Rozprawy doktorskie na temat „Organic acids”

In this study, production of organic acids from cheese-whey was studied. Optimization of organic acids production was performed in semi-batch and batch reactors. Two sets of experiments were performed. First set of experiments were performed in semi-batch reactors for the optimization of organic loading rate (OLR) and hydraulic retention time (HRT). As a result of Set 1 experiments optimum OLR was found to be 15 g COD l-1. Second set of experiments were performed in batch reactors by using the optimum OLR found in Set 1 experiments. Set 2 experiments were conducted to study the effect of using different seed cultures and Basal Media (BM) on Volatile fatty avid (VFA) production. Main acidogenesis products were acetic acid (Hac), butyric acid (Buty) and propionic acid (HPr) with smaller quantities of i-butyric acid (i-Buty), valeric acid (Val) and caproic acid (Cap). It was seen that BM had a suppressive effect on ethanol (EtOH) production while it stimulated the VFA production. Higher VFA productions and variety of VFA types were observed in Test Reactors seeded with acidogenic culture (R3 and R6).

Abstract Purpose – The purpose of this paper is to supplement the scant previous investigations on the corrosion behaviour of 2205 and 2507 duplex stainless steels in selected organic acids containing chloride additions. Design/methodology/approach – Microstructural examination of the alloys was first carried out, after which the corrosion behaviour of the alloys in citric, oxalic, formic and acetic acids containing chloride additions at varying temperatures was studied using electrochemical techniques. Findings – The alloy 2507 material had a larger grain size than did the alloy 2205 sample. The corrosion resistances of the alloys generally are highest in acetic acids and lowest in citric acid. The addition of chloride had a pronounced effect on their corrosion resistance. Alloy 2507 generally exhibited higher corrosion resistance in all of the acids than alloy 2205, with the exception of acetic acid at room temperature. The 50:50 ratio of ferrite to austenite composition, as revealed by phase compositional analysis, indicated no significant possibility for galvanic corrosion between the phases. This suggests that the corrosion behaviour of the alloys is controlled by their grain sizes and chemical compositions. Originality/value – Although the corrosion behaviour of duplex stainless steels in some organic acid media has been reported, this investigation covers the major organic acids not previously reported. Since in real industrial systems a mixture of both organic and minerals acids/salts may typically exist, investigations of the combined effect of chloride ions with the organic acids reported in this paper typify real industrial operations. The paper thus provides a basis for material selection for the application of 2205 and 2507 in industrial systems where organic acids are mostly used.

Organic acids have been hypothesized to be important in mobilizing nutrients in calcareous soils, however, evidence to support this was lacking. This thesis investigates the effect of increasing concentrations of H-citrate, K-citrate, H-oxalate and K-oxalate on the solubility and uptake of P, Fe, Mn, Zn and Cu in plants growing in calcareous soils. In this study, the fate and capacity of organic acids as mechanisms for solubilizing mineral nutrients was investigated by measuring the sorption, and biodegradation reactions of citrate and oxalate in soil. This study has shown that the sorption reactions of oxalate and citrate in soil are rapid and that the degree of sorption is organic acid specific and to a lesser extent soil type specific. In addition, the amount of organic 'acid sorption was strongly dependent upon the cation balancing the organic acid anion (i. e. H+ or K+). I also demonstrated that CaCO3 is a binding site for oxalate and to a lesser extent citrate in soil. The biodegradation of oxalate and citrate was fast in soil although citrate tended to be mineralized faster. When investigating the sorption and desorption reactions of organic acids in calcareous soils, the sorption of oxalate was much greater that of citrate. The amount of organic acid desorbed from the solid phase was dependent on ionic strength and composition of the desorption solution. In comparison to citrate, more oxalate could be desorbed from the soil, depending upon the initial amount of oxalate added to the soil. In addition, the test soils were extracted with organic acid solutions of different concentrations for different time periods and the amount of Fe, Mn, Zn, Cu, P and Ca mobilization into solution measured. The results showed that the presence of organic acids significantly affects the concentration of metals and anions in soil solution. Generally, organic acid concentrations >1 mM were required to mobilize nutrients into solution. Citrate tended to be more effective than oxalate at mobilizing nutrients from the soil. In most cases the mobilization was not transient and elevated levels of nutrients were seen in solution for up to 6 h after addition of the organic acids. The effects of three different organic acid application methods on the availability and uptake of P and micronutrients in wheat was also investigated. The study showed that wheat plants treated with organic acids accumulated significantly higher concentrations and amounts of micronutrients than the untreated control plants. Foliar application of organic acid without any Zn treatment proved the most effective method of increasing Fe uptake into wheat leaves. The effects of organic acids on the availability and uptake of P from the wheat rhizosphere was studied to determine the importance of organic acid type and concentration on 33P uptake by shoots. The results showed that elevated concentrations of organic acids in the rhizosphere significantly enhanced shoot 33P accumulation, while citrate was much less effective at stimulating 33P uptake. In the absence of microorganisms, both organic acids were capable of mobilizing P from the soil particularly at concentration >1 mM. Citrate mineralization by soil microorganisms proceeded at a higher rate than oxalate mineralization. Overall, the presence of organic acids significantly affects the concentration of metals in soil solution and this mobilization is dependent upon the type of organic acid, its ionic form, its concentration, reaction time and the type of soil. The response of wheat plants to different methods of organic acid addition proved variable. Organic acids did result in an increase in metal mobilization and plant uptake. In particular, oxalate resulted in a significant enhancement in plant P. This work presents evidence to show that organic acids may be important in nutrients acquisition in calcareous soils.

