The distinctive architecture of the stratum corneum with its unique nature of an interstitial lipoidal environment plays the major role in regulating the barrier function of the skin. The major problem with the transdermal delivery of 5-fluorouracil or idoxuridine is the permeation of sufficient amounts to the deeper layers of the skin and into the systemic circulation. In an attempt to enhance the transdermal permeability of 5-fluorouracil and idoxuridine, the aim of this study was to evaluate two lamellar gel phase systems (Physiogel dermaquadrille® and Physiogel NT®) and Emzaloids® as transdermal delivery vehicles for the two actives. Lamellar gel phase systems (LGPS) and Emzaloids® are both novel drug delivery systems. The epidermis of female abdominal skin was used in vertically mounted Franz diffusion cell experiments. An average amount of 250 mg of the 1% m/m LGPS was applied to cover the entire diffusion area of 1,075 cm2 of the skin, which contained 2,5 mg of the active. Samples of the actives in Emzaloids® were prepared and applied in the same way. The control solutions of the actives in water were prepared so that 1 ml of the applied solution contained the same amount of drug that was applied to the experimental cells. The entire receptor phase of the cells was removed at 2,4,6, 8, 10, 12 and 24 hours and was replaced with fresh 37°C receptor phase. The amount of active in the receptor phase was determined by HPLC analysis. Graphs of the cumulative amount of the active that permeated the skin over the 24 hour period were drawn and the slope of the graphs represented the flux in µg/ml/h. The average flux values of six experimental cells and six control cells were compared. Entrapment of the actives in the Emzaloid® vesicles was confirmed with the use of confocal laser scanning microscopy. Results for the LGPS indicate an enhancement ratio in the order of 4,2 for 5-fluorouracil and 1,7 for idoxuridine when compared to the control cells. There were no viscosity changes in the LGPS samples containing 1% m/m of the active when compared with the blank LGPS samples, suggesting that no change in the internal structure of the LGPS occurred after the addition of the actives to it. There were also no significant changes in the pH of the samples. Entrapment of the actives in the Emzaloid® vesicles occurred readily. The Emzaloid® vehicle showed a lower rate of release for idoxuridine than the LGPS did during the VanKel dissolution experiments. This suggests that higher flux values would be obtained with the LGPS for idoxuridine than with the Emzaloid® formulation, since more drug was available for permeation through the skin. This was, however, not the case. The Emzaloid® formulation showed much higher flux values, showing that even with a smaller amount of active available to permeate the skin higher flux values were obtained. Enhancement ratios of 20,33 and 3,50 were achieved with the Emzaloid® formulation for 5-fluorouracil and idoxuridine respectively. The internal LGPS structure which mimics the skins lipid components remained unchanged after the addition of the actives. Greater success might be achieved with the LGPS for different model drugs, since the drugs' physicochemical properties play an important part in its permeation through the skin. The Emzaloid® formulation, which is closely related to liposomes and transfersomes, showed great potential for commercially marketable formulations for the drugs tested but further research on the formulation has to be done. / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2005.

The distinctive architecture of the stratum corneum with its unique nature of an interstitial lipoidal environment plays the major role in regulating the barrier function of the skin. The major problem with the transdermal delivery of 5-fluorouracil or idoxuridine is the permeation of sufficient amounts to the deeper layers of the skin and into the systemic circulation. In an attempt to enhance the transdermal permeability of 5-fluorouracil and idoxuridine, the aim of this study was to evaluate two lamellar gel phase systems (Physiogel dermaquadrille® and Physiogel NT®) and Emzaloids® as transdermal delivery vehicles for the two actives. Lamellar gel phase systems (LGPS) and Emzaloids® are both novel drug delivery systems. The epidermis of female abdominal skin was used in vertically mounted Franz diffusion cell experiments. An average amount of 250 mg of the 1% m/m LGPS was applied to cover the entire diffusion area of 1,075 cm2 of the skin, which contained 2,5 mg of the active. Samples of the actives in Emzaloids® were prepared and applied in the same way. The control solutions of the actives in water were prepared so that 1 ml of the applied solution contained