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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
31

Electrochemical detection of electroactive anion by capillary electrochromatagraphy using open tubular column modified by cationic polymer (PDADMAC)

Huang, Yi-cheng 05 September 2004 (has links)
none
32

Soft Materials Derived From Bile Acid Analogues

Bhat, Shreedhar 04 1900 (has links)
Chapter 1. Introduction This chapter is an overview on the literature of self-association of small organic molecules. The chapter is presented in four parts. First, an introduction to aggregation of small molecules is given with the emphasis on micelles and gels(Parts 1 and 2) In part 3, a short overview is given on bile acid based aggregates and their applications. Lastly, the content of the thesis is outlined. Chapter 2. Solution properties of novel cationic bil salts: A structure-aggregation property study Scheme 1: Structures of Cationic bile salts(Refer PDF File) Bile Salts are biosurfactants and they are known to form micelles in aqueous medium. We studied the micellar properties of cationic bile salts(Scheme 1) and compared with their natural (anionic) counterparts. A serendipitous discovery of the gelation of a cationic bile salt(4) led us to investigate the aggregation properties of this new class of cationic hydrogelators. This chapter highlights the recent efforts on the study of side chain structure-aggregation property relationship of cationic bile salts. Bile acid analogues with a quaternary ammonium group(Scheme 1, compounds 2, 3, 4, 6, 8 and 12) on the side chain were found to efficiently gel aqueous salt solutions. Some of the cationic bile salts gelled water alone and many of them gelled aqueous salt solutions even in the presence of organic co-solvents(≤ 20%) such as ethanol, methanol, DMSO and DMF. A strong counter ion dependent gelation was observed. These gels showed interconnected fibrous networks. Unlike natural anionic bile salt gels(reported for NaDC, NaLC), the cationicgels reported here are pH independent. Cationic gels derived from DCA showed more solid-like rheological response compared to natural NaDC gels studied earlier by Tato et al. A strong structure(side-chain) andcounter-ion dependent flow of the cationic bile salt gels was seen. Chapter 3. Applications of cationic bile salts and their aggregates Cationic bile salts are useful in many ways. We have studied some of the applications of cationic bile salts(discussed in chapter 2) and their aggregates in this chapter. The chapter is presented in three parts. Part 1. Interaction of Cationic bile salts and DNA The bile acid amphiphilicity is believed to help the DNA binding process of polyamines. This has prompted us to study the DNA-bile salt binding interaction of bile salts. The binding of cationic bile salts has been expressed in terms of C50 values, which were determined from the plot of fluorescence of ethidium bromide bound DNA vs. bile salt concentration(Fig 1) The C50 values for cationic bile salts were estimated to be about 1.2 mM. Fig1: A plot of fluorescene of ethidium bromide bound DNA against bile salt concentration (Refer PDF File) Part 2. Cholesterol solubilization and crystallization studies in aqueous bile salt solutions. Dihydroxy bile salt micelles are well known for cholesterol dissolution(e.g. UDCA and CDCA). We studied the dissolution of cholesterol in the cationic bile salt micelles(of 21-25) and the results are discussed in this part. Scheme 2: Cationic bile salt chlorides studied for cholesterol dissolution (Refer PDF File) A powder dissolution method was used to study the solubility of anhydrous cholesterol in cationic bile salt solution. These cationic bile salt micelles can dissolve cholesterol to the same extent as the taurine conjugates of bile acids, but lesser than the natural anionic bile salts(Fig.2) Addition of PC(Phosphatidylcholine) to cationic bile salt micelles enhanced the micellar cholesterol solubilization. Fig 2:Cholesterol dissolution in cationic bile salt solutions(Refer PDF File) The crystal nucleation time of cholesterol did not change significantly by adding 5-30 mM of the cationic bile salts. The bile salt analogues did, however, attenuate cholesterol crystallization to a similar extent at all concentrations studied. All these effects wer comparable to those fo cholic acid. Part 3. Hydrogels as a reaction vessel for photodimerization Bile salt micelles have been shown to control the product selectivity in photochemical reactions. The dynamic nature of the bile salt micelles results in differential effects on reaction selectivity. The photodimerization of acenaphthylene(sheme 3) was studied in micellar and hydrogel medium(e.g. NaDC, 22, 28, etc.) The ratio of anti- to synphotodimer was found to be greater in gel bound state than in solution. Substitution on the CAN ring did not show larger variation on the product distribution from solution gel. Scheme 3: Photodimerization of acenaphthylene(Refer PDF File) Chapter 4. Bile acid derived sulfur analogues in designing novel materials. Part 1. A simple approach towards nanoparticle-gel hybrid material. Scheme 4: Scheme for the synthesis of thiols derived from bile acids (Refer PDF File) Our interest in bile acid based gelator molecules led us to explore the synthesis and properties of bile analogues with the side chain carboxylic acid replaced by a thiol(Scheme 4) to stabilize metal NPs. We reasoned that the specific self-aggregation modes of facially amphiphilic bile units would enable a metal NP capped by such a thiol to “lock” onto a gel fiber derived from a structurally related gelator molecule. AuNPs stabilized by 38-40 were obtained by the NaBH4 reduction of homogeneous methanolic solutions of the thiol and gold salt. These steroid capped nanoparticles were found to stay dispersed in a gel of 28, thus providing a simple approach to obtain gel-nanoparticle hybrid. A photograph of the hybrid material and their morphology are shown in Fig 3.(Refer PDF File) Chart 1: Structure of the gelator used for designing a hybrid material(Refer PDF File) Part 2. Gelation of aromatic solvents using sulfur analogues of bile acid A few of the sulfur derivatives were serendipitously fouond to gel organic solvents (Fig 4). Thiol 38 formed stable gels at room temperatures while the disulphide 36 formed stable gels below 5º C. The aggregation properties, morphology, and the melting profiles of gels of disulfides and thiols derived from bile acids have been highlighted in this part. Fig 4: A photograph of the gels derived from 38(Refer PDF File) (For Figures and Molecular Formula Pl refer the Original Thesis)
33