In order to investigate the role played by the aromatic moiety of Aromatic Peptide Nucleic Acids (APNAs) in their ability to hybridize with RNA and DNA, as well as improve the solubility of APNA oligomers in aqueous solutions, a new generation of heterocyclic monomers were designed. APNA monomers, where the nucleobase can be thymine, cytosine adenine or guanine, with backbones contain thiophene and pyridine moieties were synthesized. Suitably protected APNA-APNA and PNA-APNA dimers were also synthesized as building blocks for the solid phase synthesis of APNA-PNA chimeras and APNA homopolymers. Due to the instability of the pyridine-containing APNA oligomers to the harsh acidic conditions required to cleave oligomers from the MBHA resin, a new protocol was developed for the synthesis of these molecules on the trityl chloride resin. Oligomers of PNA and APNA-PNA chimeras were successfully synthesized on this solid support, and cleaved from the resin using mild acidic conditions.

The recent upsurge of interest in the peptide-based drug molecules has been accompanied by a great deal of attention to the design of stereochemically defined non-proteinogenic amino acids. As a continuous effort to develop efficient syntheses of χ-constrained amino acids in our group, we recently have developed a practical methodology for the asymmetric synthesis of substituted pyroglutamic acid, glutamic acid and proline analogues, which are of important use in examining the relationships between conformation and bioactivities of biologically important peptides (e.g. DPDPE, α-MSH). The key step in this method is an asymmetric Michael addition reaction between a chiral Ni(II)-complex of the glycine Schiff base (S)-NiGlyBPB, and derivatives of α,β-unsaturated carboxylic acids. This new method is the first highly diastereoselective, room temperature, organic base-catalyzed, asymmetric Michael addition reaction. Excellent chemical yields and diastereoselectivity, along with the simplicity of experimental procedure, renders the present method of immediate use for preparation of various novel beta-substituted pyroglutamic acids, glutamic acids and prolines. Decomposing the resulting addition products in acidic medium, followed by neutralizing with ammonia, gave optically pure substituted pyroglutamic; acids in good yields (>80%). The substituted pyroglutamic acids were converted to the corresponding substituted glutamic acids by hydrolysis in 6N HCl, or to substituted proline analogues by selective reduction of amide carbonyl group to a methylene group. Both novel substituted glutamic acids and prolines are being incorporated into biologically important peptide MT-II analogues for structure-activity studies.

This thesis describes progress on the application of boronic acids and borate esters as catalysts and reagents in synthetic organic chemistry, focusing on two areas: one-pot enolate formation/aldol reactions and amide bond formation. Chapter 1 introduces the reader to boronic acids and derivatives thereof, their methods of preparation and their use in synthetic organic chemistry as reactants, reagents and catalysts. Chapter 2 covers current chemical methods and cellular alternatives for amide bond formation. Here, we also discuss our use of boron reagents for the activation of carboxylic acids as well as amides. Chapter 3 introduces a new concept in catalytic aldol reactions, i.e. an alternative strategy to access boron enolates in situ. The work covers successful demonstration of the feasibility of such an approach on an intramolecular system. A novel variation of aerobic Chan–Evans– Lam coupling, an intramolecular coupling of an aliphatic alcohol with a boronic acid using catalytic copper, is also introduced Chapter 4 builds on our observations on gold catalysis and especially that in relation to electrophilic halogenations. Chapter 5 contains full details of the experimental procedures.

