les émissions de composés volatils malodorants.L’intérêt de ce travail réside dans l’approche globale de la problématique des odeurs de transpiration et dans la diversité des méthodes de mesure mises en place, tant dans l’étude de la flore microbiologique que dans les méthodes de mesures des composés odorants émis.Dans un premier temps, le dénombrement simultané de la flore bactérienne sur la peau et sur le vêtement a été réalisé sur un échantillon de 15 sujets à l’issue d’un exercice physique. Cette expérimentation a permis d’évaluer le taux de transfert bactérien moyen lors d’une activité sportive et d’étudier son rôle dans l’émission d’odeurs. Ensuite, afin d’affiner ces résultats, une méthode basée sur la biologie moléculaire a été mise en place pour réaliser le suivi qualitatif de la stabilité de la flore commensale axillaire d’un sujet pendant 3 mois. Le transfert bactérien spécifique entre la peau du testeur et le vêtement a été étudié pour 4 matières textiles sélectionnées (dont le coton et le PET). Ceci a permis de déterminer le rôle du transfert bactérien spécifique dans l’émission des odeurs à partir de textile.Enfin, le dernier chapitre est consacré à l’étude de l’émission de composés volatils et odorants à l’aide de mesures olfactives et d’un nez électronique au cours du temps par 8 composants textiles sélectionnés. Après traitement statistique par analyse en composante principale et étude détaillée des mesures, 9 composés chimiques ont été identifiés comme indicateurs d’un comportement textile malodorant. Ces derniers pourraient être utilisés dans la mise en place d’une méthode ciblée de mesure physico-chimique des mauvaises odeurs.Ce travail a permis de déterminer l’impact de chacun des facteurs sujet, flore bactérienne et textile dans l’émission d’odeurs. En outre, ce travail ouvre des perspectives sur l’étude des contaminations bactériennes par contact, mais également dans l’étude des odeurs, sur les phénomènes de désorption de molécules volatiles à partir de différentes matrices textiles et sur les solutions pouvant être envisagées pour limiter les émissions odorantes à partir de textiles. / Fresh human sweat is odorless. Odoriferous volatile compounds are produced by the metabolism of bacteria living on the skin, generating strong malodor. Sweaty body odors do also appear on clothes during use, and especially on synthetic fabrics. The aim of this document is to improve understanding of odor emission by investigating subject effect, microbiota effect and fabric effect on the emission of odoriferous volatile compounds.Odors of perspiration are hereby globally approached with a wide use of methods and experimental devices, for microbial flora study as well as for odoriferous volatile compounds emission study.First, microflora enumeration has been simultaneously processed on the skin and on the fabric after exercise for 15 subjects. This experiment allowed an evaluation of the average bacterial transfer yield during physical activity and the beginning of the investigation of its effect on odor emission.A molecular biology methodology has then been developed in order to refine these results. Monitoring of qualitative composition of the microbiota has been performed to study the stability of the armpit’s ecosystem on a subject during 3 months. Specific microbial transfer from subject’s skin to clothe has been performed for 4 textile fabrics (including cotton and PET). This leaded to characterize the effect of specific bacterial transfer on odor emission from fabric.The last chapter is dedicated to the study of the emission of odoriferous volatile compounds over time using olfactory measurements and electronic nose for 8 selected fabrics. Principal component analysis targeted 9 chemical compounds that have been selected as malodorous behavior indicators for a given fabric. Those 9 compounds could be used for setting up a fitted physicochemical method of malodor.To conclude, this study helped to understand the effect of 3 factors in odor perception from a fabric after sport : subject, microbial flora and fabric. Perspectives have been charted on contact microbial contamination, but also on odor, and especially on desorption of odoriferous volatile molecules from a textile or knitted matrix. The solutions that could be used to limit malodorous emission from fabrics have also been discussed.
