Master of Science / Department of Horticulture, Forestry, and Recreation Resources / Steven J. Keeley / Non-structural carbohydrates (NSC) are important for plant health and recovery from stress. Controlled-release N sources may moderate turfgrass vegetative growth, thereby maximizing NSC levels. Three studies were conducted to determine the effect of N source/timing on NSC levels, turfgrass visual quality, and color of ‘Midlawn’ bermudagrass and turf-type tall fescue. Additionally, the effect on low temperature tolerance of bermudagrass and brown patch incidence on tall fescue was investigated. Nitrogen sources included two polymer-coated ureas (PCU), a polymer-sulfur coated urea (SCU) and urea formaldehyde (UF). Total annual N was applied in either late summer or spring for bermudagrass, and either late summer or split between late summer and spring for tall fescue. Urea, applied at traditional timings, was a control in all studies. NSC status was determined at regular intervals by extracting two cores from each plot, defoliating, and measuring regrowth in a dark growth chamber. Turfgrass color, visual quality and brown patch incidence were rated monthly during the growing season. Bermudagrass low temperature tolerance was evaluated by subjecting plugs to a freezing regime and evaluating regrowth. Over the 2-yr study, N source did not have a significant effect on bermudagrass or tall fescue NSC levels, color, or visual quality. Timing of application, by contrast, did have a significant impact. For bermudagrass, August-applied N resulted in higher overall NSC levels and improved fall color. For tall fescue, split Sept/March applications improved color; but split Sept/ May applications reduced NSC compared to a single Sept application. Brown patch incidence was unaffected by N source or timing, though disease pressure was low. Timing of PCU application did not affect low temperature tolerance of bermudagrass, but PCU improved low temperature survival compared to urea.

Thesis (PhD (Genetics. Plant Biotechnology))--University of Stellenbosch, 2005. / The current understanding of the regulation of sucrose accumulation is still incomplete even though many scientists have investigated this subject. Components of trehalose metabolism have been implicated in the regulation of carbon flux in bacteria, yeast and more recently in plants. With a view to placing trehalose metabolism in the context of cytosolic sugarcane sucrose metabolism and carbon partitioning we have investigated the metabolites, transcripts and enzymes involved in this branch of carbohydrate metabolism in sugarcane internodal tissues. Sugarcane internodal trehalose levels varied between 0.31 ± 0.09 and 3.91 ± 0.99 nmol.g-1 fresh weight (FW). From statistical analysis of the metabolite profile it would appear that trehalose does not directly affect sucrose accumulation, although this does not preclude involvement of trehalose- 6-phosphate in the regulation of carbon partitioning. The metabolite data generated in this study demanded further investigation into the enzymes (and their transcripts) responsible for trehalose metabolism. Trehalose is synthesised in a two step process by the enzymes trehalose-6-phosphate synthase (EC 2.4.1.15, TPS) and trehalose-6-phosphate phosphatase (EC 3.1.3.12, TPP), and degraded by trehalase (EC 3.2.1.28). Two novel sugarcane partial cDNAs that coded for trehalase (tre) and actin (required for normalisation in profiling experiments) were isolated and used along with partial transcripts for TPS and TPP to determine transcript levels in different tissue- and genotypes. A putative full-length SugTPS cDNA was isolated and characterised. Enzyme activities for TPS, TPP and trehalase were measured at levels of 2.7 nmol.min-1.mg-1protein, 8.5 nmol.min-1.mg-1protein and 6.2 nmol.min-1.mg-1protein respectively, from young internodal protein extracts of sugarcane, variety N19. TPP enzyme activity and transcript levels were higher in S. spontaneum than Saccharum interspecific hybrids. Kinetic analysis of TPP and trehalase activities were performed with the purpose of providing parameters for an in silico kinetic model of trehalose and sucrose metabolism. Three isoforms of TPP were identified and desingated TPPAI, TPPAII and TPPB. Both TPPA isoforms had pH optima of 6.0, and TPPB of pH 6.5. Apparent Km values were determined as 0.447 ± 0.007 mM