189 resultados para Tetrahydrofuran
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Antioxidant activity and hepatoprotective properties of the aqueous extract and tetrahydrofuran-extracted phenolic fractions of Halimeda opuntia (Linnaeus) Lamouroux were investigated in rats with chemically induced liver injury. Total polyphenols were determined by using the Folin-Ciocalteau reagent. Liver damage was induced by CCl4 and assessed by a histological technique. Reverse transcription/polymerase chain reaction (RT/PCR) analysis showed increased superoxide dismutase (SOD) and catalase (CAT) gene expression and activities in the group treated with free phenolic acid (FPA) fractions of H. opuntia, suggesting inducing effects on both enzymes. In addition, rats treated with FPA fractions displayed lower liver thiobarbituric acid reactive substance (TBARS) levels than those observed for rats in the CCl4-treated group. These data suggest that the phenolic fractions from H. opuntia may protect the liver against oxidative stress-inducing effects of chemicals by modulating its antioxidant enzymes and oxidative status.
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In the present study the effect of relative humidity (RH) during spin-coating process on the structural characteristics of cellulose acetate (CA), cellulose acetate phthalate (C-A-P), cellulose acetate butyrate (CAB) and carboxymethyl cellulose acetate butyrate (CMCAB) films was investigated by means of atomic force microscopy (AFM), ellipsometry and contact angle measurements. All polymer solutions were prepared in tetrahydrofuran (THF), which is a good solvent for all cellulose esters, and used for spin-coating at RH of (35 +/- A 5)%, (55 +/- A 5)% or (75 +/- A 5)%. The structural features were correlated with the molecular characteristics of each cellulose ester and with the balance between surface energies of water and THF and interface energy between water and THF. CA, CAB, CMCAB and C-A-P films spin-coated at RH of (55 +/- A 5)% were exposed to THF vapor during 3, 6, 9, 60 and 720 min. The structural changes on the cellulose esters films due to THF vapor exposition were monitored by means of AFM and ellipsometry. THF vapor enabled the mobility of cellulose esters chains, causing considerable changes in the film morphology. In the case of CA films, which are thermodynamically unstable, dewetting was observed after 6 min exposure to THF vapor. On the other hand, porous structures observed for C-A-P, CAB and CMCAB turned smooth and homogeneous after only 3 min exposure to THF vapor.
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Tetrahydrofuran lignans represent a well-known group of phenolic compounds capable of acting as antiparasitic agents. In the search for new medicines for the treatment of Chagas disease, one promising compound is grandisin which has shown significant activity on trypomastigote forms of Trypanosoma cruzi. In this work, the in vitro metabolism of grandisin was studied in the pig cecum model and by biomimetic phase I reactions, aiming at an ensuing a preclinical pharmacokinetic investigation. Although grandisin exhibited no metabolization by the pig microbiota, one putative metabolite was formed in a biomimetic model using Jacobsen catalyst. The putative metabolite was tested against T. cruzi revealing loss of activity in comparison to grandisin.
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Leishmaniasis and Chagas disease are parasitic protozoan infections that affect the poorest population in the world, causing high mortality and morbidity. As a result of highly toxic and long-duration treatments, novel, safe and more efficacious drugs are essential. In this work, the methanol (MeOH) extract from the leaves of Piper malacophyllum (Piperaceae) was fractioned to afford one alkenylphenol, which was characterized as 4-[(3'E)-decenyl]phenol (gibbilimbol B) by spectroscopic methods. Anti-protozoan in vitro assays demonstrated for the first time that Leishmania (L.) infantum chagasi was susceptible to gibbilimbol B. with an in vitro EC50 of 23 mu g/mL against axenic promastigotes and an EC50 of 22 mu g/mL against intracellular amastigotes. Gibbilimbol B was also tested for anti-trypanosomal activity (Trypanosoma cruzi) and showed an EC50 value of 17 mu g/mL against trypomastigotes. To evaluate the cytotoxic parameters, this alkenylphenol was tested in vitro against NCTC cells, showing a CC50 of 59 mu g/mL and absent hemolytic activity at the highest concentration of 75 mu g/mL. Using the fluorescent probe SYTOX Green suggested that the alkenylphenol disrupted the Leishmania plasma membrane upon initial incubation. Further drug design studies aiming at derivatives could be a promising tool for the development of new therapeutic agents for leishmaniasis and Chagas disease. (C) 2012 Elsevier Inc. All rights reserved.