Various aldehydes have been reacted with methyl acrylate under Baylis-Hillman conditions, using DABCO as a catalyst, to afford a range of α-substituted acrylic esters containing an allylic hydroxy group. Selected Baylis-Hillman products have been brominated, hydrolysed and acetylated to afford substrates for the synthesis of necic acid analogues. The diastereo- and regioselectivity of nucleophilic attack, using sodium methylmercaptan, on the Baylis-Hillman products and selected brominated derivatives was investigated. The allylic hydroxy compounds favour conjugate addition with the generation of a new chiral centre, while the allylic bromo derivatives favour substitution (SN and SN') (S[subscript N] and S[subscript N]') with consequent loss of chirality. (E)-2-Isopropylcrotonic acid, a vital precursor in the synthesis of all stereoisomers of trachelanthic and viridifloric acid, was synthesised in an attempt to obtain the necic acid components required for total alkaloid synthesis of lycopsamine and its derivatives. This precursor and salicylic acid were then used to prepare esters of retronecine, a dihydroxy necine base obtained via extraction and consequent hydrolysis of retrorsine.

La presente Tesis ha sido enfocada en la síntesis de Polímeros de Coordinación (CPs) y Metal-organic frameworks (MOFs) a partir de ligandos basados en biomoléculas para la obtención de materiales nuevos y funcionales. Sobre esta premisa, la Tesis aborda dos líneas de investigación principales que han sido desarrolladas para alcanzar los objetivos propuestos: i) estudiar la influencia de la razón enantioméricos de dos ligandos quirales sobre la estructura y quiralidad en Metal-Organic Frameworks, y ii) el diseño y la síntesis de nuevos polímeros de coordinación basados en adenina, ligandos aromáticos tetracarboxílicos y metales de transición. En el Capítulo 1, mostramos un breve resumen a cerca de la química, los métodos de síntesis y las aplicaciones actuales de CPs/MOFs, como, por ejemplo, absorción de gases o catálisis, con énfasis en aquellos en los cuales se usan biomoléculas como bloques de construcción. Posteriormente, en el Capítulo 2, describimos los objetivos generales de nuestra tesis. El Capítulo 3 describe la importancia de la quiralidad como una importante propiedad en CPs/MOFs, y resume los resultados obtenido y publicados en el artículo “The influence of the enantiomeric ratio of an organic ligand on the structure and chirality of metal–organic frameworks”, Chemical Communications, 2014, 50, 13829-13832. En este trabajo, hemos mostrado la importancia de la razón enantiomérica como variable relevante en la síntesis de MOFs porosos, y que puede ser tomada en cuenta como variable con resultados sorprendentes, la cual vii nos ha permitido obtener materiales porosos variando la razón enantiomérica. En el Capítulo 4, hemos tratado de desarrollar nuevos polímeros de coordinación basados en adenina usando ácidos aromáticos tetracarboxílicos, como ligandos auxiliares y Co(II). Lo resultados han sido publicados en el artículo titulado “Two New Adenine-based Co(II) Coordination Polymers: Synthesis, Crystal Structure, Coordination Modes and Reversible Hydrochromic Behavior”, Crystal Growth and Design, 2015, 15, 3182–3189, donde hemos aprovechado de los cinco sitios potenciales de coordinación y mostrado la importancia de adenina como ligando rígido en la síntesis de polímeros funcionales.
The present Thesis has been addressed to the synthesis of bio-related metal-organic frameworks and coordination polymers as novel and functional materials. On the basis of the above, two main lines were developed to reach the objectives proposed: i) study the influence of enantiomeric ratio of two chiral ligands over the structure and chirality in Metal-Organic Frameworks, and ii) the design and synthesis of novel coordination polymers based in nucleobase-adenine, aromatic tetracarboylate ligands and transition metals. In Chapter 1, we showed a brief review about Coordination Polymers (CPs)/Metal-Organic Frameworks (MOFs), their chemistry, synthetic methods and their current applications, as gas adsorption or catalysis, with emphasis in ones which use biomolecules as building blocks for the construction of coordination polymers. Then, general objectives of this Thesis are described in Chapter 2. Chapter 3 describes the importance of chirality as an important property in CPs/MOFs, and summarized the results obtained and reported in the article “The influence of the enantiomeric ratio of an organic ligand on the structure and chirality of metal–organic frameworks”, Chemical Communications, 2014, 50, 13829-13832. In this work, we showed the importance of enantiomeric ratio as relevant variable in the synthesis of porous metal-organic frameworks, and as it might be introduced as variable with surprising results, which enabled us to obtain a porous material varying the enantiomeric ratio. v In Chapter 4, we aimed to develop new adenine-based coordination polymers using aromatic tetracarboxylic acids, as auxiliary linker and Co(II). We showed in the article titled “Two New Adenine-based Co(II) Coordination Polymers: Synthesis, Crystal Structure, Coordination Modes and Reversible Hydrochromic Behavior”, Crystal Growth and Design, 2015, 15, 3182–3189, where we took advantage of its five potential coordination sites for metal binding, showing the relevance of adenine as rigid linker in the synthesis of functional coordination polymers.

