No description available.

Unsaturated sugars constitute as an important category of carbohydrate precursors in synthesis. Specifically, 1,2- and 2,3-unsaturated glycosides are excellent intermediates to derivatize monosaccharides and as building blocks in organic synthesis. For example, a major utility of 1,2-unsaturated sugars, namely glycals, is the addition reactions to afford 2-deoxy glycosides under acidic conditions and rearrangement reactions to produce 2,3-unsaturated glycosides. Lewis acids favour the formation of 2,3-unsaturated glycosides, whereas, Brønsted acids lead to normal addition products. A mixture of both the product is obtained often, depending on the nucleophiles and the stereochemistry of glycal. Chapter 1 of the thesis describes (i) reactivities of glycals under acidic condition and (ii) a general survey of reactions involving on C2-C3 carbons of monosaccharides. Glycals are useful precursors to derive a number of functionalized monosaccharide derivatives. A well-known acid catalyzed reaction of glycals is their conversion to 2,3¬unsaturated glycosides, known as the Ferrier products. In a research programme, reactivity switching and selective activation of C-1 or C-3 of 2,3-unsaturated thioglycosides under acid catalyzed condition was undertaken. Thioglycosides are excellent glycosyl donors and can be activated easily. In identifying the reactivities of 2,3-unsaturated thioglycosides, obtained through Ce(IV)-mediated reaction of a glycal, it was intended to study the glycosylation reaction and also the reactivity control of C1-C3 carbons during a glycosylation reaction. Experiments showed that a reactivity switching was possible through activation of either C-1 or C-3. Thus, C-1 glycosylation with alcohol acceptors occurred in the presence of NIS/TfOH, without the acceptors reacting at C-3. On the other hand, reaction of 2,3-unsaturated thioglycosides with alcohols mediated by triflic acid alone led to a transposition of C-1 ethylthio-moiety to C-3 intramolecularly, to form 3-ethylthio-glycals. Resulting glycals underwent glycosylation with alcohols to afford 3-ethylthio-2-deoxy glycosides. However, when thiol was used as an acceptor, only a stereoselective addition at C-3 resulted, so as to form C-1, C-3 dithio-substituted 2-deoxypyranosides. Oxocarbenium ion is the reactive intermediate during activation of a glycosyl donor, and in the case of a 2,3-unsaturated thioglycosides, the oxocarbenium ion may stabilize further by the presence of a C2-C3 unsaturation. Reaction of a nucleophile with allylic oxocarbenium ion may lead to two regio-isomers. Initially, NIS/TfOH was attempted on 2,3–unsaturated sugar with various alcohols and it was found that C-1 was the preferred reactive centre (Scheme 1) Scheme 1 In order to optimize the reaction for selective nucleophilic attack at C-3, further study was continued by using stoichiometric TfOH, in presence of acceptors alcohols with the intension to activate the double bond. The reaction led to the formation of 2-deoxy O-glycosides with the concomitant transposition of C-1 ethylthio-moiety to C-3 (Scheme 2). Scheme 2 An important observation was that the transposition of thioethyl group from C-1 to C-3 was highly regioselective. For example, with thiocresol as the nucleophile, there was an addition across the C-2-C-3 double bond to afford C-1, C-3-dithio derivative (Scheme 2). Thus, hard-soft nature of the nucleophiles, as well as, carbon centres helped to rationalize the reactivites. It was also observed that the intramolecular transposition of thioethyl group is highly stereo-controlled by equatorial C-4 acetoxy group. Thus, thioethyl nucleophile approached selectively at C-3 and afforded trans-diequatorial products. This rationalization was further confirmed through (i) reaction of benzyl protected 2,3-unsaturated thioglycoside, wherein a C-3 epimeric mixture was observed in 1:1 ratio; (ii) galactosyl derivative under similar reaction condition afforded anomeric mixture of 3-(4-methylphenylthio)-O-glycosides, with trans-diaxial orientation of substituent at C-3 (Scheme 3). Scheme 3 These reactions confirmed the role of C-4 substituent on the carbocation at C-3, through the presence or absence of a neighbouring group participation. In summary, in Chapter 2 the selective activation of either anomeric carbon or C-3 with proper choice of activation and reactivity control at each carbon will be described. Thioglycosides are excellent glyosyl donor and their glycosylation reactions were well explored. Upon indentifying the intramolecular transposition of thioalkyl/aryl functionality from C-1 to C-3, further investigations was undertaken to utilize the newly formed carbon sulfur bonds at C-3. Realizing a potential for such 3-alkyl/aryl thio 2-deoxy sugar, the Pummerer rearrangement was investigated. For this purpose, the thioalkyl/aryl moiety at C-3 was oxidized first to a sulfoxide. The resulting sulfoxide was allowed to undergo Pummerer rearrangement to afford vinyl sulfide (Scheme 4), resulting from the elimination of HOAc in the thioacetal formed in situ. Having implemented Pummerer rearrangement on a sugar substrate, synthetic utility of the rearrangement product, namely vinyl sulfide was undertaken. An effort to implement conjugate addition reaction was undertaken, which required the conversion of vinyl sulfide to vinyl sulfoxide in the first step. The conjugate addition reactions were first conducted with alkoxide