for TPPAI, 13.82 ± 1.98 mM for TPPAII and 1.387 ± 0.18 mM for TPPB. Partial purification and characterisation of trehalase demonstrated dual pH optima of 3.5 and 6.0, with Km values between 0.345 and 0.375 mM. These data were used as the basis for a kinetic model of trehalose metabolism. A previously described kinetic model of cytosolic sucrose metabolism has been expanded to include the trehalose pathway (TPS, TPP and trehalase). The aim was to supplement the available information on cytosolic metabolism in sugarcane storage parenchyma, identify points of control between sucrose and trehalose metabolism, and provide a platform from which further experimental and in silico modelling can be launched. The model predicted trehalose in the same order of magnitude as those determined in the metabolite profiling experiments. The majority of control of flux over the trehalose pathway resided in the TPS step, with flux control coefficients > 70% of the total pathway. Incorporation of the trehalose branch into the original sucrose model showed that reactions from the original model significantly affected the steady-state attributes of the trehalose pathway. Due to the relatively low flux through the trehalose branch of the expanded model, complete recycling of trehalose, and the lack of allosteric regulation by trehalose-6-phosphate or trehalose on any of the reactions from the original sucrose model, incorporation of the trehalose branch had no significant effect on either steady-state cytosolic sucrose concentration or flux of sucrose into the vacuole. The expanded model affords a basis from which to further investigate trehalose metabolism in the context of plant sucrose accumulation.

Stellenbosch University. Faculty of AgriSciences. Dept. of Horticulture. / Thesis (PhD (Agric))--Stellenbosch University, 2006. / ENGLISH ABSTRACT: Market preferences for larger fruit have forced producers to adopt cultural practices that will ensure bigger fruit even if this comes at the expense of reduced total yields. In order to obtain acceptable fruit size there must be an adequate supply of photosynthetic carbon products especially during the cell division stage of fruit growth. Competition between fruits and between fruit and vegetative growth, as well as adverse climatic conditions, may limit the carbon supply to the fruits at this critical period and thus limit the final fruit size. Growers are showing renewed interest in the use of girdling or scoring in combination with the usual fruit thinning program to achieve growth control and increase fruit size. A new and milder chemical growth retardant, prohexadione-calcium (ProCa), is now also available for vegetative growth control of apple trees. [n this study, the effects of, and potential interaction between scoring, ProCa and fruit thinning were investigated, with respect to shoot and fruit growth, yield and photosynthetic capacity, in 'Royal Gala" 'Fuji' and 'Cripps' Pink' apple trees. ProCa decreased final extension shoot length in all three cultivars. Extension shoots were generally more sensitive than bourse shoots to scoring and ProCa. ProCa seems to be a more effective way of controlling shoot growth than scoring, with 'Fuji' and 'Cripps' Pink' being more sensitive than 'Royal Gala' to the application of ProCa. Scoring led to increased fruit growth rates during the first 40 days after full bloom (DAFB), and culminated in better fruit size at harvest. Scoring improved the total soluble solids concentration (TSS) of 'Fuji' and 'Cripps' Pink' compared to control and ProCa treatments. ProCa inhibited shoot growth effectively, but no evidence was found for improved carbon allocation to fruits and reproductive buds. Yield efficiencies of scored trees were significantly improved in all cultivars during the second season, due to better reproductive bud development after the first year of scoring. On 'Royal Gala' and 'Cripps' Pink', the efficiency of scoring to stimulate reproductive bud development on old and new spurs declined after 4 weeks after full bloom (WAFB). In 'Fuji', scoring later than I WAFB led to a decreasing positive response on old and new spurs. In contrast, reproductive bud development on long shoots increased with later scoring (6 and 8 W AFB) on all cultivars. It seems that the most beneficial time of scoring is 2-4 W AFB, as early as possible during the cell division stage