Surfactant characterization to improve water recovery in shale gas reservoirs

Huynh, Uyen T. 04 April 2014 (has links)
After a fracturing job in a shale reservoir, only a fraction of injected water is recovered. Water is trapped inside the reservoir and reduces the relative permeability of gas. By reducing the interfacial tension between water and hydrocarbon, more water can be recovered thus increasing overall gas production. By adding surfactants into the fracturing fluid, the IFT can be reduced and will help mobilize trapped water. From previous research, two types of surfactant have been identified to be CO₂ soluble. These are the ethoxylated tallow amine and ethoxylated coco amine with varying ethoxylate length. Experiments were performed to test the solubility of these surfactants in water, observe how they change the interaction between HC and water, and measure the IFT reduction between HC and water. Surfactants with more than 10 EO groups were soluble at all salinities, temperature and pH. They also form a non-typical water-in-oil emulsion at all salinities. The surfactants, Ethomeen T/25, T/30, C/15, and C/25 were used in the IFT measurements. They showed interesting trends that exhibit their hydrophilic/hydrophobic nature. These surfactants reduce the IFT between pentane and water to approximately 5 mN/m. The results show that these surfactants do reduce the IFT between water and hydrocarbon, but not as well as conventional EOR surfactants. They do have other added benefits such as being CO₂ soluble, form water in oil emulsions, and tolerant to high temperature and salinity. / text
34