the same amount of drug that was applied to the experimental cells. The entire receptor phase of the cells was removed at 2,4,6, 8, 10, 12 and 24 hours and was replaced with fresh 37°C receptor phase. The amount of active in the receptor phase was determined by HPLC analysis. Graphs of the cumulative amount of the active that permeated the skin over the 24 hour period were drawn and the slope of the graphs represented the flux in µg/ml/h. The average flux values of six experimental cells and six control cells were compared. Entrapment of the actives in the Emzaloid® vesicles was confirmed with the use of confocal laser scanning microscopy. Results for the LGPS indicate an enhancement ratio in the order of 4,2 for 5-fluorouracil and 1,7 for idoxuridine when compared to the control cells. There were no viscosity changes in the LGPS samples containing 1% m/m of the active when compared with the blank LGPS samples, suggesting that no change in the internal structure of the LGPS occurred after the addition of the actives to it. There were also no significant changes in the pH of the samples. Entrapment of the actives in the Emzaloid® vesicles occurred readily. The Emzaloid® vehicle showed a lower rate of release for idoxuridine than the LGPS did during the VanKel dissolution experiments. This suggests that higher flux values would be obtained with the LGPS for idoxuridine than with the Emzaloid® formulation, since more drug was available for permeation through the skin. This was, however, not the case. The Emzaloid® formulation showed much higher flux values, showing that even with a smaller amount of active available to permeate the skin higher flux values were obtained. Enhancement ratios of 20,33 and 3,50 were achieved with the Emzaloid® formulation for 5-fluorouracil and idoxuridine respectively. The internal LGPS structure which mimics the skins lipid components remained unchanged after the addition of the actives. Greater success might be achieved with the LGPS for different model drugs, since the drugs' physicochemical properties play an important part in its permeation through the skin. The Emzaloid® formulation, which is closely related to liposomes and transfersomes, showed great potential for commercially marketable formulations for the drugs tested but further research on the formulation has to be done. / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2005.

O objetivo desta pesquisa foi desenvolver e aperfeiçoar uma formulação com fase gel lamelar contendo óleo de Calendula officinalis e avaliar seu potencial na atividade cicatrizante de úlceras em ratos. A formulação estudada possui valor de EHL 6,0, constituída por óleo de calêndula e sistema tensoativo formado por derivados etoxilados dos alcoóis cetílico e estearílico (Ceteth 2/Steareth 20). Primeiramente, determinou-se a região do diagrama ternário de fases em que se encontravam as emulsões com fase gel lamelares (EFGL), macroscopicamente estáveis. Em seguida foi avaliada a estabilidade do sistema e parâmetros que poderiam influenciar na formação das estruturas anisotrópicas. Avaliou-se o comportamento das emulsões utilizando o teste de perda de massa por evaporação. Na avaliação in vitro, foram realizados testes de citotoxidade do óleo de calêndula frente às células de fibroblastos da linhagem L929 através do ensaio de apoptose e necrose. O teste in vivo foi realizado através do Índice de Cicatrização de Úlceras (ICU) no modelo em dorso de ratos (úlcera excisional contrátil) a fim de avaliar o potencial cicatrizante da emulsão proposta comparando com o sham (grupo controle). As úlceras foram avaliadas mediante análise de imagem nos tempos de 0, 2, 7, 14 e 21 dias após o procedimento cirúrgico. A EFGL demonstrou maior estabilidade frente aos testes de estabilidade preliminar e acelerada em relação as demais formulações. Além disso, esta formulação demonstrou menor área de histerese (tixotropia), portanto menor grau de espalhabilidade e com maior tempo de contato com a úlcera. Durante a evaporação das emulsões houve manutenção das estruturas anisotrópicas O óleo bruto da Calendula officinalis não apresentou interferência na via da apoptose e necrose na concentração de até 1000 ?g/mL em fibroblastos L929. A formulação proposta promoveu melhor cicatrização no modelo de úlcera cutânea (ICU) na região dorsal de ratos, supondo- se modular a fase inflamatória do processo de cicatrização, pois o maior recrutamento de células inflamatórias bem como a colagênese, diminuída no grupo EFGL, foram fatores essenciais que permitiram a total reepitelização das úlceras cutâneas. Portanto, pode-se concluir que a metodologia utilizada nesta pesquisa foi útil para a obtenção de emulsões com fase gel lamelar, sendo que a formação dessa