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Several studies on polythiophene gas sensors, based mainly on electrochemical and gravimetric principles can be found in the literature. However, other principles of gas detection, such as optical and thermal, are still little studied. Optical sensing is suitable for remote detection and offers great versatility at low cost. Here,we report on the use of thin films of seven polythiophene derivatives as active layer in optical sensors for the detection of six volatile organic compounds (n-hexane, toluene, tetrahydrofuran, chloroform, dichloromethane and methanol) and water vapor, in concentration range of 500-30,000 ppm. The results showed that it is possible to use different polythiophene derivatives to differentiate VOCs by optical sensing. Differentiation can be performed based on the presence or not of response to an analyte and the sensitivity value of the sensors for the analytes. Another important feature is the lack of the effect of humidity on the response of most films, which could be a major drawback in the application of these sensors. (C) 2011 Elsevier B.V. All rights reserved.
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Nanopartikel durch Strukturfixierung mizellarer Assoziate aus amphiphilen, endgruppenfunktionalisierten Diblockcopolymeren Zwei unterschiedliche Diblockcopolymersysteme mit Molmassen unterhalb von Mw = 10 000 g/mol wurden über anionische Polymerisation synthetisiert. Ein hetero-telecheles a,w-Poly(dimethylsiloxan)-b-Poly(ethylenoxid) (PDMS-PEO) Diblockcopolymer wurde mit einer Methacrylatendgruppe am PDMS und entweder einer Benzyl-, Hydroxy- oder Carboxylatendgruppe am PEO funktionalisiert. Ein Poly(butadien)-b-Poly(ethylenoxid) (PB-PEO) Diblockcopolymer wurde am PEO ebenfalls entweder mit einer Benzyl-, Hydroxy- oder Carboxylatendgruppe funktionalisiert. In selektiven Lösungsmitteln wie Wasser oder Methanol bilden beide Diblockcopolymersysteme supramolekulare Strukturen mit sphärischer, zylindrischer oder toroider Geometrie aus, die mit statischer und dynamischer Lichtstreuung in Lösung und mit Rasterkraftmikroskopie (AFM) und Transmissionselektronenmikroskopie (TEM) auf der Oberfläche untersucht wurden. Durch Zusatz eines Vernetzers und Initiators wurden die selbstassoziierenden Mizellen des PDMS-PEO Diblockcopolymers permanent durch radikalische Polymerisation mit UV-Licht fixiert. Mizellen des PB-PEO Diblockcopolymers wurden über Bestrahlung mit gamma-Strahlen permanent fixiert. Die Untersuchung der resultierenden Nanopartikel beider Diblockcopolymersysteme mit AFM und TEM zeigte, daß diese sogar in nicht selektiven Lösungsmitteln wie Tetrahydrofuran formstabil bleiben.
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In questo lavoro di tesi sono state sviluppate reazioni domino, tandem e procedure one-pot per ottenere eterocicli enatioarricchiti. Lo sviluppo di queste metodologie sintetiche è molto importante perché permettono di ottenere molecole complesse partendo da prodotti semplici, senza effettuare ripetuti passaggi di purificazione (stop-and-go or step-by-step synthesis). Lo scopo di questo lavoro è di ottenere derivati tetraidrofuranici modificati e derivati ossoazzolinici enantioarrichiti tramite reazioni SN2-Michael o tramite reazioni aldolica-ciclizzazione-Michael usando la catalisi asimmetrica a trasferimento di fase (PTC). Come catalizzatori PTC per imprimere enantioselezione sono stati utilizzati sali di ammonio quaternario derivati dagli alcaloidi della Cinchona. Sono state ottimizzate le condizioni di reazione (base inorganica, temperatura, solvente, tempo di reazione) per i diversi substrati presi in considerazione. I prodotti target sono stati ottenuti con buone rese, ottime diastereoselezioni ma con bassa enantioselezione. I risultati ottenuti richiedono un’ulteriore ottimizzazione e dovranno essere valutate variazioni strutturali dei nucleofili utilizzati. In this thesis were developed domino, tandem reactions and one-pot procedures to obtained enantioenriched heterocycles. The development of these methodologies is very fundamental because they allow to obtain complex molecules starting from raw materials, without carrying out repeated purification steps (stop-and-go or step-by-step synthesis). The purpose of this work is to obtain enantioenriched tetrahydrofuran and oxazoline derivatives through a SN2-Michael reaction or a aldol- cyclization-Michael reaction using the phase-transfer asymmetric catalysis (PTC). For imprint enantioselection we used Cinchona alkaloids quaternary ammonium salts derivatives. The reaction conditions (inorganic base, temperature, solvent, reaction time) were optimised for the different substrates taken into account. The target products were obtained with good yields, excellent diastereoselections but with low enantioselections. The obtained results require further optimization and structural changes in the nucleophiles used must be evaluated.