pH-responsive polymer nanoparticles synthesized using ARGET ATRP

Forbes, Diane Christine 24 February 2015 (has links)
Polycationic nanoparticles were synthesized with an activators regenerated by electron transfer for atom transfer radical polymerization-based (ARGET ATRP-based) emulsion in water method and investigated for their utility as biomaterials for drug delivery. The polycationic nanoparticles were composed of 2-(diethylamino)ethyl methacrylate (DEAEMA) for pH-responsiveness, poly(ethylene glycol) methyl ether methacrylate (PEGMA) for improved biocompatibility, tert-butyl methacrylate (tBMA) to impart hydrophobicity, and a tetraethylene glycol dimethacrylate (TEGDMA) cross-linking agent for enhanced colloidal stability. Dynamic light scattering demonstrated pH-responsive swelling, and cell-based assays demonstrated pH-dependent membrane disruption. The polycationic nanoparticles demonstrated low toxicity to cells. The polycationic nanoparticles were evaluated for use as drug delivery biomaterials by investigating the interactions with the drug and cells. Delivery remains a major challenge for translating small interfering RNA (siRNA) to the clinic, and overcoming the delivery challenge requires effective siRNA delivery vehicles. The polycationic nanoparticles demonstrated efficient siRNA loading. Evidence of siRNA-induced knockdown in cells was observed following transfection with the polycationic nanoparticle/siRNA complexes. Imaging techniques confirmed enhanced siRNA internalization using the polycationic nanoparticle/siRNA complexes compared to naked siRNA. An array of polycationic nanoparticles synthesized using ARGET ATRP or UV-initiated polymerization methods was characterized to examine the effect of polymerization method on material properties and the connection to molecular structure. An improved understanding of molecular structure, and its connection to polymerization method and material characteristics, may aid the design of advanced materials. The ARGET ATRP polycationic nanoparticles demonstrated increased nanoscale homogeneity compared to the UV-initiated polymerization polycationic nanoparticles; increased nanoscale heterogeneity in the UV-initiated polymerization polycationic nanoparticles was associated with broader transitions. The polycationic nanoparticles promoted cellular uptake of siRNA and induced knockdown, thus demonstrating potential as siRNA delivery vehicles. The ARGET ATRP method provides an alternative route to creating polycationic nanoparticles with improved nanoscale homogeneity. / text
35

Soybean oil based copolymers containing silicon, boron or phosphorus: polymerization, characterization and fire retardance properties