estrutura é importante para a estabilidade do sistema, podendo ser utilizada como uma formulação viável e eficaz no processo cicatricial de feridas. / The aim of this research was to improve a lamellar gel phase emulsion containing Calendula officinalis oil and to investigate its potential as a modern wound dressing. First, we determined the region of the ternary phase diagram in which the emulsions were stable and we also evaluated the intrinsic stability of the system and the action of some parameters which may influence the formation of lamellar gel phase. In addition, we analyzed the samples\' behavior during the evaporation process. Moreover, an in vitro cytotoxicity assay of the calendula oil was performed in order to evaluate apoptosis and necrosis in fibroblast cell line L929. Then, an in vivo test was carried out by the wound healing rate (WHR), using a specific model of ulcer in rats (excisional contractile ulcer), in order to assess potential healing of the proposed emulsion (LGP) by comparing with the sham group. The ulcers were evaluated by image analysis at 0, 2, 7, 14 and 21 days after surgery. The emulsion 6 \'showed greater stability in the preliminary and accelerated stability tests in relation to the previous studied formulation. Moreover, this formulation presented more compatible characteristics, because it showed smaller hysteresis area of ? (thixotropy), therefore a lower degree of spreadability and, accordingly, the formulation may increase contact span with ulcer, which is a desirable characteristic. During evaporation of the emulsions, the anisotropic structures were maintained, but their type varied depending on the decreased amount of water in the system. The crude oil of Calendula officinalis showed no interference with the pathway of apoptosis and necrosis in the concentration of 1000 mg / mL in L929 fibroblasts. The proposed model has promoted better wound healing rate in the ulcers in the dorsal region of rats. It seemed to modulate the inflammatory phase of the healing process, because of the increased recruitment of inflammatory cells as well as collagenesis, once LGP emulsion decreased in the group, were factors essential that allowed total reepithelialization of skin ulcers in rats treated with LGP emulsion. In conclusion, this study produced an enhanced and useful LGP which can be used as a new approach to stimulate the healing process and treat wounds efficiently.

<p>Glycoconjugates are biologically important molecules with diverse functions. They consist of carbohydrates of varying size and complexity, attached to a non-sugar moiety as a lipid or a protein. Glycoconjugate structures are often very complex and their intricate biosynthetic pathways makes overexpression difficult. This renders the isolation of pure, structurally defined compounds from natural sources cumbersome. Therefore, to better address questions in glycobiology, synthetic glycoconjugates are an appealing alternative. In addition, synthetic methods allow for the preparation of non-natural glycoconjugates that can enhance the understanding of the influence of structural features on the biological responses.</p><p>In this thesis, synthetic methods for the preparation of glycoconjugates, especially glycolipid analogues, have been developed. These methods make use of solid-phase chemistry and are amenable to library synthesis of series of similar compounds. Solid-phase synthesis is a technique where the starting material of the reaction is attached to small plastic beads through a linker. This allows large excess of reagents to speed up the reactions and the sometimes difficult purifications of intermediate products are reduced to simple washings of the beads.</p><p>One problem with solid-phase synthesis is the difficulties to monitor the reactions and characterize the intermediate products. Gel-phase 19 F-NMR spectroscopy, using fluorinated linkers and protecting groups, is an excellent tool to overcome this problem and to monitor solid-phase synthesis of e.g. glycoconjugates. Two novel fluorinated linkers for the attachment of carboxylic acids have been developed and are presented in the thesis. These linkers can be cleaved with both acids of varying strengths and nucleophiles like hydroxide ions, and they are stable to glycosylation conditions. In addition, a novel filter reactor for solid-phase synthesis was designed. The reactor fits into an ordinary NMR spectrometer to facilitate the reaction monitoring with gel-phase 19 F-NMR spectroscopy.