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During the last years great effort has been devoted to the fabrication of superhydrophobic surfaces because of their self-cleaning properties. A water drop on a superhydrophobic surface rolls off even at inclinations of only a few degrees while taking up contaminants encountered on its way. rnSuperhydrophobic, self-cleaning coatings are desirable for convenient and cost-effective maintenance of a variety of surfaces. Ideally, such coatings should be easy to make and apply, mechanically resistant, and long-term stable. None of the existing methods have yet mastered the challenge of meeting all of these criteria.rnSuperhydrophobicity is associated with surface roughness. The lotus leave, with its dual scale roughness, is one of the most efficient examples of superhydrophobic surface. This thesis work proposes a novel technique to prepare superhydrophobic surfaces that introduces the two length scale roughness by growing silica particles (~100 nm in diameter) onto micrometer-sized polystyrene particles using the well-established Stöber synthesis. Mechanical resistance is conferred to the resulting “raspberries” by the synthesis of a thin silica shell on their surface. Besides of being easy to make and handle, these particles offer the possibility for improving suitability or technical applications: since they disperse in water, multi-layers can be prepared on substrates by simple drop casting even on surfaces with grooves and slots. The solution of the main problem – stabilizing the multilayer – also lies in the design of the particles: the shells – although mechanically stable – are porous enough to allow for leakage of polystyrene from the core. Under tetrahydrofuran vapor polystyrene bridges form between the particles that render the multilayer-film stable. rnMulti-layers are good candidate to design surfaces whose roughness is preserved after scratch. If the top-most layer is removed, the roughness can still be ensured by the underlying layer.rnAfter hydrophobization by chemical vapor deposition (CVD) of a semi-fluorinated silane, the surfaces are superhydrophobic with a tilting angle of a few degrees. rnrnrn
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The pulsed jet Fourier transform microwave spectroscopy have been applied to several molecular complexes involving H2O, freons, methane, carboxylic acids, and rare gas. The obtained results showcase the suitability of this technique for studying the intermolecular interactions. The rotational spectra of three water adducts of halogenated organic molecules, i.e. chlorotrifluoroethylene, isoflurane and alfa,alfa,alfa,-trifluoroanisole, have been investigated. It has been found that, the halogenation of the partner molecules definitely changes the way in which water will link to the partner molecule. Quadrupole hyperfine structures and/or the tunneling splittings have been observed in the rotational spectra of difluoromethane-dichloromethane, chlorotrifluorometane-fluoromethane, difluoromethane-formaldehyde and trifluoromethane-benzene. These features have been useful to describe their intermolecular interactions (weak hydrogen bonds or halogen bonds), and to size the potential energy surfaces of their internal motions. The rotational spectrum of pyridine-methane pointed out that methane prefers to locate above the ring and link to pyridine through a C-H•••π weak hydrogen bond, rather than the C-H•••n interaction. This behavior, typical of complexes of pyridine with rare gases, suggests classifying CH4, in relation to its ability to form molecular complexes with aromatic molecules, as a pseudo rare gas. The conformational equilibria of three bi-molecules of carboxylic acids, acrylic acid-trifluoroacetic acid, difluoroacetic acid-formic acid and acrylic acid-fluoroacetic acid have been studied. The increase of the hydrogen bond length upon H→D isotopic substitution (Ubbelohde effect) has been deduced from the elongation of the carboxylic carbons C•••C distance. The van der Waals complex tetrahydrofuran-krypton shows that the systematic doubling of the rotational lines has been attributed to the residual pseudo-rotation of tetrahydrofuran in the complex, based on the values of the Coriolis coupling constants, and on the type (mu_b) of the interstate transitions.