nucleophiles. The reaction showed that addition of nucleophiles occurred from axial face to furnish manno-configured derivatives as a single diastereomer at sulfinyl sulfur in a moderate yield along with O-deacetylated product. It was also found that O-benzyl protected sugar vinyl sulfoxide was totally resistant to the conjugate addition reaction (Scheme 4). Scheme 4 In order to find the influence of the substituents in sulfoxide moiety in the addition of nucleophiles, additional study was conducted in which a less hindered thioethyl moiety was installed in place of p-tolylthio moiety. To install ethylthio moiety, a similar sequence of reaction was undertaken as described previously in Scheme 4. Conjugate addition reaction with alkoxide nucleophiles was conducted and analysis of the reaction showed that the addition of alkoxides remained similar, leading to the formation of manno-configuration of substituents (Scheme 5). Scheme 5 The configuration of the Michael adducts were ascertained from 1H NMR, as well as 2D NMR spectroscopies. H-1 of all adducts appeared as an apparent singlet, consistent with very small J1,2 values. Aryl vinyl sulfoxide afforded conjugate addition product at much higher ratio than corresponding alkyl vinyl sulfoxide. Thus, among aryl and alkyl vinyl sulfoxides, conjugate addition occurred better with the aryl vinyl sulfoxide, indicating a strong electronic effect of aryl group in stabilizing the conjugate anion which would form in situ during nucleophilic addition with vinyl sulfoxide. Therefore, p-tolylthio substituted vinyl sulfoxide served as a more efficient Michael acceptor when compared to the thioethyl substituted vinyl sulfoxide. Asymmetric environment of vinyl sulfoxides play a vital role during the reaction. Vinyl sulfoxides can exist in two stereochemically distinct conformation which makes the vinyl group electronically dissimilar. In one of the conformer S-O and C-C bonds are coplanar, whereas in the other conformation, these two bonds are opposite to each other. It is agreed generally that vinyl sulfoxides generally try to adopt the most reactive conformer during the reaction in which the C-C and S-O bonds are syn to each other. Thus, the preference for an axial attack would originate from a face anti to the lone pair of electrons on the sulfur of sulfoxide functionality, leading to the formation of the product with manno-configuration. As O-deacetylated vinyl sulfoxide was obtained along with the Michael adducts, it was assumed that one of the epimers of vinyl sulfoxide appeared to be more reactive when compared to the other. Chapter 3 describes implementation of a Pummerer rearrangement in order to synthesize a sugar vinyl sulfoxide and its conjugate addition reactions with alkoxide nucleophiles. The nucleophilic addition reactions of vinyl sulfoxide with other nucleophiles were studied further. The effect of the substituents of chiral sulfoxides in conjugate addition reactions was also incorporated in the course of reactions. Reactions of amines, carbon and sulfur nucleophiles were undertaken with p-tolylthio-substituted vinyl sulfoxides. The reactions showed formation of the addition-elimination products (Scheme 6). All primary amines, carbon and sulfur nucleophiles afforded C-2 axial epimer, namely, threo-epimer exclusively, wherein secondary amines furnished the equatorial vs axial epimer in 3:1 ratio. Scheme 6 In order to assess the course of the reaction, vinyl sulfoxide presenting a p-cumenethio¬moiety was installed in place of p-tolylthio moiety. Conjugate addition reactions were performed with both primary as well as secondary amines that showed formation of the C-2 epimeric mixtures. With both the primary and secondary amines C-2 equatorial epimer was found to be as the major product (Scheme 7). Scheme 7 In conjugate addition of vinyl sulfoxides, nucleophiles approach the olefinic face preferentially, which is anti to the electron rich sulfur lone pair of electrons and syn to the bulky aryl group. Therefore, C-2 axial epimer was observed as most favourable product. However, secondary amines remarkably influenced the pattern as well as selectivity of the reaction. Steric considerations were likely to dictate the overall reactivity with secondary amines which was even more pronounced when using p-cumenethio-substituted vinyl sulfoxide. Chapter 4 describes the conjugate additions as well as remote effect of aryl substituent on the selectivity of addition of amines on sugar sulfoxide In summary, the Thesis establishes: A new reactivity of switching and a selective activation of 2,3-unsaturated thioglycoside; A Pummerer rearrangement route in order to synthesize sugar vinyl sulfide for the first time, which on selective oxidation furnish a sugar vinyl sulfoxide, a useful precursor for conjugate addition reactions; An assessment of the stereoelectronic, as well as, steric effect of the chiral vinyl sulfoxide with various nucleophiles in conjugate addition reactions; Influence of the protecting groups were also studied in conjugate addition reactions. Overall the study presented in the Thesis provides a new insight to unsaturated sugars. The salient features of the present findings also showed that the intermediates such as C-3 substituted thioalkyl/aryl glycosides, vinyl sulfides, a variety of new C-2 substituted vinyl sulfoxides are also the potential sites for many types of modifications in monosaccharides. (For structural formula pl see the pdf file)