Sacristán Benito, Marta 24 February 2010 (has links)
Introducción y antecedentes El concepto de desarrollo sostenible surgió como idea principal tras la reunión de la comisión Brundtland en 1987. Esta reunión fue organizada por Naciones Unidas con el fin de tratar el deterioro del medio ambiente, originado por el desarrollo descontrolado de la humanidad. El desarrollo sostenible fue definido como un avance social y económico que asegure una vida sana y productiva al ser humano, pero que no comprometa las posibilidades de desarrollo de las generaciones venideras. Entre las conclusiones alcanzadas, se resaltó la necesitad de disponer de una mayor variedad de fuentes de energía. La filosofía de esta cumbre fue recogida en Agenda 21, un documento que pretendía servir como guía general de actuación para alcanzar un desarrollo sostenible a todos los niveles. Respecto a las ciencias, Agenda 21 subrayaba la necesidad de emplear todo el conocimiento científico en la consecución de los objetivos del desarrollo sostenible. En este sentido, la Environmental Protection Agency acuñó en 1998 un término, Green Chemistry, que reunía estas ideas y las aplicaba a la química a través de 12 principios que debían ser cumplidos en el camino hacia una química sostenible. Entre estos principios, el uso de fuentes renovables para la obtención de materias primas ha adquirido gran relevancia debido a las previsiones de agotamiento de una de las fuentes de energía y materias primas más importantes: el petróleo. Los aceites vegetales se incluyen entre estas fuentes renovables de materias primas, siendo actualmente una de las fuentes renovables más utilizadas por la industria química. Los aceites vegetales están básicamente compuestos por triglicéridos, que son moléculas formadas por glicerol y tres ácidos grasos. En general los ácidos grasos pueden ser completamente saturados o contener varios dobles enlaces que en algunos casos pueden encontrarse conjugados, pero también existen ácidos grasos que contienen grupos hidroxilo o epóxido. Cada aceite vegetal posee una distribución característica de ácidos grasos que determina sus propiedades físicas y químicas. En lo que respecta a la química de los polímeros, los aceites vegetales constituyen una atractiva materia prima debido a la amplia gama de transformaciones químicas que pueden llevarse a cabo para sintetizar monómeros de diversa naturaleza. La epoxidación de los dobles enlaces internos es la transformación más común, ya que permite, a través de la apertura del anillo oxiránico con diferentes reactivos, la introducción de una gran variedad de grupos funcionales. Los dobles enlaces internos pueden polimerizarse directamente en condiciones térmicas, con iniciadores de radicales o por polimerización catiónica. / Introducction The sustainable development concept came out of the United Nations Commision on Environment and Development in 1987 (Bruntland Commission) and it is defined as "the development that meets the needs of the present without compromising the ability of future generations to meet their own needs". From this point, both the society and the industry have considered what a sustainable development really means and the best ways to start to achieve it from their own standpoints. The principles of the United Nations Conference on environment and Development (UNCED) held in June 1992 in Rio de Janeiro, and Agenda 21, were formulated with the aim of preparing the world for the challenges of the 21st century. In this context, during the early 1990s the US Environmental Protection Agency (EPA) coined the phrase Green Chemistry "To promote innovative chemical technologies that reduce or eliminate the use of generation of hazardous substances in the design, manufacture and use of chemical products". The main challenges of Green Chemistry and Engineeiring can be summarized as: · utilizing renewable instead of scarce resources. · avoiding toxic/dangerous chemicals in safer processes to obtain safer products. · minimizing energy use. · minimizing waste and resource use, re-using products, recovering and recycling materials. So making processes globally more efficient. Plant oils are one of the most widely applied renewable raw materials in the chemical industry for non-fuel applications. Vegetable oils are triglycerides (tri-esters of glycerol with long-chain fatty acids) with varying composition of fatty acids depending on the plant they are extracted from. Depending on the composition of plant oils, their Chemicals and physical properties are different.Vegetable oils are very used in polymer chemistry. Triglycerides have different reactive points through which we can obtain polymers from plant oils.There are two main approaches:The first one is the chemical modification of the triglycerides obtaining a large number of polymerizable monomers like expoxides or alcohols. The second approach is the direct polymerization of the carbon-carbon doubles bonds of plant oils through a free radical or a cationic mechanism.The free radical polymerization of double bonds has received less attention than cationic mechanism which has been very studied by Larock's group.In both cases thermosetting polymers with comparable properties to those of industrial can be obtained. Because of increasing use of synthetic polymeric materials during the lasts decades and the large fraction of the fire load in homes, it is necessary the use of fire retardants to reduce combustibility of the polymers, and smoke or toxic fume production. To get these requirements, the development of effective flame retardant materials is a key factor. To reduce the flammability, flame retardants can act in the gas phase or in condensed phase. In the gas phase fire retardants act as scavengers of the highly reactive radical species that propagate the combustion. In the condensed-phase fire retardants interfere in the thermal degradation processes modifying the reaction pathways and promoting the formation of char instead of volatile degradation products. Finally some flame retardants can act in both phases. Objectives The main objective of this Thesis was to develop new fire retardant biobased thermosets from vegetable oils as renewable resources. To achieve this goal it was carried out the cationic copolymerization of soybean oil, styrene and divinylbenzene with different silicon-or boron-or phosphorus containing comonomers.
36

Emulsion Polymerization Using Switchable Surfactants

FOWLER, CANDACE IRENE 26 September 2011 (has links)
The work presented herein focuses on expanding the use of CO2-triggered switchable surfactants in emulsion polymerization of hydrophobic and hydrophilic monomers. Bicarbonate salts of the following compounds were employed as surfactants in the emulsion polymerization of styrene, methyl methacrylate (MMA) and/or butyl methacrylate (BMA): N’-hexadecyl-N,N-dimethylacetamidine (1a), N’-dodecyl N,N-dimethylacetamidine (2a) and N’-(4-decylphenyl)-N,N-dimethylacetamidine (3a). A systematic study of the effects of surfactant and initiator concentrations and solids content on the resulting particle size and ζ-potential was carried out, showing that a wide range of particle sizes (40 – 470 nm) can be obtained. It was found that as the basicity of the surfactant decreased, the particle size generated from emulsion polymerization increased. Destabilization of these latexes did not require the addition of salts and was carried out using only non-acidic gases and heat. It was shown that solids content, temperature, particle size and surfactant basicity greatly affect the rate of destabilization of latexes. The area occupied by N’-dodecyl-N,N-dimethylacetamidinium acetate on PMMA particles was determined to be 104 Å2. The monomer-D2O partition coefficient of 2a was determined to be 21 for styrene and 2.2 for MMA. The monomer-D2O partition coefficient of the bicarbonate salt of 2a was determined to be 1.2 for styrene and 0.85 for MMA. An initial assessment of the use of switchable surfactants in the generation of inverse emulsions was carried out. It was determined that butylated polyethyleneimine (BPEI) can successfully stabilize inverse emulsions of cyclohexane and aqueous 2-(dimethylamino)ethyl methacrylate. Upon CO2 introduction, this emulsion separates into two distinct phases. / Thesis (Master, Chemistry) -- Queen's University, 2011-09-26 11:10:14.053
37

