The research presented in this thesis includes a detailed investigation into factors influencing ionic conductivity in the crystalline polymer electrolyte PEO₆:LiPF₆. It has previously been shown that preparing PEO₆:LiPF₆ with PEO modified with larger –OC₂H₅ end groups increases ionic conductivity by one order of magnitude [¹],primarily due to disruption of the crystal structure caused by the inclusion of the larger end groups. In this study it is shown that by reducing PEO molecular weight in crystalline PEO₆:LiPF₆ ionic conductivity is also increased. This was attributed to an increasing concentration of polymer chain end regions upon lowering molecular weight resulting in the creation of more defects, as well as possible increases in crystallite size resulting in longer continuous pathways for ion transport. Similar results were observed using both polydispersed and monodispersed PEO to prepare complexes. In addition, it is demonstrated here that ionic conductivity in crystalline polymerelectrolytes is not confined to PEO₆:LiXF₆ (X=P, As, Sb)[²][³] type materials. The structures and ionic conductivity data are reported for a series of new crystalline polymer complexes: the alkali metal electrolytes. They are composed of low molecular weight PEO and different alkali metal hexafluoro salts (Na⁺, K⁺ and Rb⁺), and include the best conductor poly(ethylene oxide)₈:NaAsF₆ discovered to date [⁴], with a conductivity 1.5 orders of magnitude higher than poly(ethylene oxide)₆:LiAsF₆. A new class of solid ion conductor is reported: the crystalline small-molecule electrolytes. Such materials consist of lithium salts dissolved in low molecular weight glyme molecules [CH₃O(CH₂CH₂O)[subscript(n)]CH₃, n=1-12], forming crystalline complexes [⁵][⁶]. These materials are soft solids unlike ceramic electrolytes and unlike polymer electrolytes they are highly crystalline, are of low molecular weight and have no polydispersity. By varying the number of repeat units in the glyme molecule, many complexes may be prepared with a wide variety of structures. Here, ionic conductivity and cation transference number (t₊) data for several such complexes is presented [⁷][⁸][⁹].These complexes have appreciable ionic conductivities for crystalline complexes and their t₊ values vary markedly depending on the glyme molecule utilized. The differences in t₊ values can be directly attributed to differences in their crystal structures. [¹] Staunton, E., Andreev, Y.G. & Bruce, P.G. Factors influencing the conductivity of crystalline polymer electrolytes. Faraday Discussions 134, 143-156 (2007). [²] Gadjourova, Z., Andreev, Y.G., Tunstall, D.P. & Bruce, P.G. Ionic conductivity in crystalline polymer electrolytes. Nature 412, 6846 (2001). [³] Stoeva, Z., Martin-Litas, I., Staunton, I., Andreev, Y.G. & Bruce, B.G. Ionic Conductivity in the Crystalline Polymer Electrolytes PEO₆:LiXF₆, X = P, As, Sb. J. Am. Chem. Soc. 125, 4619-4626(2003). [⁴] Zhang, C., Gamble, S., Ainsworth, D., Slawin, A.M.Z., Andreev, Y.G. & Bruce, P.G. Alkali metal crystalline polymer electrolytes. Nature Materials 8, 580-584 (2009). [⁵] Henderson, W.A., Brooks, N.R., Brennessel, W.W. & Young Jr, V.G. Triglyme-Li⁺ Cation Solvate Structures: Models for Amorphous Concentrated Liquid and Polymer Electrolytes (I). Chem. Mater. 15, 4679-4684 (2003). [⁶] Henderson, W.A., Brooks, N.R. & Young Jr, V.G. Tetraglyme-Li⁺ Cation Solvate Structures: Models for Amorphous Concentrated Liquid and Polymer Electrolytes (II). Chem. Mater. 15, 4685-4690 (2003). [⁷] Zhang, C., Andreev, Y.G. & Bruce, P.G. Crystalline small-molecule electrolytes. Angewandte Chemie, International Edition 46, 2848-2850 (2007). [⁸] Zhang, C., Ainsworth, D., Andreev, Y.G. & Bruce, P.G. Ionic Conductivity in the Solid Glyme Complexes [CH₃O(CH₂CH₂O)[subscript(n)]CH₃]:LiAsF₆ (n = 3,4). J. Am. Chem. Soc. 129, 8700- 8701 (2007). [⁹] Zhang, C., Lilley, S.J., Ainsworth, D., Staunton, E., Andreev, Y.G., Slawin, A.M.Z. & Bruce, P.G. Structure and Conductivity of Small-Molecule Electrolytes [CH₃O(CH₂CH₂O)[subscript(n)]CH₃]:LiAsF₆ (n = 8-12). Chem. Mater. 20, 4039-4044 (2008).