Ruminant products, meat and milk, were long ago discovered to contain a high content of saturated fat associated with various chronic diseases in human, including coronary heart disease. Increased consumption of n-3 fatty acids, linolenic (LNA; 18:3n-3), eicosapentaenoic acid (EPA; 20:5n-3) and docosahexaenoic acid (DHA; 22:6n-3) by man has been linked with reduced incidences of these diseases. Therefore, in vitro experiments carried out in this thesis investigated the possibility that the dietary inclusion of essential oil compounds (EOC) might modify ruminal biohydrogenation of polyunsaturated fatty acids (PUFA), and thereby improve the fatty acid profiles of ruminant derived foods. In the first experiment, twenty EOC were screened, of which carvacrol, thymol, cis/trans-citral, geraniol, nerol, (+)-α-pinene, l-menthone, linalyl acetate and (R)-(+)-pulegone were most effective at protecting the PUFA from biohydrogenation. The reduced accumulation of stearic acid with concomitant increases in vaccenic acid following the addition of the EOC confirmed their capacity to inhibit biohydrogenation of both LA and LNA. However, the observed decreases in total volatile fatty acids concentrations suggested that the inclusion of these compounds at 300 mg l-1 also suppressed microbial fermentation. Of these EOC, carvacrol and thymol were the most potent inhibitors of fermentation as they decreased total VFA concentrations by ≥60% from those of the control. In the second experiment, selected EOC, namely linalyl acetate, l-menthone and (+)-α-pinene, were tested at lower doses. It was observed that these EOC when added at 100 and 200 mg l-1 also inhibited biohydrogenation with minimal effect on VFA concentration. In experiment 3, pure culture work was undertaken to assess the effects of EOC on three key Butyrivibrio spp., involved in the biohydrogenation process, namely B. fibrisolvens, B. hungatei and B. proteoclasticus. The EOC inhibited biohydrogenation through their bacteriostatic effects on these bacteria. In conclusion, these studies revealed that EOC have the potential to modify ruminal biohydrogenation to varying extents depending on the type of compound used and the dose applied. Consequently, they might be useful at improving the healthiness of ruminant products, however their effects have to be confirmed in vivo and ensure that they do not cause significant inhibition of fibre digestion.

published_or_final_version / Zoology / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

No description available.