ENGLISH ABSTRACT: The first successful captive spawning of the South African abalone Haliotis midae occurred in the 1980’s and subsequently the commercial abalone industry in South Africa has developed, with an estimated investment of US$ 12 million and annual output of 500 to 800 tons by 2001, making South Africa the biggest abalone producer outside of Asia. Natural kelp is currently the major feed and the development of a suitable substitute, and improved disease management in abalone culture are seen as the primary factors limiting expansion of the industry in South Africa. Further, abalone growth rates are very slow and improvements in growth rate will lead to shortened production times with benefits to producers. Diseases in aquaculture have traditionally been combated using antibiotics as treatment (therapeutic usage) and preventative measure (prophylactic usage). In terrestrial livestock management, antibiotics are also used as growth promoters. The use of antibiotics in aquaculture has recently sparked concerns about the development of antibiotic resistance in pathogens of humans and aquaculture organisms, and alternative strategies to using antibiotics mainly focus on manipulating the microbial composition in the host organism, in order to establish a beneficial microbial population to prevent disease. The role that organic acids and their salts can play as growth promoters in the South African abalone Haliotis midae, and as manipulators of the gut microflora of this species of abalone was investigated and compared to the effects of antibiotics. Three different treatments were tested against a negative control and a positive control containing 30ppm avilamycin, a commercial antibiotic growth promoter (AGP) used in the pig and poultry industry. The 3 treatments consisted of 1% acetic and 1% formic acid (treatment AF), 1% sodium benzoate and 1% potassium sorbate (treatment SBPS), and 1% benzoic and 1% sorbic acid (treatment BS). Three different experiments were conducted to test the effects of the different acids and salts. The first experiment was under controlled optimum water temperature conditions (16.5ºC), another at elevated water temperature (20.5ºC) in order to test response during temperature stress conditions, and the final trial was conducted under uncontrolled practical production conditions. In an attempt to establish the mechanism by which the treatments have their effects (if any), the composition of the gut microflora of the abalone was monitored. It was found that the organic acids and salts investigated can enhance the growth rate of Haliotis midae in the size class 23 mm to 33 mm mean length significantly when compared to both control treatments. It was further found that the tested AGP had no effect on growth rate. None of the treatments had a significant effect on feed conversion ratio (FCR), Incidence cost (IC) or feed intake. It could also not be shown that the treatments affected the intestinal microflora of the abalone, although this might be due to inadequate microbiological methods. The mechanism by which the acids and salts have their effects could not be established. It was found that the animals in the controlled system underwent an initial adaptation period, which led to improvement in specific growth rate (SGR), FCR and IC as the experiment progressed during the controlled optimal conditions experiment. Large differences in FCR and IC was seen for controlled optimal conditions and production conditions which means that there is still a large scope for developing methods to improve practical on-farm feed utilisation by abalone. SGR, FCR and IC were negatively influenced by raising water temperature from 16.5ºC to 20.5ºC. The composition of the gut microflora of the abalone also changed significantly after the water temperature was raised. It appears that animal weight gain and shell growth respond differently to changing water temperatures, which is reflected in a change in Fulton condition factor. A relationship between the length and weight of abalone between 15 mm and 47 mm was established and it was found that Haliotis midae does not follow an isometric growth relationship. This relation can be used as a tool to improve farm management and therefore also profitability. Various micro-organisms were isolated from Haliotis midae during the trial, but their relationship and interaction with abalone is not clear. Clear dominance by specific species of bacteria was observed during certain periods. The current research has clearly showed the potential of organic acids and their salts to act as growth promoters in the South African abalone Haliotis midae, with application in both the local aquaculture and feed manufacturing industries. The possibility further exists that some aspects of the current research can be adapted to be applicable in other abalone species and even in other aquaculture species.