</p><p>The biological applications of the synthesized glycolipids were demonstrated in two different settings. The CD1d restricted binding of glycolipids carrying the monosaccharide α-GalNAc as carbohydrate could be detected on viable cells of mouse origin. CD1d is one of several antigen presenting molecules (the CD1 proteins) that presents lipids and glycolipids to circulating T-cells that in turn can initiate an immune response. The CD1 molecules are relatively sparsely investigated, and the method to measure glycolipid binding on viable cells, as described in the thesis, has the possibility to greatly enhance the knowledge of the structural requirements for CD1-binding.</p><p>Serine-based neoglycolipids with terminal carboxylic acids were used to prepare glycoconjugate arrays with covalent bonds to secondary amines on microtiter plates. Carbohydrate arrays have great possibilities to simplify the study of interactions between carbohydrates and e.g. proteins and microbes. The usefulness of the glycolipid arrays constructed in the thesis was illustrated with two lectins, RCA120 from Ricinus communis and BS-1 from Bandeiraea simplicifolia. Both lectins bound to the array of neoglycolipids in agreement with their respective specificity for galactosides.</p><p>Glycobiology is a large area of great interest and the methods described in this thesis can be used to answer a variety of glycoconjugaterelated biological questions.</p>

Glycoconjugates are biologically important molecules with diverse functions. They consist of carbohydrates of varying size and complexity, attached to a non-sugar moiety as a lipid or a protein. Glycoconjugate structures are often very complex and their intricate biosynthetic pathways makes overexpression difficult. This renders the isolation of pure, structurally defined compounds from natural sources cumbersome. Therefore, to better address questions in glycobiology, synthetic glycoconjugates are an appealing alternative. In addition, synthetic methods allow for the preparation of non-natural glycoconjugates that can enhance the understanding of the influence of structural features on the biological responses. In this thesis, synthetic methods for the preparation of glycoconjugates, especially glycolipid analogues, have been developed. These methods make use of solid-phase chemistry and are amenable to library synthesis of series of similar compounds. Solid-phase synthesis is a technique where the starting material of the reaction is attached to small plastic beads through a linker. This allows large excess of reagents to speed up the reactions and the sometimes difficult purifications of intermediate products are reduced to simple washings of the beads. One problem with solid-phase synthesis is the difficulties to monitor the reactions and characterize the intermediate products. Gel-phase 19 F-NMR spectroscopy, using fluorinated linkers and protecting groups, is an excellent tool to overcome this problem and to monitor solid-phase synthesis of e.g. glycoconjugates. Two novel fluorinated linkers for the attachment of carboxylic acids have been developed and are presented in the thesis. These linkers can be cleaved with both acids of varying strengths and nucleophiles like hydroxide ions, and they are stable to glycosylation conditions. In addition, a novel filter reactor for solid-phase synthesis was designed. The reactor fits into an ordinary NMR spectrometer to facilitate the reaction monitoring with gel-phase 19 F-NMR spectroscopy. The biological applications of the synthesized glycolipids were demonstrated in two different settings. The CD1d restricted binding of glycolipids carrying the monosaccharide α-GalNAc as carbohydrate could be detected on viable cells of mouse origin. CD1d is one of several antigen presenting molecules (the CD1 proteins) that presents lipids and glycolipids to circulating T-cells that in turn can initiate an immune response. The CD1 molecules are relatively sparsely investigated, and the method to measure glycolipid binding on viable cells, as described in the thesis, has the possibility to greatly enhance the knowledge of the structural requirements for CD1-binding. Serine-based neoglycolipids with terminal carboxylic acids were used to prepare glycoconjugate arrays with covalent bonds to secondary amines on microtiter plates. Carbohydrate arrays have great possibilities to simplify the study of interactions between carbohydrates and e.g. proteins and microbes. The usefulness of the glycolipid arrays constructed in the thesis was illustrated with two lectins, RCA120 from Ricinus communis and BS-1 from Bandeiraea simplicifolia. Both lectins bound to the array of neoglycolipids in agreement with their respective specificity for galactosides. Glycobiology is a large area of great interest and the methods described in this thesis can be used to answer a variety of glycoconjugaterelated biological questions.