Design and synthesis of cationic amphiphiles

Findlay, Brandon January 2012 (has links)
Cationic antimicrobial peptides (CAMPs) are produced by plants, animals and bacteria to protect their host against antagonistic microbes. The antitheses of selective antibiotics, these peptides are drawn by electrostatic and hydrophobic interactions to targets as diverse as the bacterial membrane, nucleic acids and serum proteins. This lack of specificity is their greatest strength, as mutations to single genes rarely lead to bacterial resistance. Resistance may be conferred by large scale alterations in cell envelope composition, which generally reduces bacterial fitness in the absence of peptide. Clinical applications of natural CAMPs are limited, as the peptides are toxic to mammalian cells and rapidly inactivated in vivo by serum albumin and proteases. Faced with these challenges we have prepared a number of CAMP analogues, with the goal of creating lead compounds for further development of antibacterial therapeutics. Much of our work has focused on ultrashort lipopeptides and lipopeptoids, which have properties similar to natural CAMPs and extremely abbreviated sequences. The simple structure of these scaffolds allows rapid creation of CAMP analogues in a brief period of time, allowing us to rapidly explore the structural requirements for CAMP activity. The balance of this work focuses on imparting CAMP-like behaviour to known antibiotics, in order to expand their spectrum of susceptible bacteria and combat the development of drug-resistant bacteria. In particular, the aminoglycosides neomycin and tobramycin have been fused to phenolic disinfectants such as triclosan and biclotymol, in order to improve their diffusion across the bacterial envelope and activity against Gram-negative bacteria.
38

Design and synthesis of cationic amphiphiles

Findlay, Brandon January 2012 (has links)
Cationic antimicrobial peptides (CAMPs) are produced by plants, animals and bacteria to protect their host against antagonistic microbes. The antitheses of selective antibiotics, these peptides are drawn by electrostatic and hydrophobic interactions to targets as diverse as the bacterial membrane, nucleic acids and serum proteins. This lack of specificity is their greatest strength, as mutations to single genes rarely lead to bacterial resistance. Resistance may be conferred by large scale alterations in cell envelope composition, which generally reduces bacterial fitness in the absence of peptide. Clinical applications of natural CAMPs are limited, as the peptides are toxic to mammalian cells and rapidly inactivated in vivo by serum albumin and proteases. Faced with these challenges we have prepared a number of CAMP analogues, with the goal of creating lead compounds for further development of antibacterial therapeutics. Much of our work has focused on ultrashort lipopeptides and lipopeptoids, which have properties similar to natural CAMPs and extremely abbreviated sequences. The simple structure of these scaffolds allows rapid creation of CAMP analogues in a brief period of time, allowing us to rapidly explore the structural requirements for CAMP activity. The balance of this work focuses on imparting CAMP-like behaviour to known antibiotics, in order to expand their spectrum of susceptible bacteria and combat the development of drug-resistant bacteria. In particular, the aminoglycosides neomycin and tobramycin have been fused to phenolic disinfectants such as triclosan and biclotymol, in order to improve their diffusion across the bacterial envelope and activity against Gram-negative bacteria.
39

Evaluation and expression of indolicidins and polyphemusin variants in plants for broad-spectrum disease resistance