AFRIKAANSE OPSOMMING: Die eerste suksesvolle aanteel van die Suid-Afrikaanse perlemoen Haliotis midae in gevangeskap is in die 1980’s gerapporteer, waarna ‘n suksesvolle akwakultuur industrie ontwikkel het met ‘n geskatte produksievermoë van 500 tot 800 ton en kapitaalbelegging van US$ 12 miljoen in 2001. Suid-Afrika is tans die grootste perlemoen-produserende land wat buite Asië geleë is. Die ontwikkeling van ‘n geskikte alternatiewe voedselbron vir natuurlike kelp (tans die algemeenste voedselbron wat gebruik word in die kweek van perlemoen), sowel as verbeterde siektebestryding word tans gesien as die hooffaktore wat verdere uitbreiding in die Suid-Afrikaanse industrie beperk. Perlemoen het verder baie stadige groeitempo’s en enige verbetering in hierdie verband sal produksietye verkort en dus produsente bevoordeel. Siektes in akwakultuur word tradisioneel bestry deur gebruik te maak van antibiotiese behandeling (terapeutiese bestryding) of van voorkomende behandeling (profilaktiese bestryding). In gewone diereproduksie-sisteme (bv. varke en hoenders) word antibiotika ook gebruik as groeistimulante. Die gebruik van antibiotika in akwakultuur het onlangs die bekommernis laat ontstaan dat sekere menslike en dierepatogene weerstand kan ontwikkel teen sommige middels, wat die behoefte laat ontstaan het om siektebestryding sonder die gebruik van antibiotika te ontwikkel. Alternatiewe strategieë fokus grootliks daarop om die samestelling van die mikrobiese bevolking van die gasheer te manipuleer en sodoende ‘n voordelige bevolking in die gasheer te vestig, wat dan siektes voorkom. Daar is ondersoek ingestel na die rol van organiese sure en hul soute as groeistimulante en manipuleerders van die mikrobiese bevolking in die Suid-Afrikaanse perlemoen Haliotis midae. Drie verskillende behandelings is getoets en vergelyk met beide ‘n negatiewe- en positiewe kontrole (wat 30 dele per miljoen van ‘n kommersiële antibiotiese groeistimulant bevat het). Die drie formulasies het onderskeidelik bestaan uit ‘n mengsel van 1% etanoëen 1% metanoësuur (behandeling AF), 1% bensoë- en 1% sorbiensuur (behandeling BS) en 1% natriumbensoaat en 1% kaliumsorbaat (behandeling SBPS). Om die effekte van hierdie formulasies te toets, is daar 3 proewe gedoen. Een proef is gedoen onder temperatuurbeheerde toestande teen ‘n optimum watertemperatuur van 16.5ºC terwyl ‘n ander gedoen is onder onbeheerde, praktiese produksie-omstandighede. ‘n Verdere beheerde proef is gedoen teen ‘n watertemperatuur van 20.5ºC om die effek van die verskillende formulasies te toets wanneer die diere aan temperatuur-spanning blootgestel word. Die samestelling van die mikrobiese bevolking in die dunderm van die perlemoen is deurentyd gemonitor in ‘n poging om die meganisme vas te stel waarvolgens die sure en soute hul effek het, indien daar enige effek waargeneem word. Daar is gevind dat die onderskeie sure en suursoute die groeitempo van Haliotis midae met ‘n gemiddelde lengte van 23 mm tot 33 mm beduidend kan verhoog in vergelyking met die groeitempo’s van beide kontroles. Daar is gevind dat die antibiotiese groeistimulant geen effek het op die groei van die diere nie en dat geen behandelings ‘n beduidende effek op voeromsetting, voerkoste of voerinname gehad het nie. Daar kon nie bewys word dat enige van die formulasies of die antibiotika ‘n effek gehad het op die mikrobes in die spysverteringskanaal van die perlemoene in die sisteem nie, alhoewel die gebrek aan ‘n effek moontlik toegeskryf kan word aan die onakkurate en onvoldoende mikrobiologiese metodes wat gebruik is tydens die studie. Die meganisme waarvolgens die sure werk kon nie vasgestel word nie. Daar is verder gevind dat die diere in die temperatuur-beheerde eksperiment aanvaklik deur ‘n aanpassingsperiode gegaan het, wat tot gevolg gehad het dat die spesifieke groeitempo, voeromsetting en voerkoste verbeter het met die verloop van die eksperiment. Daar is groot verskille gevind in die voeromsetting van beheerde optimale toestande en onbeheerde produksietoestande, wat impliseer dat daar nog baie ruimte en geleenthede is om metodes te ontwikkel wat beter voeromsetting bewerkstellig tydens perlemoenproduksie. Spesifieke groeitempo, voeromsetting en voerkoste is nadelig beïnvloed toe die watertemperatuur verhoog is vanaf 16.5ºC na 20.5ºC. Die samestelling van die mikrobiese bevolking in die spysverteringskanaal van die perlemoen het ook beduidende veranderinge ondergaan tydens hierdie temperatuur verhoging. Dit wil voorkom asof die lengtegroei van die dop en die toename in massa verskillend reageer op ‘n verandering in watertemperatuur en hierdie effek word weerspieël in die verandering in Fulton-kondisiefaktor. ‘n Verwantskap tussen totale doplengte en totale gewig van Haliotis midae kon vasgestel word vir diere tussen 15 mm en 47 mm en daar is gewys dat H. midae nie ‘n isometriese groeipatroon volg nie. Hierdie verwantskap kan aangewend word tydens produksiebestuur om produksie te verbeter en daardeur ook winsgewendheid te verhoog. Verskeie mikrobes is tydens die verloop van die proef geïsoleer, maar die rol van en interaksie tussen hierdie mikrobes en die Suid-Afrikaanse perlemoen is nie duidelik nie. Sekere bakterieë het die mikrobiese bevolking in die spysverteringskanaal van die perlemoen in hierdie proef oorheers tydens sekere groeiperiodes. Die huidige navorsing het duidelik aangetoon dat organiese sure en hul soute as groeistimulante kan optree in die Suid-Afrikaanse perlemoen Haliotis midae, met toepassings in die plaaslike akwakultuur- en voervervaardigins-industrieë. Dit beskik verder oor die potensiaal om aangepas te word sodat dit toepaslik is in ander perlemoenspesies en selfs ander akwakultuur organismes.