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Conductive membranes were prepared by magnetic alignment of graphite-coated iron nanoparticles (GCINs) in a polyisobutylene (PIB) matrix, which was cast onto an interdigitated surface electrode. Toluene and tetrahydrofuran (THF) were used as solvents for the casting solution. Different molecular weights of PIB and solutions with concentrations ranging from 0.05- to 50-wt% were explored to optimize the mechanical and physical properties of the membrane. The amount of GCINs used in the membranes ranged from 0.1- to 2.5-wt%, and a sonicator was used to disperse the particles in the membrane. Sedimentation and surfactant studies were conducted to investigate the dispersion of GCINs in solutions. Progresses were made to find an optimal combination of various parameters in order to attain thin homogenous membranes for fast response.
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No presente trabalho foram estudadas as separações de 18 flavonóides (9 agliconas e 9 glicosídeos) pelas técnicas de Cromatografia Líquida de Alta Eficiência em fase reversa (RP-HPLC) e Cromatografia Micelar Eletrocinética em fluxo reverso (RF-Meck). Em ambas as técnicas foram avaliados solventes puros (metanol, acetonitrila e tetrahidrofurano) e suas misturas como formas de promover a variação de seletividade, através da modificação da fase móvel em HPLC, e da natureza do aditivo orgânico em RF-Meck. Nos estudos efetuados em HPLC utilizando-se gradiente, pode-se comprovar a possibilidade da modelagem do fator de retenção em funçã da proporção de solvente utilizados (MeOH, ACN, THF e suas misturas). Pode-se ainda, com base nos dados de retenção e na análise hierárquica de c1usters, diferenciar quatro diferentes grupos de sistemas cromatográficos com diferentes seletividades para flavonóides agliconas, e outros quatro com diferentes seletividades para glicosídeos. Os sistemas cromatográficos mais ortogonais (cada um pertencente a um grupo de seletividade) foram aplicados na separação de uma planta modelo (Azadirachta indica), de onde pode-se escolher a fase móvel mais seletiva para se otimizar a separação dos flavonóides glicosilados presentes nas folhas desta planta. No método final otimizado pode-se identificar e quantificar cinco dos flavonóides majoritários presentes, sendo três glicosídeos de quercetina (rutina, isoquercitrina e quercitrina) e dois glicosídeos de kaempferol (astragalin e nicotiflorin), em amostras de duas diferentes procedências (Piracicaba-SP e Silvânia-GO). Nos estudos envolvendo a separação dos dezoito flavonóides por RFMEKC pode-se comprovar diferenças significativas de seletividade quando se varia a natureza do solvente orgânico utilizado como aditivo, além de se observar tendências na migração em função das propriedades do solvente adicionado e da estrutura molecular do flavonóide. O solvente de menor eficiência para separação dos flavonóides foi o MeOH. Através da análise dos eletroferogramas obtidos através de um planejamento experimental de misturas, e das trocas de pares críticos observadas nos vários eletrólitos utilizados, obteve-se um método de separação com apenas um par crítico em menos de 12 minutos de corrida. O coeficiente de variação obtido para o fator de retenção foi de 1,5% e para área de 3%, considerando-se cinco injeções. O método desenvolvido foi aplicado com sucesso na identificação dos flavonóides majoritários presentes na planta modelo (Neem), obtendo-se o mesmo resultado do estudo anterior. Como forma de avaliar a concentração de flavonóides totais presentes em espécies vegetais é comum a análise de extratos após hidrólise ácida (conversão de todos glicosídeos em agliconas). Desta forma otimizou-se uma metodologia de separação em RP-HPLC de 8 flavonóides agliconas comumente presentes em alimentos e extratos vegetais de uso cosmético. A otimização foi efetuada mediante um planejamento experimental de misturas, para escolha da fase móvel mais seletiva, e de um planejamento fatorial composto central, para otimização das condições de gradiente. O método obtido foi o mais rápido já visto dentro da literatura consultada. A separação em linha de base foi efetuada em menos de 15 minutos, com coeficientes de variação de área entre 0,1 e 1,8%, coeficiente de correlação de 0,9993 a 0,9994 na faixa de 5 a 100 µg/mL, e limites de quantificação estimados na faixa de 0,1 a 0,21µg/mL. O método desenvolvido foi aplicado na otimização das condições de hidrólise de um extrato de Neem. A otimização foi efetuada através de metodologia de superfície de resposta, levando-se em consideração a concentração de ácido adicionada, o tempo de reação, a temperatura, e a concentração de um antioxidante (ácido ascórbico) adicionado. O resultado da otimização foi uma metodologia de hidrólise com tempo