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2011. / ENGLISH ABSTRACT: Positron annihilation lifetime spectroscopy (PALS) is well established as a novel method currently available for the study of polymers at a molecular level because of its sensitivity to the microstructural changes in the polymer matrix. The technique provides unique, but limited, information of the solid state structure – primarily on the nature of the free volume (or unoccupied space) in the polymer due to the less dense packing of polymer chains relative to in other solid materials. In the case of completely homogeneous polymer materials the measurement and interpretation of the positron annihilation parameters is relatively simple. However, in the case of polymers with more complex morphologies the situation becomes less clear. This is due to the possibility of the formation, localization and subsequent annihilation of o-Ps (ortho-positronium) within different areas of the complex morphology. This can result in more than one o-Ps lifetime component being present, and each of the different components corresponds to areas with differing types and amounts of 'open spaces'. In this study a detailed and systematic approach was taken to study the positron annihilation parameters in various semi-crystalline polymers and to correlate these to the chain structure and morphology of the materials. The study focused specifically on polyolefin polymers as these are the most widely used semi-crystalline materials, but more importantly, they offer the possibility to produce a variety of morphological complexity by simple manipulation of the chain structure – while there is essentially no difference in the chemical composition of the materials. The copolymers were selected to study the influence of short-chain branching (amount and length), short-chain branching distribution and tacticity on the morphology, and subsequent positron annihilation lifetime parameters. Three separate topics were addressed. First, preparative temperature rising elution fractionation was used to isolate polymer samples that are homogeneously crystallisable and to produce a series of polymers with differing chain structure and resultant morphologies. Second, additional series were produced by removing specific crystallisable fractions from the bulk materials. Third, the temperature variation of the samples as they approach and go through the crystalline melting point was studied. All the raw positron data were found to be best fitted with a four-component positron annihilation lifetime analysis. The longest lifetime (which is attributed to annihilation of o-Ps in the amorphous phase of the materials) showed systematic variations with the degree and nature of the short-chain branding, tacticity variation, a combination of both short-chain branching and tacticity, and changes in the amorphous phase as a result of heating. The third lifetime component (which is attributed to o-Ps annihilation in or around the crystalline areas of the materials) showed less variation across the sample series. Typically, greater variations were observed in the propylene copolymers than in the ethylene copolymers, which are reflective of the more complex chain structure and corresponding morphology in the propylene copolymer series. Direct evidence for a contribution from the nature of the amorphous phase to the bulk microhardness of the sample was also found. / AFRIKAANSE OPSOMMING: Positronvernietigingsleeftydspektroskopie (PALS) is goed gevestig as ‘n nuwe metode vir die studie van polimere op molekulêrevlak agv die sensitiwiteit van die metode vir mikrostrukturele veranderings in die polimeermatriks. Hierdie tegniek verskaf unieke, maar beperkte, inligting aangaande die vastetoestandstruktuur – veral aangaande die aard van die vryevolume (of onbesette spasie) in die polimeer as gevolg van die minder digte verpakking van polimeerkettings relatief tot in ander vastestowwe. In die geval van volledig homogene polimeriese materiale is die meet en interpretasie van die positronvernietigingsparameters relatief eenvoudig. Maar in die geval van polimere met meer komplekse morfologieë is die situasie minder duidelik. Die rede hiervoor is die moontlikheid vir die formasie, lokalisering en gevolglike vernietiging van o-Ps (orto-positronium) in die verskillende areas van die komplekse morfologie. Dit kan tot gevolg hê dat meer as een o-Ps komponent teenwoordig is en waar elk van die verskillende komponente ooreenstem met areas met verskillende tipes en hoeveelhede 'oop spasies'. In hierdie studie is ‘n sistematiese, in-diepte benadering gebruik om die positronvernietigingsparameters