Distributions of water transit times (TTDs), and related storage-selection (SAS) distributions, are spatially integrated metrics of hydrological transport within landscapes. Recent works confirm that the form of TTDs and SAS distributions should be considered time variant-possibly depending, in predictable ways, on the dynamic storage of water within the landscape. We report on a 28 day periodic-steady-state-tracer experiment performed on a model hillslope contained within a 1 m3 sloping lysimeter. Using experimental data, we calibrate physically based, spatially distributed flow and transport models, and use the calibrated models to generate time-variable SAS distributions, which are subsequently compared to those directly observed from the actual experiment. The objective is to use the spatially distributed estimates of storage and flux from the model to characterize how temporal variation in water storage influences temporal variation in flow path configurations, and resulting SAS distributions. The simulated SAS distributions mimicked well the shape of observed distributions, once the model domain reflected the spatial heterogeneity of the lysimeter soil. The spatially distributed flux vectors illustrate how the magnitude and directionality of water flux changes as the water table surface rises and falls, yielding greater contributions of younger water when the water table surface rises nearer to the soil surface. The illustrated mechanism is compliant with conclusions drawn from other recent studies and supports the notion of an inverse-storage effect, whereby the probability of younger water exiting the system increases with storage. This mechanism may be prevalent in hillslopes and headwater catchments where discharge dynamics are controlled by vertical fluctuations in the water table surface of an unconfined aquifer. Plain Language Summary Volumes of water reside within landscapes for varying amounts of time before they are discharged to a stream. That length of time determines how long the water has to interact chemically with soil and rock, and therefore influences the chemistry of water that ends up in stream channels. Quantifying the full range and variability of those travel times remains a challenge. We built an experimental hillslope, which allows us to keep track of all the water that enters and exits the soilsomething that is difficult to accomplish in open environmental systems. We introduced chemically distinct water into the hillslope at specific points in time and followed the movement of that water within, and upon exit from the soil. We discovered that the water being discharged from the hillslope tends to have resided in the landscape for shorter lengths of time when the hillslope is very wet (like a wetted sponge) than when it is very dry (like a dry sponge). This insight helps us understand how different rainfall regimes, and the associated wetness of the landscape, can potentially influence water transit times through the landscape, and their relationship with stream chemistry.

No description available.

David Chi-cheong Wan. / Bibliography: leaves 75-85 / Thesis (M.Ph.)--Chinese University of Hong Kong, 1984

Styrene (C2H3-C6H5) is expected to have a more complex reaction process due to active reaction sites located in both vinyl group and phenyl group. Our exploration indicates that the adsorption products are coverage dependent. At low coverage, both vinyl group and phenyl group are possible to take part in the adsorption process. A new AsymT adsorption state covered two adjacent Si dimers is identified through two [4+2] cycloaddition. At high coverage, only vinyl group can interact with Si dimer to form cis and trans stereoisomers with different thermal energies and kinetic reaction barriers. STM images and vibrational frequencies are also explored to further support the experimental observations. / The adsorption of unsaturated organic molecules on reconstructed Si(100) surface is widely applied in the modification and functionalization of silicon surface to design new semiconductor materials. The present project is devoted to explore the adsorption mechanisms and the related properties of adsorption species for unsaturated organic molecules: acetylene (C2H 2), ethylene (C2H4), vinyl bromide (C2H 3Br) and styrene (C8H8) by quantum chemical calculation, based on density functional theory (DFT) method with pseudopotentials and plane wave basis set. / The investigation of vinyl bromide (C2H3Br) chemisorption on Si(100) resolves the conflicting conclusions between previous experimental and theoretical studies. The orientation of the vinyl bromide molecule relative to the titled silicon dimer is found to be an important factor for both the stability and reactivity of the precursor state. A new precursor pi-complex is identified, which is metastable and trapped by barriers around 0.1eV. Comparisons between theoretical and experimental vibrational frequencies support the conclusion that such a pi-complex is present on the surface at very low temperature. Careful analysis on the electronic structure also demonstrates that it is indeed a pi-complex rather than a diradical as previously suggested. Reaction mechanisms at higher vinyl bromide coverage are also modeled to explain the decrease in activation barrier observed in experiments. / The reaction processes for acetylene (C2H2) and ethylene (C2H4) chemisorption on the surface silicon dimer and the sub-layer silicon atoms are compared. Acetylene can undergo a new type of cycloaddition on sub-layer Si atoms (called sub-di-sigma) with no barrier, which is identified by ab initio Molecular Dynamics. The related properties including vibrational frequencies and STM images are calculated and found to be similar with those of the end-bridge adsorption structure. The identification of such a sub-di-sigma adsorption structure explains the discrepancy between STM experiments and theoretical calculations. In addition, the analysis of calculated vibrational frequencies, simulated STM images and the reaction barriers for di-sigma and end-bridge structures indicate that inter-dimer reaction for C2H4 is possible. / Zhang, Qiuji. / Adviser: Zhi Feng Liu. / Source: Dissertation Abstracts International, Volume: 70-09, Section: B, page: . / Thesis submitted in: October 2008. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 86-87). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.