de reação igual a 5 minutos, utilizando-se 1,4 mol/L de HCI, 119°C e 500 µg/mL de ácido ascórbico. Através das metodologias de análise e de hidrólise desenvolvidas pode-se constatar a presença e quantificar no extrato de Neem os flavonóides agliconas quercetina, kaempferol e miricetina. Com o objetivo de se avaliar quais os componentes presentes em extratos vegetais são os responsáveis pelo poder antioxidante atribuído a determinadas plantas, foi montado um sistema de avaliação de poder antioxidante \"on-line\" com reação pós-coluna em HPLC (baseado na literatura) utilizando-se como \"radical livre modelo\" o ABTS. A análise da planta modelo (Neem) neste sistema mostrou que os flavonóides glicosilados identificados nas partes anteriores deste trabalho são os responsáveis pelo poder antioxidante atribuído a esta planta. De posse desta informação, e visando a obtenção de extratos para aplicações cosméticas com poder antioxidante, modelou-se a extração dos flavonóide do Neem em função da composição do solvente extrator (água, etanol , propilenoglicol e suas misturas), de acordo com um planejamento simplex centróide ampliado. Além da previsão da concentração dos princípios ativos pode-se ainda prever outras propriedades dos extratos obtidos, tais como, índice de refração e densidade, muitas vezes constituintes de especificações técnicas de acordo com as aplicações a que se destinam (cremes, xampús, etc).
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A strategy for a simple dispersion of commercial multi-walled carbon nanotubes (MWCNTs) using two organosilicones, polycarbosilane SMP10 and polysilazane Ceraset PSZ20, in organic solvents such as cyclohexane, tetrahydrofuran (THF), m-xylene and chloroform is presented. In just a few minutes the combined action of sonication and the presence of Pt(0) catalyst is sufficient to obtain a homogeneous suspension, thanks to the rapid hydrosilylation reaction between SiH groups of the polymer and the CNT sidewall. The as-produced suspensions have a particle size distribution <1μm and remain unchanged after several months. A maximum of 0.47 and 0.50mg/ml was achieved, respectively, for Ceraset in THF and SMP10 in chloroform. Possible applications as polymeric and ceramic thin films or aerogels are presented.
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A study has been made of the anionic polymerization of methyl methacrylate using butyllithium and polystyryl lithium as initiators and using aluminium triisobutyl as a cocatalyst. The aspects of the polymerization that were examined were the effect of changing the order of addition of reagents, the temperature at which polymerization takes place and the polarity of the solvent. Trends were assessed in terms of molecular weight, molecular weight distribution and tacticity. In addition, a second monomer addition test was carried out to verify that the polymerization was truly a living one, and a kinetic study was attempted. Studies to investigate the effect of changing the order of addition of reagents showed that polymer with similar polydispersities and tacticities are produced whether the pre-mixing (mixing initiator and cocatalyst before addition of monomer) or the post-mixing (mixing monomer and cocatalyst before addition of initiator) method were used. However, polymerizations using the post-mixing mixing method demonstrated lower initiator efficiencies, possibly indicating a different initiating species. Investigations into the effect of changing the polymerization temperature show the molecular weight distribution to narrow as the temperature decreases, although a small amount of low molecular weight tailing was also observed at low temperature. A clear relationship between tacticity and temperature was observed with syndiotacticity increasing with decreasing temperature. Changes in solvent polarity were achieved by using mixtures of the standard solvent, toluene, with varying amounts of cyclohexane, tetrahydrofuran or dichloromethane. Experiments at low solvent polarity (using toluene/cyclohexane mixtures) showed problems with initiator solubility but produced polymer with lower polydispersity and higher syndiotacticity than in toluene alone. Experiments using toluene/THF mixtures yielded no polymer, thought to be owing to a side reaction between THF and aluminium triisobutyl. Increased solvent polarity, achieved using toluene/dichloromethane mixtures produced polymer with higher polydispersity and at lower yields than the conventional system, but also with higher syndiotacticity. Second monomer addition reactions demonstrated that the polymerization was 'living' since an increase in molecular weight was observed with no increase in polydispersity. Kinetic studies demonstrated the high speed of the polymerization but yielded no useful data.