The only treatment for coeliac disease, a common autoimmune disorder, is life-long adherence to a gluten-free diet. However, the replacement of wheat gluten, a key structural and functional component in bread, poses a major technological challenge for food scientists. The use of non-wheat cereal proteins, as alternatives to gluten, shows much promise in gluten-free bread making. Literature has shown that when zein, the maize prolamin protein, is subjected to wet heat above its glass transition temperature (Tg), the protein becomes viscoelastic, rubbery and dough-like. Gluten-like fibrils are visible, which form complex protein networks similar to those found in wheat dough. The resulting zein dough has viscoelastic characteristics and can be successfully used with hydrocolloids to produce gluten-free bread. This project examined the influence of wet heat treatment and dilute organic acids (lactic acid and acetic acid) on the dough-making quality of non-wheat cereal proteins, such as kafirin and zein. Zein was the only non-wheat cereal protein to show any physical change when it was subjected to wet heat treatments, forming a dough-like substance. Acidification of the zein dough prepared at 40°C with concentrations of 0.7, 1.3 and 5.4% (v/v) organic acid in distilled water solutions, showed that the higher the concentration of acid used, the greater its effect on the dough's rheological properties. Tensile tests using a Keifer rig on zein dough showed that as the concentration of organic acid was increased from 0.7 to 1.3 and to 5.4% (v/v) the dough become softer and increasingly more extensible. The dough also exhibited less resistance to extension and reduced elasticity. CLSM revealed that the zein doughs contained a protein network, made up of fine protein fibrils, which became smoother and more homogenous as the concentration of acid was increased. Although SDS-PAGE revealed that no oligomerization took place with acid addition, iv FTIR showed that zein dough prepared with distilled water at 40°C had elevated levels of β-sheets. When organic acids were added in increasing levels, corresponding increases in the quantities of α-helices in the protein were observed. Alveography showed that zein-based doughs prepared with dilute organic acids retained gases well and that the concentration of dilute organic acids influenced dough distensibility (biaxial extensibility) and stability (the ability of the dough to retain gas). Low concentration of acids (0.7 and 1.3%) increased dough stability to levels similar to that of strong wheat flour, 103 mm H2O, but higher concentrations of acids (5.4%) led to a marked reduction in dough stability. Thus, by increasing zein dough functionality to such an extent, the apparent usefulness of the doughs and their ability to retain gases produced during fermentation is reduced. Simple distensibility tests on zein doughs showed that added organic acids promoted ‘clumping’ of the fine protein fibrils in the dough network into pronounced fibres. This would account for the decreased dough stability when high levels (5.4%) of organic acids were used. Baking trials with zein doughs were not successful as adequate leavening was impossible without an acid-tolerant leavening agent. It is believed that dilute organic acids influence the rheological properties of zein dough by creating a positively charged environment, in which the protein is partially solubilized. The higher the level of organic acid used, the greater the positive net charge and the more pronounced the effect on the protein network structure. Organic acids could also improve fluidity of the zein dough by acting as plasticizers. From this work it can be seen that although a protein network is present in all zein-based doughs, the ability of this network to retain gases is dependant on the level of organic acids present. The functional properties of zein-doughs made with low levels of organic acids (0.7 and 1.3%) shows potential in the production of gluten-free bread for individuals suffering from coeliac disease.
Dissertation (MSc)--University of Pretoria, 2013.