offruit growth, but not before natural drop has occurred. The combination of early-season scoring and application of ProCa seems to hold potential for increasing carbon allocation to the fruit and improving fruit size and quality attributes. Scoring early in the season reduced photosynthetic capacity, and this reduction in carbon availability led to earlier cessation of shoot growth as well as shorter shoots. Later in the season, reduced fruit numbers led to a decrease in photosynthesis. The optimum temperature range for photosynthesis was found to adjust according to seasonal temperature variations. The harvest-induced reduction in sink strength changed stomatal sensitivity to higher temperature. Due to a reduced demand for carbohydrates by the plant, the maximum rate of photosynthesis (Amax) was reduced post-harvest. Following this reduction in sink strength and Am .. , stomata became more sensitive to high leaf temperatures, thus restricting water loss. Pre-harvest there was a strong demand for carbohydrates, therefore stomata were kept open at higher temperatures to ensure a high rate of C02 incorporation, but at a cost with regard to water use efficiency. The sharp increase in dark respiration (Rd) in leaves and fruit with an increase in temperature would mean that significant carbohydrate shortages could occur in trees during source limited periods early in the season, especially under warm weather conditions commonly experienced in the Western Cape region. / AFRIKAANSE OPSOMMING: Die effek van omgewings- en interne faktore op koolstofproduksie en -allokasie in appelbome (Malus domestlca Borkh.). Mark voorkeur vir groter vrugte forseer produsente om tegnieke te gebruik wat groter vrugte sal verseker selfs al beteken dit verlaagde totale opbrengste. Om aanvaarbare vruggrootte te bereik moet daar voldoende voorsiening van fotosinteties geproduseerde koolstofprodukte aan die vrug wees, veral gedurende die selverdelingstadium van vruggroei. Kompetisie tussen vrugte, en tussen vrugte en vegetatiewe groei sal die voorsiening van koolstof gedurende die kritieke stadium aan die vrug beperk en so vruggroote benadeel. Daar is dus hernude belangstelling in die gebruik van ringelering in kombinasie met die gewone vrug uitdunprogramme om groei te beheer en vruggrootte te verbeter. 'n Nuwe, sagter chemiese groeireguleerder, proheksadioon-kalsium (ProCa) is ook nou beskikbaar vir groeibeheer op appelbome. In hierdie studie is die effekte van, en moontlike interaksie tussen ringelering, ProCa en vruguitdunning ondersoek ten opsigte van loot- en vruggroei en opbrengs, sowel as die effekte op gaswisseling op 'Royal Gala', 'Fuji' en 'Cripps' Pink' appelbome. ProCa veroorsaak korter lote in aJ drie kultivars. Verlengingslote is meer sensitief as beurslote vir ringelering en ProCa. ProCa is effektiewer as ringelering om lootgroei te beheer, en 'Fuji' en 'Cripps' Pink' is sensitiewer as 'Royal Gala'. Ringelering lei tot verbeterde vruggroeitempos gedurende die eerste 40 dae na volblom en verbeterde vruggrootte by oes. Ringelering verbeter die totale oplosbare vastestotkonsentrasie (TOVS) van 'Fuji' en 'Cripps' Pink' in vergelyking met kontrole- en ProCa-behandelings, onderskeideHk. ProCa inhibeer lootgroei effektief, maar geen bewyse van verbeterde koolstomllokasie na vrugte en reproduktiewe knoppe is gevind nie. Opbrengseffektiwiteit van geringeleerde borne verhoog gedurende die tweede seisoen van ringelering weens beter reproduktiewe knopontwikkeling. Ringelering later as 4 weke na volblom (WNVB) is minder effektief om reproduktiewe knopontwikkeling op ou en nuwe spore in 'Royal Gala' en 'Cripps' Pink' te stimuleer. Die positiewe effek van ringelering op reproduktiewe knoppe op 'Fuji' verminder sodra dit later as I WNVB gedoen word. Op langlote het 'n laat ringelering (6 en 8 WNVB) die beste effek op reproduktiewe knopontwikkeling. Die mees voordelige tyd om te ringeIeer was 2-4 WNVB, so vroeg as moontlik gedurende die selverdelingstadium van vruggroei, maar nie voor natuurlike vrugval voltooi is nie. Die kombinasie van vroei! ringelering en die toediening van ProCa het potensiaal om koolstofallokasie na die vrug te verbeter, met die gepaardgaande verbetering in vruggrootte en -kwaliteit. RingeJering vroeg in die seisoen inhibeer fotosintese en hierdie verlaging in koolstof beskikbaarheid het tot gevolg dat lootgroei vroei!r gestaak