Bhargava, Apurva January 2005 (has links)
The cationic antimicrobial peptides, indolicidins and polyphemusins, have shown activity against animal pathogenic viruses. The aim of this work was to evaluate the efficacy of these peptides for engineering plants with a broad-spectrum disease resistance, including viral diseases. TTC, Evan's blue and phytotoxicity assays showed low cytotoxicity of indolicidin and polyphemusin variants (10R, 11R and PV5) on tobacco leaf discs, protoplasts and plantlets. In vitro assays using these variants showed a broad-spectrum activity against plant pathogenic bacteria, fungi and viruses. An assessment of in planta activity was performed by expressing these cationic peptides in transgenic tobacco (Nicotiana tabacum var Xanthi). The disease assays using detached leaves from transgenic tobacco plants showed a broad-spectrum disease resistance against bacteria, fungi and 'TMV. Further work is needed on optimization of expression of these peptides and their combinations for successful application of this approach under greenhouse and field conditions.
40

Charged Liposaccharide Based Drug Delivery Systems

Adel Abdel Rahim Unknown Date (has links)
Abstract Many hydrophilic drugs do not easily cross biological membranes. One approach to improve intestinal absorption of hydrophilic compounds is to co-administer these drug molecules with absorption enhancers to optimize their physico-chemical properties. In this project, novel liposaccharides were used to modulate the aqueous solubility as well as increase the lipophilicity, improve the intestinal permeability and hence, oral bioavailability of hydrophilic molecules. However, the solubility of the drug/liposaccharide mixtures in aqueous system might be poor, therefore, introducing a hydrophilic component such as quaternization of amine derivatives or sodium salt of carboxylic acid is required to modulate hydrophilic/lipophilic balance and in the same time and promote surfactant and ion pairing characteristics of these derivatives. This dissertation illustrates the development of novel liposaccharide absorption enhancers to be used for oral delivery of hydrophilic drugs. This research includes chemical synthesis of new ionic liposaccharides, examination of their physico-chemical properties, and their in vitro and in vivo biological examinations. The work consists of two parts; cationic and anionic liposaccharide absorption enhancers. a) Cationic Liposaccharide Absorption Enhancers The focus of this work was on the molecular design, synthesis, and evaluation of novel cationic liposaccharide derivatives as drug delivery agents to improve the oral bioavailability of piperacillin as a model hydrophilic drug. These derivatives were designed to possess surfactant as well as ion pairing properties, and were synthesized from biocompatible and biodegradable materials such as glucose, lipoamino acids and lipophilic amino acids. Thermodynamic profiles of these derivatives as well as haemolytic activity were examined. Minimum inhibitory concentrations of piperacillin/liposaccharide conjugates were studied to investigate the effect of liposaccharides on piperacillin activity. The usefulness of these derivatives as absorption enhancers for the oral delivery of piperacillin was assessed in vitro (Caco-2 cells) and in vivo (rat oral absorption). It was concluded that these derivatives did show hemolytic activity in low concentration (suitable for enhancing activity), while they increased permeability of piperacillin through Caco-2 cells. However, these promising results obtained from in vitro assay were not confirmed in vivo. viii b) Anionic Liposaccharide Absorption Enhancers In this thesis, molecular design, synthesis, and evaluation of novel anionic liposaccharide derivatives as absorption enhancers to improve the intestinal permeability of a model hydrophilic drug such as tobramycin were carried out. These derivatives were designed to have surfactant as well as ion pairing properties, and were synthesized from biocompatible materials such as sugar, lipoamino acids and amino acids. Thermodynamic profiles of these derivatives as well as haemolytic activity were examined. Many absorption enhancers have (to some extent) cytotoxic activity, therefore, cytotoxic activity of the novel anionic liposaccharides were examined. The usefulness of these derivatives as absorption enhancers to increase the lipophilicity of tobramycin and hence, its oral bioavailability, was evaluated through carrying out partition coefficient examination. It was concluded that these derivatives did not show haemolytic and cytotoxic activities in low concentration (suitable for enhancing activity). In addition, the permeability of tobramycin into the organic phase (n-octanol) was increased when liposaccharide derivatives were used. The obtained results are promising and encouraging to continue the work to include Caco-2 cells assay (in vitro assay) and oral absorption in rats (in vivo assay) as a prospective work in the future.

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