gm2014
Food Science
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E-glass has been widely used as a reinforcing material for years, especially as a plastic reinforcer in the production of GRP (Glass Reinforced Plastic). Failure of GRP materials under stress came in to the picture quite recently. Since then studies have been conducted in an attempt to understand the causes and the underlying behaviour.Except for the last section of the research (analysis using a kinetic approach) where glass fibre was cut out to weigh approximately 1.0g, standard sized specimens were soaked in the required acid solutions of desired concentrations for varying temperatures and time frames. Wherever tensile strength retention was measured, LLOYD instrument was employed. Leaching of the cations were analysed using Inductively Coupled Plasma – Optical Emission Spectroscopy (ICP-OES and also know and ICP-AES).The scope of this project can be divided in to four sections; first section involved investigating the effects of malonic acid. The study of malonic acid was narrowed to investigating the trend in strength retention. A rapid strength loss was observed initially followed by a much steady decline in the strength. However the continuation of the loss of strength was unmistakable throughout the time period of exposure. Furthermore, temperature can be observed as a facilitating factor in this degradation reaction.Secondly the corrosive effect of glyoxylic acid on E-glass fibre was studied. This was explored at two different temperatures for two specific time frames using various concentrations of the acid of interest. The influence of this acid on the glass fibre was found out in terms of strength retention and loss of cations from the glass matrix. The mildness of this acid was accentuated by the fact that 70% or more of the strength was retained at all the conditions employed. A minima in strength retention was observed at 2M acid concentration similar to the trends observed in the past (Betz and Jones 2003 and Jones and Chandler 1986). Leaching of cations reflected this trend. The large strength retention could be related to the fewer amounts of Ca and K leached from the glass matrix (Kumosa and Qui, 1997). Similar to malonic acid, an unusually large amount of B was leached out that could be due to the favourable orientation of the anion with the trivalent ions during the complex formation. Yet again temperature was found to enhance the degradation process.Next the extent of passivation (if any) showed by malonic acid was investigated using E-glass fibre pre-treated in 5M malonic acid and post treated in known corrosive acids hydrochloric acid and oxalic acid. Passivation of malonic acid was put to test through examination of strength retention of the fibres under these conditions. This segment was carried out as an extension of a finding (a behaviour synonymous to passivation) shown by malonic that surfaced the previous year by the present researcher. Increasing the pre-treatment time showed a great improvement in the retained strength for all the post-treatment acid mediums. Furthermore, while Jones and Betz (2004) featured 20-40% strength retention within a short time frame in 3M HCl, the immense amount of strength retention (60-70%) preceding pre-treatment should definitely be noted. Similarly strength retention of about 80% was observed when post-treated with the severely corrosive oxalic acid. Hence its is clear that passivation can be induced through prolonged pre-treatment in 5M malonic acid that could inhibit the attack of corrosive acid at least for a period of time.The last fragment of the study focussed on understanding and working out the mechanism behind the reactions between the E-glass fibre and acid medium in terms of kinetics. The acids utilized were 1.5M malonic acid and 3M glyoxylic acid and the assessments were made through the analysis of the weight changes brought about by the acid medium at various temperatures and time frames. In addition leaching patterns of cations were evaluated as this could contribute in achieving the objective. Maximum weight loss reached 4% in glyoxylic acid while that for malonic acid exceeded 20%. The general trend was that the glass fibres lost weight in both acids for a period of time followed by an evident weight gain. Furthermore the weight loss results fit the first order rate law. While the leaching of cations reflects the weight loss for the shorter time frames, steady loss of ions was visible even for the longer time frames where the weight has increased. The weight gain could be explained in terms of binding of anions to certain cations on the glass surface, accounting for the hindrance in the loss of cations at the longer time frames as well. About 50% of weight loss was associated to Ca while 20% was to Al, leaving 6% to B where as the rest of the ions had shown almost insignificant contribution to the weight loss.

E-glass has been widely used as a reinforcing material for years, especially as a plastic reinforcer in the production of GRP (Glass Reinforced Plastic). Failure of GRP materials under stress came in to the picture quite recently. Since then studies have been conducted in an attempt to understand the causes and the underlying behaviour.
Except for the last section of the research (analysis using a kinetic approach) where glass fibre was cut out to weigh approximately 1.0g, standard sized specimens were soaked in the required acid solutions of desired concentrations for varying temperatures and time frames. Wherever tensile strength retention was measured, LLOYD instrument was employed. Leaching of the cations were analysed using Inductively Coupled Plasma – Optical Emission Spectroscopy (ICP-OES and also know and ICP-AES).
The scope of this project can be divided in to four sections; first section involved investigating the effects of malonic acid. The study of malonic acid was narrowed to investigating the trend in strength retention. A rapid strength loss was observed initially followed by a much steady decline in the strength. However the continuation of the loss of strength was unmistakable throughout the time period of exposure. Furthermore, temperature can be observed as a facilitating factor in this degradation reaction.
Secondly the corrosive effect of glyoxylic acid on E-glass fibre was studied. This was explored at two different temperatures for two specific time frames using various concentrations of the acid of interest. The influence of this acid on the glass fibre was found out in terms of strength retention and loss of cations from the glass matrix. The mildness of this acid was accentuated by the fact that 70% or more of the strength was retained at all the conditions employed. A minima in strength retention was observed at 2M acid concentration similar to the trends observed in the past (Betz and Jones 2003 and Jones and Chandler 1986). Leaching of cations reflected this trend. The large strength retention could be related to the fewer amounts of Ca and K leached from the glass matrix (Kumosa and Qui, 1997). Similar to malonic acid, an unusually large amount of B was leached out that could be due to the favourable orientation of the anion with the trivalent ions during the complex formation. Yet again temperature was found to enhance the degradation process.