word. Later in die seisoen veroorsaak verlaagde vruggetalle 'n afname in fotosintese. Die optimum temperatuur vir fotosintese verander na gelang van heersende lugtemperature. Die oes-geinduseerde verlaging in sinksterkte verander stomatale sensitiwiteit vir hoo temperature. Weens 'n verJaagde aanvraag vir koolhidrate deur die plant word fotosintese verlaag na-oes. Weens die verlaging is stomata sensitiewer vir hoer temperature en beperk dus waterverlies. V oor oes is daar 'n hoo aanvraag na koolhidrate dus word stomata oop gehou selfs by hoe temperature ten koste van watergebruiksdoeltreffendheid. Die skerp styging in donker respirasie in blare en vrugte met 'n verhoging in temperature sal beteken dat koolhidraat-tekorte kan ontstaan in bome gedurende die bron-beperkte periodes vroeg in die seisoen, veral onder warm toestande 500S wat algemeen ervaar word in die Wes Kaap.

Glycosylation, the addition of one or more carbohydrates molecules to a protein, is crucial for many cellular processes. Aberrant glycosylation is a key marker for various diseases such as cancer and rheumatoid arthritis. It has also recently been discovered that glycosylation is important in the ability of the Human Immunodeficiency Virus (HIV) to evade recognition by the immune system. Given the importance of glycosylation in disease, major efforts are underway in life science research to investigate the glycome, the entire glycosylation profile of an organelle, cell or tissue type. To date, little bioinformatics research has been performed in glycomics due to the complexity of glycan structures and the low throughput of carbohydrate analysis. Recent advances in mass spectrometry (MS) have greatly facilitated the analysis of the glycome. Increasingly, this technology is preferred over traditional methods of carbohydrate analysis which are often laborious and unsuitable for low abundance glycoproteins. When subject to mass spectrometry with collision-induced dissociation, glycopeptides produce characteristic MS/MS spectra that can be detected by visual inspection. However, given the high volume of data output from proteome studies today, manually searching for glycopeptides is an impractical task. In this thesis, we present a tool to automate the identification of glycopeptide spectra from MS/MS data. Further, we discuss some methodologies to automate the elucidation of the structure of the carbohydrate moiety of glycopeptides by adapting traditional MS/MS ion searching techniques employed in peptide sequence determination. MS/MS ion searching, a common technique in proteomics, aims to interpret MS/MS spectra by correlating structures from a database to the patterns represented in the spectrum. The tool was tested on high throughput proteomics data and was shown to identify 97% of all glycopeptides present in the test data. Further, the tool assigned correct carbohydrate structures to many of these glycopeptide MS/MS spectra. Applications of the tool in a proteomics environment for the analysis of glycopeptide expression in cancer tissue are also be presented.

Carbohydrates have an essentials role in wide range of biological phenomena. It is well known that most of the eukaryotic proteins are glycosylated and that their glycosylation undergoes dynamic changes, nevertheless the biological imperative for these modifications is still not fully understood. However, one area in which the importace of cell surface glycosylation has recently been the subject of active investigations is the tumor plasma membrane biology, where many changes in glycosylation have been found useful for diagnosis, and mostly recent, even for the therapies of malignant disease. Interestingly cell surface glycoconjugates, namely N-linked and O-linked oligosaccharides have been found therapeutically attractive for treatment of certain tumors. And although our understanding of the participation of these principal glycan classes in tumorigenesis is far from complete, there are already several examples of carbohydrate-based antitumor vaccines. Therefore, we decided to give this issue more attention, especially the molecular mechanisms responsible for identifying changes in glycosylation of the surface of tumor cells of the immune system. Although in the past in our laboratory identified a receptor-type lectin specific lectin receptors on natural killer cells, very little is yet known...