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This thesis is primarily concerned with the synthesis and polymerization of 5-methyl-1;3, 2-dioxathiolan-4-one-2-oxide (lactic acid anhydrosulphite (LAAS)) using anionic initiators under various conditions. Poly(lactic acid) is a biodegradable polymer which finds many uses in biomedical applications such as drug-delivery and wound-support systems. For such applications it is desirable to produce polymers having predictable molecular weight distributions and crystallinity, The use of anionic initiators offers a potential route to the creation of living polymers. The synthesis of LAAS was achieved by means of an established route though the procedure was modified to some extent and a new method of purification of the monomer using copper oxides was introduced, Chromatographic purification methods were also examined but found to be ineffective. An unusual impurity was discovered in some syntheses and this was identified by means of 1H and 13C NMR, elemental analysis and GC-MS. Since poly-α-esters having hydroxyl-bearing substituents might be expected to have high equilibrium water contents and hence low surface tension characteristics which might aid bio-compatibility, synthesis of gluconic acid anhydrosulphite was also attempted and the product characterised by 1H and 13C NMR. The kinetics of the decomposition of lactic acid anhydrosulphite by lithium tert-butoxide in nitrobenzene has been examined by means of gas evolution measurements. The kinetics of the reaction with potassium tert-butoxide (and also sec-butyl lithium) in tetrahydrofuran has been studied using calorimetric techniques. LAAS was block co-polymerized with styrene and also with 1,3-butadiene in tetrahydrofuran (in the latter case a statistical co-polymer was also produced).
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The enzyme catalysed polytransesterification of diesters with diols was investigated under various conditions. The most consistent results were obtained using crude porcine pancreatic lipase (PPL) suspended in anhydrous diethyl ether. Addition of molecular sieve to the above system gave higher molecular weight products. The PPL catalysed reaction of bis(2,2,2-trichlorethyl) adipate and glutarate with butane-1,4-diol in anhydrous ether with and without molecular sieve was investigated over a range of times from 8 to 240 hours. The 72 hour adipate reaction with molecular sieve gave the highest molecular weight polymer (Mn 6,500 and Mw 9,400). The glutarate gave the maximum molecular weight polyester after 24 hours (Mn 5,700 and Mw 9,500). Occasionally the glutarate reaction produced very high molecular weight polyester-enzyme complexes. Toluene generally gave lower molecular weight products than diethyl ether. Dichloromethane and tetrahydrofuran gave mainly dimers and trimers. Alternative enzyme and diol systems were also investigated. These yielded no polymeric products. The molecular weights of the polyesters were determined by 1H NMR end-group analysis and by GPC. The molecular weights determined by NMR were on average about twice as great as those determined by GPC. The synthesis of the following diesters is described: i)Bis(2,2,2-trichloroethyl) succinate, glutarate, adipate, trans-3-hexenedioate, and trans-3,4-epoxyadipate. ii) Diphenyl glutarate and adipate.iii)Bis(2,2,2-fluoroethyl) glutarate and trans-3-hexendioate.iv) Divinyl glutarate. v) N,N'Glutaryl dicyclohexanone oxime.The polytransesterification of all the above esters with diols was investigated. The easily synthesised bis(2,2,2-trichloroethyl) glutarate and adipate gave the best results and the work was concentrated on these two esters.