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Valorisation d'espèces envahissantes des genres Xanthium et Senecio : caractérisation, variabilité chimique et activités des huiles essentielles / Valuation of invasive species and genera Xanthium Senecio : characterization, chemical variability and activities essential oilsAndreani, Stéphane 09 December 2014 (has links)
La prolifération d’espèces invasives est un problème mondial. Après la pollution et la destruction des habitats, l’introduction d’espèces exogènes est une des principales causes de la disparition de la biodiversité animale et végétale dans le monde. La Corse n’est pas épargnée par le phénomène ; en effet, chaque année nous dénombrons de plus en plus d’espèces végétales introduites, potentiellement envahissantes et dangereuses pour l’écosystème insulaire. Si elles ne sont pas contrôlées, ces plantes peuvent rapidement gagner du terrain et s’installer durablement en raison de leurs facultés d’adaptation à divers écosystèmes.C’est dans ce contexte que nous sommes intéressés à quatre plantes de la famille des Astéracées considérées comme envahissantes : deux espèces du genre Xanthium (Xanthium italicum et X. spinosum) et deux espèces du genre Senecio (Senecio angulatus et S. inaequidens). L’objectif principal était d’initier une possible voie de valorisation de ces espèces par la production d’huile essentielle ; cela permettrait d’une part de limiter la dissémination et d’autre part, de générer un débouché économique.Par ailleurs, nous avons étendu ce travail à Limbarda crithmoides et à six espèces du genre Senecio poussant à l’état spontané en Corse. Une approche chimiotaxonomique réalisée à partir de 180 échantillons d’huiles essentielles du genre Senecio a conduit à différencier les espèces dites halotolérantes (S. aquaticus, S. transiens et S. cineraria) des espèces plus « terrestres » (S. vulgaris, S. angulatus, S. inaequidens, S. serpentinicola et S. lividus). L’étude de la variabilité chimique intraspécifique a permis de mettre en évidence des corrélations entre la composition chimique des huiles essentielles et le polymorphisme des taxons et/ou des facteurs édaphiques. L’étude du genre Senecio a également conduit à la caractérisation de deux nouvelles molécules, l’oxyde d’acétoxybisabolène et le 8-acétoxybisabolène 1,9-diol, isolées de l’huile essentielle de S. transiens (espèce endémique de Corse).D’un point de vue plus appliqué, les mesures des activités anti-radicalaires et anticorrosives des huiles essentielles ont démontré le potentiel de certaines espèces comme sources d’anti-oxydants naturels (notamment, Xanthium italicum et X. spinosum) mais aussi le pouvoir anticorrosif de la cacalohastine, isolée de l’huile essentielle de S. inaequidens (espèce invasive). / The proliferation of invasive species is a global problem. The introduction of exogenous species is after pollution and habitat destruction a major cause of the disappearance of the worldwide plant and animal biodiversity. Corsica is not spare to the phenomenon and every year there are numerous dangerous species which are introduced to the island ecosystem.In this study, we have studied four invasive species of Asteraceae (X. italicum, X. spinosum, S. angulatus and S. inaequidens) from Corsica. The aim of this study is to initiate a possible valuation pathway of these species by production of their essential oils. For this purpose, we investigated the chemical variability of each essential oil and their antioxidant and anticorrosive activities. Then we have extended our investigations to the others species of Senecio genus and to Limbarda crithmoides, anciently parented taxa.GC and GC/MS analysis allowed the identification of 107 and 74 components which accounted for 98.7 and 93.5% of the X. italicum and X. spinosum essential oils, respectively. Essential oils of X. italicum and X. spinosum were dominated by hydrocarbon monoterpenes (66.2%) and oxygenated sesquiterpenes (41.5%), respectively. The same metabolomic pathways seem occur for both species during the vegetative cycle of the plant: oxygenated sesquiterpene-production was higher during the flowering stage. Moreover the study of 25 sample oils of X. italicum and X. spinosum showed that the chemical variability of both essential oils could be linked to morphological characters.A comprehensive work on the chemical variability of 180 sample oils of Senecio was carried out and 251 components were identified. Among them, using mono and bi-dimensional NMR the structures of 8-acetoxybisabolene-1,9-diol and 8-acetoxy-1,9-oxobisabolene, two new components of S. transiens essential oil were described for the first time. Corsican Senecio species exhibited interspecies chemical variability: the halotolerant Senecio species (S. transiens, S. cineraria and S. aquaticus erraticus) were characterized by essential oils dominated by non-terpenic compounds while the so-called “terrestrial” Senecio species (S. angulatus, S. ineaquidens, S. lividus, S. vulgaris and S. serpentinicola) exhibited terpenic component-rich oils. The study of intra-species chemical variability highlighted direct correlations between the plant-production of secondary metabolites and the nature of soils on which S. lividus, S. vulgaris and S. transiens grows. Hence essential oil compositions and morphological polymorphism are indirectly related. In the same way, the chemical variability of S. cineraria essential oils seems to be linked to the geology of the soils while the oil diversity of the invasive S. angulatus, could be linked to the both spots of introduction on Corsica Island. In addition, an original chiral-gas chromatographic method was improved and applied to the main components of the essential oils in order to complement the chemical composition of the Senecio sample oils.Furthermore the originality of Corsican Limbarda crithmoides essential was highlighted by the occurrence of two p-cymenene derivatives, never reported in the related studies from literature. The investigation of 25 Corsican L. crithmoides focuses on a direct correlation between the water salinities of the plant locations and the chemical compositions of the essential oils.Finally the antioxidant activities, anti-free radical and reducing power, were measured on some essential oils of the studied species. Essential oils of the Xanthium genus appeared to be most effectives. In addition, anticorrosion properties of the essential oils were investigated and the best corrosion inhibiting activity was exhibited by those of S. inaequidens . Anticorrosion activity could be attributed to the cacalohastine, a naphtalofuranic component, isolated form the whole essential oil after column chromatography.