Les glycosaminoglycannes (GAGs) sont des molécules polysaccharidiques polysulfatées intervenant dans des processus aussi variés que la prolifération, différenciation ou migration cellulaire, la coagulation sanguine ou l‟infection virale. Il est généralement admis qu‟une séquence particulière de GAG doit être associée à une fonction biologique spécifique. Les structures chimiques globales des GAGs sont connues. Cependant, contrairement au séquençage des gènes ou des protéines, la détermination de la séquence saccharidique exacte impliquée dans une fonction biologique particulière n‟est encore pas possible. Le séquençage « glycomique » constitue donc un enjeu majeur. L‟une des technologies les plus novatrices pour aborder ce problème de séquençage des GAGs semble être l‟impression moléculaire. En effet, elle permet d‟obtenir des polymères (MIPs pour Molecular Imprinted Polymer) spécifiquement imprimés par la forme structurale d‟une molécule cible.En nous appuyant sur des travaux antérieurs réalisés avec des modèles saccharidiques sulfatés simples, nous avons appliqué cette technologie à la reconnaissance de glycannes sulfatés complexes d‟intérêt biologique tels qu‟une héparine de bas poids moléculaire ou un mimétique ayant une activité anticoagulante. Il a été démontré une reconnaissance spécifique et sélective selon la molécule étudiée à l‟aide de MIPs spécialement conçus pour chaque GAG. De plus, nous avons obtenu des MIPs qui, en immobilisant temporairement un sucre, permettraient leur substitution de façon stéréospécifique. La détermination des conditions optimales de synthèse des MIPs s‟est avéré une étape nécessaire à l‟obtention d‟une bonne reconnaissance. Ces travaux ouvrent des perspectives d‟application de la technique d‟impression moléculaire à l‟analyse des séquences de GAGs d‟intérêt biologique / Glycosaminoglycans (GAGs) are polysulfated polysaccharide molecules involved in many biological processes such as cellular proliferation, differentiation or migration, blood clotting or viral infection. It is generally admitted that a particular GAG sequence is connected to a specific biological function. Depending on their composition in disaccharides, GAGs are classified into subfamilies whose overall chemical structures are known. Unlike gene or protein sequencing, determination of the exact saccharidic sequence involved in a particular biological function is not yet possible with the available technological tools. "Glycomics" is a real challenge nowadays. One of the most innovative technologies to achieve this goal seems to be the molecular imprinting. Indeed, it provides polymers (MIPs for Molecular Imprinted Polymer) imprinted by the structural form of a target molecule.Based on previous studies performed with simple sulfated saccharides, this technology has been applied to the recognition of complex sulfated glycans. MIPs were achieved demonstrating specific and selective recognition for a Low Molecular Weight Heparin or a synthetic anticoagulant mimetic. Other MIPs were able to temporally immobilize sugars which make them available for stereo-specific modifications. Screening of optimal synthesis conditions of MIPs appeared a necessary step to obtain a specific and selective recognition. These studies open further possibilities to analyze GAG sequences carrying biological functions by the molecular imprinting technology

Low molecular weight gelators (LMWGs) are small molecules that are capable of entrapping solvents to form a gel in organic solvents or aqueous solution. These compounds rely solely on noncovalent forces to form the fibrous networks necessary to entrap a variety of solvents. The organogels and hydrogels thus formed could have applications in a variety of fields from environmental to biological to medicinal. Carbohydrates are ideal starting materials to synthesize LMWGs, because of their natural abundance, dense chirality, and biocompatibility. D-Glucose is the most common monosaccharide and D-glucosamine is isolated from natural sources, such as crab shells. Several series of compounds were synthesized using compounds 1-3 as the starting materials. These include esters, carbamates, amides, and ureas. The structure and gelation relationship was analyzed to obtain guidelines for designing new LMWGs. Compound 1 is a simple derivative of D-glucose and its terminal alkynyl esters and saturated carbamates are effective gelators. Compound 2 is a simple derivative of D-glucosamine and its amide and urea derivatives are also effective gelators. Compound 3 is formed from the deoxygenation of D-glucose. 1OOHOOCH3OHOPh2OOHOOCH3NH2OPh3OOHOOHOPh The design, synthesis and gelation properties of several classes of sugar based low molecular organo/hydrogelators will be discussed in this thesis in chapters 2, 3, and 4. After obtaining highly effective organo/hydrogelators, potential applications of these novel molecular systems can be explored. Some preliminary study on using one of the gelator in enzyme assay has shown that it is possible to utilize the hydrogels to immobilize enzymes. However, future research can explore further on the applications of these gelators.