O objetivo desta pesquisa foi desenvolver e aperfeiçoar uma formulação com fase gel lamelar contendo óleo de Calendula officinalis e avaliar seu potencial na atividade cicatrizante de úlceras em ratos. A formulação estudada possui valor de EHL 6,0, constituída por óleo de calêndula e sistema tensoativo formado por derivados etoxilados dos alcoóis cetílico e estearílico (Ceteth 2/Steareth 20). Primeiramente, determinou-se a região do diagrama ternário de fases em que se encontravam as emulsões com fase gel lamelares (EFGL), macroscopicamente estáveis. Em seguida foi avaliada a estabilidade do sistema e parâmetros que poderiam influenciar na formação das estruturas anisotrópicas. Avaliou-se o comportamento das emulsões utilizando o teste de perda de massa por evaporação. Na avaliação in vitro, foram realizados testes de citotoxidade do óleo de calêndula frente às células de fibroblastos da linhagem L929 através do ensaio de apoptose e necrose. O teste in vivo foi realizado através do Índice de Cicatrização de Úlceras (ICU) no modelo em dorso de ratos (úlcera excisional contrátil) a fim de avaliar o potencial cicatrizante da emulsão proposta comparando com o sham (grupo controle). As úlceras foram avaliadas mediante análise de imagem nos tempos de 0, 2, 7, 14 e 21 dias após o procedimento cirúrgico. A EFGL demonstrou maior estabilidade frente aos testes de estabilidade preliminar e acelerada em relação as demais formulações. Além disso, esta formulação demonstrou menor área de histerese (tixotropia), portanto menor grau de espalhabilidade e com maior tempo de contato com a úlcera. Durante a evaporação das emulsões houve manutenção das estruturas anisotrópicas O óleo bruto da Calendula officinalis não apresentou interferência na via da apoptose e necrose na concentração de até 1000 ?g/mL em fibroblastos L929. A formulação proposta promoveu melhor cicatrização no modelo de úlcera cutânea (ICU) na região dorsal de ratos, supondo- se modular a fase inflamatória do processo de cicatrização, pois o maior recrutamento de células inflamatórias bem como a colagênese, diminuída no grupo EFGL, foram fatores essenciais que permitiram a total reepitelização das úlceras cutâneas. Portanto, pode-se concluir que a metodologia utilizada nesta pesquisa foi útil para a obtenção de emulsões com fase gel lamelar, sendo que a formação dessa estrutura é importante para a estabilidade do sistema, podendo ser utilizada como uma formulação viável e eficaz no processo cicatricial de feridas. / The aim of this research was to improve a lamellar gel phase emulsion containing Calendula officinalis oil and to investigate its potential as a modern wound dressing. First, we determined the region of the ternary phase diagram in which the emulsions were stable and we also evaluated the intrinsic stability of the system and the action of some parameters which may influence the formation of lamellar gel phase. In addition, we analyzed the samples\' behavior during the evaporation process. Moreover, an in vitro cytotoxicity assay of the calendula oil was performed in order to evaluate apoptosis and necrosis in fibroblast cell line L929. Then, an in vivo test was carried out by the wound healing rate (WHR), using a specific model of ulcer in rats (excisional contractile ulcer), in order to assess potential healing of the proposed emulsion (LGP) by comparing with the sham group. The ulcers were evaluated by image analysis at 0, 2, 7, 14 and 21 days after surgery. The emulsion 6 \'showed greater stability in the preliminary and accelerated stability tests in relation to the previous studied formulation. Moreover, this formulation presented more compatible characteristics, because it showed smaller hysteresis area of ? (thixotropy), therefore a lower degree of spreadability and, accordingly, the formulation may increase contact span with ulcer, which is a desirable characteristic. During evaporation of the emulsions, the anisotropic structures were maintained, but their type varied depending on the decreased amount of water in the system. The crude oil of Calendula officinalis showed no interference with the pathway of apoptosis and necrosis in the concentration of 1000 mg / mL in L929 fibroblasts. The proposed model has promoted better wound healing rate in the ulcers in the dorsal region of rats. It seemed to modulate the inflammatory phase of the healing process, because of the increased recruitment of inflammatory cells as well as collagenesis, once LGP emulsion decreased in the group, were factors essential that allowed total reepithelialization of skin ulcers in rats treated with LGP emulsion. In conclusion, this study produced an enhanced and useful LGP which can be used as a new approach to stimulate the healing process and treat wounds efficiently.

No description available.