Next the extent of passivation (if any) showed by malonic acid was investigated using E-glass fibre pre-treated in 5M malonic acid and post treated in known corrosive acids hydrochloric acid and oxalic acid. Passivation of malonic acid was put to test through examination of strength retention of the fibres under these conditions. This segment was carried out as an extension of a finding (a behaviour synonymous to passivation) shown by malonic that surfaced the previous year by the present researcher. Increasing the pre-treatment time showed a great improvement in the retained strength for all the post-treatment acid mediums. Furthermore, while Jones and Betz (2004) featured 20-40% strength retention within a short time frame in 3M HCl, the immense amount of strength retention (60-70%) preceding pre-treatment should definitely be noted. Similarly strength retention of about 80% was observed when post-treated with the severely corrosive oxalic acid. Hence its is clear that passivation can be induced through prolonged pre-treatment in 5M malonic acid that could inhibit the attack of corrosive acid at least for a period of time.
The last fragment of the study focussed on understanding and working out the mechanism behind the reactions between the E-glass fibre and acid medium in terms of kinetics. The acids utilized were 1.5M malonic acid and 3M glyoxylic acid and the assessments were made through the analysis of the weight changes brought about by the acid medium at various temperatures and time frames. In addition leaching patterns of cations were evaluated as this could contribute in achieving the objective. Maximum weight loss reached 4% in glyoxylic acid while that for malonic acid exceeded 20%. The general trend was that the glass fibres lost weight in both acids for a period of time followed by an evident weight gain. Furthermore the weight loss results fit the first order rate law. While the leaching of cations reflects the weight loss for the shorter time frames, steady loss of ions was visible even for the longer time frames where the weight has increased. The weight gain could be explained in terms of binding of anions to certain cations on the glass surface, accounting for the hindrance in the loss of cations at the longer time frames as well. About 50% of weight loss was associated to Ca while 20% was to Al, leaving 6% to B where as the rest of the ions had shown almost insignificant contribution to the weight loss.

A substrate structure rule to predict the enantioselectivity of Candida rugosa lipase (CRL) towards $ alpha$-substituted carboxylic acids is proposed. Lipase from Candida rugosa resolved methyl $ alpha$-substituted phenylacetates -5. These substrates were examined to understand the influence of steric and the electronic nature of the substituents at the chiral center on the enantioselectivity. Crude CRL was partially enantioselective towards substrates -3, and highly selective towards and, E $>$ 100. Partial purification of crude CRL by 2-propanol extraction and separation by an ion exchange chromatography, dramatically improved the enantioselectivity towards -3, E $>$ 100. One main lipase fraction, F$ sb{ rm C}$ was obtained with 58 fold purification and 62% yield. This improvement in enantioselectivity was achieved with a simple dialysis against deionized water or 50% 2-propanol extraction. Lauric acid (10 mM), partially reversed the increase in the enantioselectivity. The absolute configuration of the favored enantiomer for crude and partially purified lipase preparations, was S. Other lipases with opposite stereoselectivities were not identified.
Based on literature and our results, it is believed that the size of the substituents at the stereogenic carbon center can account for the enantioselectivity of CRL catalyzed hydrolysis. The opposite configuration is not preferred when the electronic nature of the medium size substituent is varied. The rule can predict the selectivity data for partially purified CRL preparations. We believe that the accuracy of the rule can be improved if more examples of partially purified CRL reactions are examined.

[11C]Carbon monoxide in low concentrations has been used in palladium- or seleniummediated carbonylation reactions such as the synthesis of 11C-imides, hydrazides, amides, carboxylic acids, esters, carbothioates, ketones and carbamoyl compounds. In these reactions aryl iodides have been used in most cases. However, less reactive aryl triflate, chloride and bromides were activated using tetrabutylammonium iodide. The reactivities of nucleophiles may have influence on the radiochemical yield of the 11Clabelled compounds. Carboxyamination of aryl halides using aniline derivatives yielded 10% of the corresponding 11C-amide. However, the radiochemical yields increased significantly when the aniline derivatives were treated with lithium bis(trimethylsilyl)amide. In contrast, this reagent did not improve the radiochemical yields when primary amines such as methylamine and benzylamine were used. In these cases the radiochemical yields were improved by using pempidine. 11C-Esterification usually gave low yields. However, the radiochemical yields of 11C-esters could be improved by using magnesium bromide and pempidine. An excess of ligand may have a significant impact on palladium-promoted carbonylation reaction. The radiochemical yields of 11C-ketones were improved when using excess amounts of tri-o-tolylphosphine. (13C)Carbon monoxide may be utilized for the synthesis of 13C-substituated compounds in order to confirm the position of 11C-labelling.