Carbohydrate molecules are essential parts of living cells. They are used as energy storage and signal substances, and they can be found incorporated in the cell membranes as attachments to glycoproteins and glycolipids, but also as free molecules. In this thesis the effect of carbohydrate molecules on phospholipid model membranes have been investigated by the means of Molecular Dynamics (MD) computer simulations. The most abundant glycolipid in nature is the non-bilayer forming monogalactosyldiacylglycerol (MGDG). It is known to be important for the membrane stacking typical for the thylakoid membranes in plants, and has also been found essential for processes related to photosynthesis. In Paper I, MD simulations were used to characterize structural and dynamical changes in a lipid bilayer when MGDG is present. The simulations were validated by direct comparisons between dipolar couplings calculated from the MD trajectories, and those determined from NMR experiments on similar systems. We could show that most structural changes of the bilayer were a consequence of lipid packing and the molecular shape of MGDG. In certain plants and organisms, the enrichment of small sugars such as sucrose and trehalose close to the membrane interfaces, are known to be one of the strategies to survive freezing and dehydration. The cryoprotecting abilities of these sugar molecules are long known, but the mechanisms at the molecular level are still debated. In Papers II–IV, the interactions of trehalose with a lipid bilayer were investigated. Calculations of structural and dynamical properties, together with free energy calculations, were used to characterize the effect of trehalose on bilayer properties. We could show that the binding of trehalose to the lipid bilayer follows a simple two state binding model, in agreement with recent experimental investigations, and confirm some of the proposed hypotheses for membrane–sugar interactions. The simulations were validated by dipolar couplings from our NMR investigations of TRH in a dilute liquid crystal (bicelles). Furthermore, the assumption about molecular structure being equal in the ordered and isotropic phases was tested and verified. This assumption is central for the interpretation of experimentally determined dipolar couplings in weakly ordered systems. In addition, a coarse grain model was used to tackle some of the problems with slow dynamics that were encountered for trehalose in interaction with the bilayer. It was found that further developments of the interaction models are needed to properly describe the membrane–sugar interactions. Lastly, from investigations of trehalose curvature sensing, we concluded that it preferably interacts in bilayer regions with high negative curvature. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript.</p>

Carbohydrates are essential biomolecules that decorate cell membranes and proteins in organisms. They are important both as structural elements and as identification markers. Many biological and pathogenic processes rely on the identification of carbohydrates by proteins, thereby making them attractive as molecular blueprints for drugs. This thesis describes how NMR spectroscopy can be utilized to study carbohydrates in solution at a molecular level. This versatile technique facilitates for investigations of (i) shapes, (ii) motions and (iii) interactions. A conformational study of an E. coli O-antigen was performed by calculating atomic distances from NMR NOESY experiments. The acquired data was utilized to validate MD simulations of the LPS embedded in a membrane. The agreement between experimental and calculated data was good and deviations were proven to arise from spin-diffusion. In another study presented herein, both the conformation and the dynamic behavior of amide side-chains linked to derivatives of D-Fucp3N, a sugar found in the O-antigen of bacteria, were investigated. J-couplings facilitated a conformational analysis and 13C saturation transfer NMR experiments were utilized to measure rate constants of amide cis-trans isomerizations. 