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STUDIES ON THE SIZE AND NON-PLANARITY OF AROMATIC STACKING MOIETY ON CONFORMATION SELECTIVITY AND THERMAL STABILIZATION OF G-QUADRUPLEXESSingh, Mandeep 01 January 2020 (has links) (PDF)
Targeting DNA has the advantage over proteins for cancer remediation because of the fewer copies of the ligands required for the desired therapeutic effect. Traditionally, covalent DNA binders like alkylating agents have been used to induce genetic instability through the formation of DNA lesions and strand breaks, leading to cellular apoptosis. The primary drawback of this treatment is the non-specific binding that affects both cancerous and non-cancerous cells. G-quadruplexes are the DNA secondary structures that are present in abundance near the promoter regions of the oncogenes and are involved in the regulation of their activities. A ligand-mediated stabilization of G-quadruplexes in the promoter regions and down-regulation of the associated oncogenes have been validated. In contrast to alkylating agents, G-quadruplex ligands induce genetic stabilization through non-covalent interactions. They can be designed to interact specifically with G-quadruplex DNA over duplex DNA, which reduce side effects arising from the off-targeting. G-quadruplex ligands invariably have the large planar aromatic moiety to interact with G-quadruplexes through π- π stacking interactions. For determining the size effect of the aromatic moiety on stabilization of G-quadruplexes, a series of ligands were synthesized by conjugating nucleobases or 1,10-phenanthroline with an aminoglycoside, neomycin. The resulting conjugates increased the binding affinity synergistically and enabled us to study the effect of the stacking moiety required for G-quadruplex stabilization. Nucleobase-neomycin conjugates did not show stabilization stabilize of human telomeric G-quadruplex. 1,10-Phenanthroline-neomycin conjugate (7b) on the other hand binds to human telomeric G-quadruplex with a Ka of (8.92.4)×108 M-1 and inhibits telomerase activity at 1.56 µM probably through G-quadruplex stabilization. Moving forward, we further enlarged the aromatic moiety by tethering two 1,10-phenantholine molecules together through a five-atom linker. The resulting molecule (2-Clip-phen) was conjugated with various amino-containing side chains. 2-Clip-phen derivatives showed at least 30 times weaker binding to duplex DNA over G-quadruplex DNA. In addition, compounds showed a preference for the antiparallel G-quadruplex conformation over parallel and hybrid G-quadruplex conformations, as shown in the CD spectroscopy studies. Ligands 11 and 13 induced the formation of an antiparallel G-quadruplex from random coils and stabilize it to 60 oC (Tm) in a salt-free condition. Mass spectrometry study showed the formation of a two-tetrad G-quadruplex with the 2-Clip-phen ligand. Docking study showed that the ligand interacts most favorably with antiparallel G-quadruplex conformation, which is supported further by the larger thermal stabilization effect on antiparallel G-quadruplex compared with other G-quadruplex conformations. Our study suggests that 2-Clip-phen can be used as a scaffold for designing G-quadruplex binding ligands that preferentially bind to antiparallel G-quadruplexes, which has never been reported before.
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