Atualmente, tem se dado grande importância à criação de novos sistemas de liberação de princípios ativos. Na área cosmética, os sistemas em destaque são nanoemulsões, emulsões múltiplas e emulsões contendo cristais líquidos/fase gel lamelar. Nas emulsões múltiplas coexistem emulsões dos tipos O/A e A/O. Elas possuem inúmeras vantagens sobre outros sistemas de liberação, como por exemplo, a possibilidade de veicular dois ativos incompatíveis em compartimentos diferentes e controlar o perfil de liberação dos mesmos. Além disso, possuem biocompatibilidade, completa biodegradabilidade e podem ser usados diferentes óleos e tensoativos. Outra tendência recente em cosmetologia é o emprego de matérias-primas vegetais associadas a sistemas de liberação de princípios ativos, para formulação de novos produtos com apelo comercial e sustentável. O objetivo deste trabalho foi desenvolver um novo sistema de emulsão múltipla, por etapa única, que tivesse estabilidade características diferenciadas. Para tanto, elegeu-se dois óleos vegetais: girassol e gergelim, que foram usados separadamente no desenvolvimento dessas emulsões. O método de emulsificação utilizado foi o método de inversão de fases (EPI). Foi determinado o EHL crítico para cada um dos óleos, 6,5 para o óleo de girassol e 5,0 para o óleo de gergelim. Os pares de tensoativos escolhidos para o estudo foram Steareth 2 - Steareth 20 para óleo de girassol e Span® 60 - R400 para óleo de gergelim. Foram construídos dois diagramas pseudoternários, um para cada sistema, com o objetivo de definir variáveis relevantes à composição (fração aquosa, fração oleosa, porcentagem de tensoativo). Foram selecionadas as melhores emulsões para prosseguimento dos estudos de estabilidade, avaliada por meio dos seguintes testes físico-químicos: medições de pH, condutividade elétrica, granulometria e medidas reológicas. O método de emulsificação em etapa única por inversão de fases se mostrou eficiente na produção de emulsões múltiplas estáveis. Foi desenvolvida uma emulsão múltipla com características diferenciadas a partir do óleo de girassol: emulsão múltipla contendo fase gel-lamelar, um sistema ainda não descrito na literatura. As características das emulsões múltiplas descritas nesse trabalho, a saber: o uso de óleos vegetais como os óleos de girassol e gergelim; baixas concentrações de tensoativos; multiplicidade dos glóbulos e fase gel lamelar no mesmo sistema; são características desejáveis para a indústria cosmética, o que as tornam potenciais sistemas de liberação de ativos. / Currently, it has been given great importance to the creation of new delivery systems for active ingredients. In the cosmetic area, the highlighted systems are nanoemulsions, multiple emulsions and liquid crystal/lamellar gel phase emulsions. In multiple emulsions coexist O/W and W/O types of emulsions. They have several advantages over other delivery systems, such as the possibility of carry out two incompatible active ingredients in different compartments and the control of the release of the same. Moreover, they have biocompatibility, biodegradability and different oils and surfactants can be used. Another recent trend in cosmetology is the use of vegetable raw materials associated with the delivery systems for active ingredients, to formulate new products with commercial and sustainable appeal. The objective of this study was to develop a new system of multiple emulsion, in one step emulsification, which have stability and distinctive features. It was selected two vegetable oils: sunflower and sesame, which were used separately in the development of the multiple emulsions. The method of emulsification used was emulsion phase inversion (EPI). The critical HLB of oils was, 6.5 for sunflower oil and 5.0 for sesame oil, respectively. The pairs of surfactants chosen for the study were Steareth 2 - Steareth 20 for sunflower oil and Span® 60 - R400 for sesame oil. We constructed two pseudo-ternary diagrams, one for each system, in order to define variables relevant to the composition (water and oil fraction, percentage of surfactant). We selected the best emulsions for further investigation. Stability of the emulsions was evaluated by the following physico-chemical tests: measurements of pH, electrical conductivity, particle size and rheological measurements. The method of one-step emulsification was efficient in producing stable multiple emulsions. A multiple emulsion from sunflower oil was developed with distinctive features: gel-lamellar phase multiple emulsion, a system not described yet. The characteristics of multiple emulsions described in this work, to know: use of vegetable oils, as sunflower and sesame oils; low concentrations of surfactants; multiplicity of droplets and lamellar gel phase at same system; they are desirable characteristics for the cosmetic industry, and they make these multiple emulsion potential delivery systems.

<p>An efficient and versatile non-destructive method to analyze the progress of solid-phase glycoconjugate synthesis with gel-phase ¹⁹F NMR spectroscopy is described. The method relies on use of fluorinated linkers and building blocks carrying fluorinated protective groups. Commercially available fluorinated reagents have been utilized to attach the protective groups. </p><p>The influence of resin structures for seven commercial resins upon resolution of gel-phase ¹⁹F NMR spectra was investigated. Two different linkers for oligosaccharide synthesis were also developed and successfully employed in preparation of α-Gal trisaccharides and a n-pentenyl glycoside. Finally, reaction conditions for solid-phase peptide glycosylations were established.</p>

An efficient and versatile non-destructive method to analyze the progress of solid-phase glycoconjugate synthesis with gel-phase 19F NMR spectroscopy is described. The method relies on use of fluorinated linkers and building blocks carrying fluorinated protective groups. Commercially available fluorinated reagents have been utilized to attach the protective groups. The influence of resin structures for seven commercial resins upon resolution of gel-phase 19F NMR spectra was investigated. Two different linkers for oligosaccharide synthesis were also developed and successfully employed in preparation of α-Gal trisaccharides and a n-pentenyl glycoside. Finally, reaction conditions for solid-phase peptide glycosylations were established.