13C NMR relaxation and 1H PFG diffusion measurements were carried out to explore and describe the molecular motion of mannofullerenes. The dominating motions of the mannofullerene spectral density were found to be related to pulsating motions of the linkers rather than global rotational diffusion. The promising inhibition of Ebola viruses identified for a larger mannofullerene can thus be explained by an efficient rebinding mechanism that arises from the observed flexibility in the linker. Molecular interactions between sugars and caffeine in water were studied by monitoring chemical shift displacements in titrations. The magnitude of the chemical shift displacements indicate that the binding occurs by a face to face stacking of the aromatic plane of caffeine to the ring plane of the sugar, and that the interaction is at least partly driven by solvation effects. Also, the binding of a Shigella flexneri serotype Y octasaccharide to a bacteriophage Sf6 tail spike protein was investigated. This interaction was studied by 1H STD NMR and trNOESY experiments. A quantitative analysis of the STD data was performed employing a newly developed method, CORCEMA-ST-CSD, that is able to simulate STD data more accurately since the line broadening of protein resonances are accounted for in the calculations. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 4: Manuscript. Paper 5: Manuscript.</p>

The non-sustainable nature of fossil fuels as feedstocks for valuable chemicals, combined with the environmental damage caused by their extraction and combustion, increases the need for the development of a bio-based economy. While industry and public opinion are slowly shifting towards acceptance of this change, efficient technologies for the depolymerization and subsequent separation of lignocellulosic biomass fall short of the ever-increasing demand. In particular, there are currently no efficient, sustainable mass scale methods to convert lignin, the most abundant source of aromatic molecules on Earth. The use of oxovanadium(V) catalyst complexes to aerobically cleave C‒C bonds has been demonstrated previously and remains an attractive option for incorporation into a sustainable bio-based economy. Two new triphenoxyamine oxovanadium(V) catalysts with reduced steric bulk and electron density at the metal center (vs. previously reported complexes) have been synthesized for aerobic oxidative diol C‒C bond cleavage. These complexes were found to cleave less activated and more complex substrates than previous generations, including cyclic diols and polyalcohols. Several insights into the reaction pathways of this class of complex were elucidated through a series of kinetic studies. Experimentally, the rate of C‒C bond cleavage of both pinacol and hydrobenzoin was determined to be unaffected by substitution of the O‒H bonds with deuterium, suggesting that currently proposed mechanisms need to be revised. Multiple catalytic regimes were observed during anaerobic reaction, which were not altered significantly by the brief addition of O2. A series of density functional theory calculations revealed a plausible mechanism for the trialkoxy complex that did not involve a proton transfer in the rate determining step, instead suggesting that ligand-arm dissociation-reassociation play a significant role in the reaction. In a second project, new bisphenoxyamine-N-appended base ligand with less steric hindrance and electron density at the metal center, has been synthesized utilizing similar design principles gained from work with triphenoxyamine catalysts. When reacting with lignin model compound 1,2-diphenyl-2-methoxyethanol, this new complex displays a higher selectivity towards aldehydes and esters (relative to previous bisphenoxyamine-N-appended ligands), leading to a higher rate of C‒C bond cleavage. Investigations into the mechanism of bisphenoxy complexes, as well as the role of the N-appended base in reactivity, were performed using substrate pre-complexed bisphenoxy compounds. Thermolysis at 60 and 100 °C produced almost exclusively oxidative C‒H bond cleavage product benzyl methyl ether, with evidence for overoxidation product benzoic acid observed. Thermolysis of labelled substrate pre-complexed revealed that N-appended base may impede C‒C cleavage of 1,2-diphenyl-2-methoxyethanol by forcing the methyl ether away from the oxovanadium(V) center. Through the use of these multidentate phenoxyamine ligands, advances have been made towards sustainable oxovanadium catalysis in the pursuit of efficient and selective lignocellulosic disassembly for a sustainable bio-based economy.