Novel sugar phosphorus ylides: Their synthesis, structure and reactivity. Synthesis of a series of sugar-derived phosphorus ylides from protected sugar derivatives and beta-oxo ylides as a route to novel alkynes and trioxo compounds.
AuthorSahabo, Nina Carole
KeywordSugar phosphorus ylides
ß,ß'-dioxo sugar-derived phosphorus ylides
Rights© 2010 Sahabo, N. C. This work is licensed under a Creative Commons Attribution-Non-Commercial-Share-Alike License (http://creativecommons.org/licenses/by-nc-nd/2.0/uk).
InstitutionUniversity of Bradford
DepartmentSchool of Life Sciences
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AbstractHigher carbon chain sugars have gained increased interest recently; they are important building blocks of natural and unnatural products with biological properties. The synthesis of these higher sugar skeletons is commonly known to be achieved with the Wittig methodology which exploits phosphorus ylide chemistry. This method has been successfully used for the synthesis of the higher carbon sugars. The aim of this project was to synthesise ß,ß'-dioxo sugar-derived phosphorus ylides, a new class of ylides, as versatile intermediates to valuable higher carbon sugar derivatives and carbohydrate mimics. Model reactions were initially conducted; tetrahydro-2-furoic acid and tetrahydro-2H-pyran-4-carboxylic acid, compounds which are structurally similar to the precursor sugars, were identified as suitable model compounds. These compounds were converted to acyl chlorides and then converted to ß,ß'-dioxo phosphorus ylides precursors by acylation. The methodology proved successful and 8 examples were isolated. However, low yields were obtained due to the inevitable formation of triphenylphosphine oxide. The method was then extended to sugar derivatives, prepared using standard protecting group chemistry. It was found that acylation could be achieved using the simple acyl chloride route or peptide coupling methodology for sugar derivatives which were acid sensitive. ß,ß'-dioxo sugar-derived phosphorus ylides (16 examples) were successfully isolated in low yields. The oxidation and thermal reactivity of the ß,ß'-dioxo ylides were studied. Oxidation resulted in the successful synthesis of vicinal tricarbonyls, isolated as a mixture with the gem-diols (hydrates). The thermal decomposition of the ylides gave alkynes in moderate yields.
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A solid-state NMR study of molecular mobility and phase separation in co-spray-dried protein-sugar particlesForbes, Robert T.; Apperley, D.C.; Suihko, E.J. (2005)Molecular mobility and physical form of co-spray-dried sugar¿lysozyme formulations were evaluated. Co-spray-dried trehalose:lysozyme and sucrose:lysozyme formulations in 1:9, 1:1 and 9:1 ratios (w:w) were stored at 0% RH and 75% RH for 5¿6 days. Molecular mobility and physical form of the co-spray-dried formulations after storage were determined by using 13C and 1H solid-state NMR as well as X-ray powder diffractometry. The results showed that increasing sugar content in co-spray-dried formulations stored at 0% RH decreased molecular mobility of the amorphous formulations indicating a close association of the protein and sugar. Exposure of sugar¿lysozyme 1:1 and 9:1 formulations to 75% RH led to separation of sugar and protein phases, where the sugar phase was crystalline. The intimate sugar¿lysozyme interaction of the formulations stored at 0% RH and the phase separation of the sugar-rich formulations stored at 75% RH were also confirmed by using 13C solid-state NMR spin-lattice relaxation time-filter (T1-filter) measurements. The propensity of sucrose and trehalose to crystallise was similar; however, the results suggest that part of the sugar in the phase-separated formulations remained amorphous and in close association with lysozyme.
Effect of post-harvest treatment on ripening and quality of tomato fruit using ozone. Application of different ozone doses as controlled atmosphere storage for delay ripening and maintaining the quality of tomatoes and effect of ozone on antioxidant and sugar compounds at different stages of tomato fruit ripening.Karodia, Nazira; Tizaoui, Chedly; Shalluf, Milad A. (University of BradfordSchool of Engineering, Design and Technology, 2010-10-15)Tomatoes are widely produced and consumed due to their nutritional content and versatility. However, the tomato is a soft fruit liable to damage and flavour deterioration. Hence, the main challenge for the tomato producing industry is to prevent the high loss incurred during harvest, handling and transportation of the crops. The objective of this study was to investigate the overall nutritional implication of controlled storage of tomatoes using ozone on the ripening process and the basic nutritional components of tomatoes. This investigation was also designed to focus on the effect of different ozone doses on the basic components and properties (carotenoids, ascorbic acid, total antioxidant activity and soluble sugars content) of the quality and dynamic maturity of tomatoes. Green tomatoes (Rio Grande) were treated in glass chambers with ozone enriched air [(air + 2, 7 and 21 mg O3/g tomato) and control (air only)] under humidity and temperature of 90-95% and 14-17 oC respectively. Tomatoes were sampled after 14 days of ozone treatment in the storage chamber and analyzed for different quality parameters (appearance, weight loss, Total Soluble Solids (TSS), titratable acidity, total ascorbic acid and carotene) of the ripening. The variety Elegance tomatoes were selected and the fruits were graded by colour and subjected to treatment with ozone (in doses 0 (clean air), 0.25, 0.50, and1.00 mg O3/g tomatoes) during storage for 6 days under the same humidity and temperature conditions. The fruits were analysed for carotenoids, ascorbic acid content, total antioxidant activity and soluble sugars.Analysis of the fruits clearly showed that ozone significantly delayed the development of colour on the surface, particularly in the low doses, and caused black spots on the surface of the tomatoes, particularly in higher ozone doses. Ozone did not affect the ascorbic acid and titratable acidity content. However ozone did reduce the Total Soluble Solids (TSS) by about 10% at the lowest ozone dose. A high inhibition of accumulation of carotenoids, particularly at low dose, of the tomatoes (Rio Grande) was also observed. Tomatoes (Elegance) under ozone treatments contained higher ß-carotene than those under the control treatment and lycopene content increased during storage in the red stage of tomato fruits. Ascorbic acid (AsA), dehydroascorbic acid (DHA) and the total of AsA and DHA concentrations, and ratios of redox (ASA/ (ASA + DHA) and DHA/AsA in pericarp and pulp of tomatoes tissue, did not show clear differences between the different treatments. The concentrations of the glucose and fructose increased in the tomatoes which were subjected to ozone treatments. Results from this study show that controlled atmosphere storage of tomatoes using ozone is a viable technique which warrants further study.
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