in verskeie semikristallyne polimere te bestudeer en hulle te korreleer met dié van die kettingstruktuur en die morfologieë van die materiale. Hierdie studie het spesifiek gefokus op poliolefiene aangesien hulle die mees algemene semikristallyne materiale is wat gebruik word en, nog meer belangrik, hulle bied die geleentheid om verskeie komplekse morfologieë te lewer dmv eenvoudige manipulasie van die kettingstrukture – terwyl daar basies geen verandering in die chemiesesamestelling van die materiale is nie. Die kopolimere is gekies om die invloed van kort-ketting vertakking (lengte en hoeveelheid), kort-ketting vertakking verspreiding en taktisiteit op die morfologie en vervolgens die positronvernietigingsleeftyd parameters te bestudeer. Drie onderwerpe is aangespreek. Eerstens, preparatiewe temperatuurstygingelueringsfraksionering (prep-TREF) is gebruik om polimeermonsters wat homogeenkristalliseerbaar is te isoleer om sodoende 'n reeks polimere met verskillende kettingstrukture, en gevolglike morfologieë, te lewer. Tweedens, 'n addisionele reekse monsters is berei deur die verwydering van spesifieke kristalliseerbare fraksies vanaf die grootmaatmonsters. Derdens, die temperatuurverandering van die monsters wanneer die monsters naby aan die kristallyne smeltpunt is en wanneer hulle deur die kristallyne smeltpunt gaan is bestudeer. Daar is bevind dat alle rou positrondata ten beste gepas het in 'n vier-komponent positronvernietigingsleeftydanalise. Die langste leeftyd (wat toegeskryf is aan vernietiging van o-Ps in die amorfe fase van die materiaal) het sistematiese variasies getoon met die volgende: hoeveelheid en aard van die kort-kettingvertaking, verandering in taktisiteit, 'n kombinasie van beide kort-kettingvertakking en taktisiteit en veranderings in die amorfiesefase as gevolg van verhitting. Die derde leeftyd komponent (wat toegeskryf is aan die o-Ps vernietiging in of rondom die kristallyne areas van die materiale) het minder variasie in hierdie reeks monsters getoon. Daar is tipies meer variasie waargeneem in die propileenkopolimere as in die etileenkopolimere, wat ’n weerspieëling is van die meer komplekse kettingstruktuur en ooreenstemmende morfologie in die propileenkopolomeerreeks. Direkte bewys vir 'n bydrag van die aard van die amorfe fase tot die grootmaat mikrohardheid van monsters is ook bevind.

Thesis (PhD)--Stellenbosch University, 2001 / ENGLISH ABSTRACT: The eye is that biological instrument which conveys the light of the external world into the inner world of the mind, wherein we receive the miraculous gift of vision. So precious is this gift, that Science must search for ways to keep this portal clear for the flow of light. Indeed, Science is called upon to “make war upon the bloody tyrant, Time.” (Shakespeare W. Sonnet No. 16). For, in the course of ageing, the lens grows cloudy and cataractous. In this battle between Science and Time, we are fortunate to live in an era in which Science is uncovering the molecular basis for the various obstacles to vision. The question arises, whether or not, the ruinous hand of time can be stayed. Due to unrelenting, progressive lens opacification, most of the elderly are destined to be subjected to loss of vision and with passage of time, even blindness. Globally the cataract surgery rate is inadequate to keep pace with the ever growing demand on financial and human resources created by the cataract problem. An immense challenge therefore is directed to primary eye care: “Can cataract be prevented or can its onset at least be postponed?” This laudable ultimate aim can only be achieved once the etiology of cataractogenesis is well understood. This dissertation seeks to examine two previously unrecognized etiological aspects that, if correctly understood and managed, have the potential to achieve preventive ophthalmological goals that may indeed help to stay the ‘ruinous hand of time’. The first aspect deals with the role of lipids and was examined using a study group of dyslipidemic subjects. The first part of the study concluded that dyslipidemic patients develop cortical lens opacities more frequently and at an earlier age than the normal population, and that cortical lens opacities should be regarded as one of the most reliable clinical signs of dyslipidemia. Furthermore, an extremely strong correlation was found to exist between low HDL Cholesterol levels and the development of opacities. Below a HDL-Cholesterol level of 1,5mmol/l, subjects had more than seven-fold higher risk of falling in the lens opacity subgroup than those with HDLCholesterol levels above 1,5mmol/l. An equally strong correlation was demonstrated between high (>5) LDLHDL ratios and the development of lens opacities. Subjects with a LDL:HDL-C ratio below 5 possessed a 2.35 times greater risk of having lenticular opacities than the group with a LDL:HDL-C ratio greater than 5. The prevention or retardation of dyslipidemia associated lens opacities is therefore possible, provided patients with a genetic predisposition are detected early and their blood lipids managed adequately. The second aspect deals with the relationship between age related cataracts and the acetylation status of the individual. This study compellingly submits that the slow acetylator pheno- and genotype may be regarded as a genetic indicator of risk for age related cataract. The ability accurately to classify a patient genotypically and phenotypically, may henceforth be useful in health counseling since, if an individual is identified as being a slow acetylator, additional preventative and precautionary measures may be taken, i.e. the prevention of UVexposure to the eye and caution with the ingestion of xenobiotics like caffeine, commercial dyes, food preservatives, and drugs. Furthermore, such a finding should be taken into account in the long term therapeutic management of glaucoma, with special regard to carbonic anhydrase inhibitors which are sulphonamide-related drugs and totally dependent on the N-acetyltransferase pathway for metabolism. These drugs may accumulate in the slow acetylator over time and exert toxic effects intra-ocularly, conceivably including cataractogenesis. The search for genetic and metabolic mechanisms that may contribute to human cataractogenesis should be pursued with great enthusiasm. This endeavour may help Science to achieve its primary objective, ablate the effects of Time and really aid in preventing cataracts in man. / AFRIKAANSE OPSOMMING: Die wondergawe van visie word vir ons moontlik gemaak deur die oog wat as biologiese instrument die lig van die buitewereld inlaat na die binnewereld van die brein. So kosbaar is hierdie gawe dat die Wetenskap deurgaans moet poog om die poort oop te hou. Inteendeel, die Wetenskap word gemaan deur Shakespeare in sy Sonnet nommer 16 om “oorlog te maak teen die bloeddorstige tiran, Tyd”. Soos ‘n mens ouer word, word die lens dof en ‘n katarak mag vorm. Ten spyte van hierdie stryd tussen ‘Wetenskap’ en ‘Tyd’ leef ons in die gelukkige era waarin die Wetenskap meer en meer leer van die verskeie obstruksies tot visie. Die vraag ontstaan of die rinnewerende hand van ‘Tyd’ gestuit sal kan word. Vanwee ongenaakbare, progressiewe lensvertroebeling is die meeste bejaardes bestem om aan visie verlies, en met verloop van tyd selfs blindheid, te ly. Die wereldwye katarakchirurgie tempo is nie voldoende om by te hou by die immergroeiende finansiele en mannekrag eise wat deur die katarak probleem gestel word nie. Daar word dus ‘n reuse uitdaging aan primere oogsorg gestel naamlik: “Kan katarakte nie eerder voorkom of die aanvang daarvan ten minste uitgestel word nie?” Hierdie prysenswaardige doelwit kan nie bereik word alvorens die etiologie van kataraktogenese goed verstaan word nie. Hierdie tesis ondersoek twee voorheen onerkende etiologiese aspekte wat, indien hulle korrek verstaan en hanteer word, beslis die potensiaal het om die gemelde voorkomende doelwitte te bereik en sekerlik te kan bydrae om die rinnewerende hand van Tyd te stuit. Die eerste aspek spreek die rol van lipiede aan deur te kyk na 'n studiegroep van dislipidemiese persone. Die eerste deel van die studie kom tot die gevolgtrekking dat dislipidemiese pasiente kortikale lens opasiteite meer dikwels en op ‘n vroeer ouderdom ontwikkel as die normale populasie en dat sulke opasiteite beskou moet word as een van die mees betroubare kliniese tekens van dislipidemie. Daar is ook ‘n baie sterk korrelasie gevind tussen lae HDL cholesterol vlakke en die voorkoms van opasiteite. Persone in die studie met ‘n HDL cholesterol vlak laer as 1,5mmol/l het ‘n sewe keer hoer kans gehad om in die lensopasiteit subgroep te val as die met ‘n HDL cholesterol vlak laer as 1,5mmol/l. ‘n Sterk korrelasie tussen ‘n hoe (>5) LDLHDL verhouding en die voorkoms van lens opasiteite is ook gevind. Persone met ‘n LDLHDL verhouding >5 het ‘n 2.35 maal groter risiko gehad om lensopasiteite te he as die met ‘n LDL:HDL verhouding van <5. Die voorkoming of vertraging van dislipiedemie geassosieerde lens opasiteite is dus moontlik, solank persone met ‘n genetiese geneigdheid daartoe vroeg ontdek en hulle bloedlipiede voldoende beheer word. Die tweede deel van die tesis handel oor die verhouding tussen ouderdoms verwante katarakte en die asetilasie status van die individu. Met oortuiging kom hierdie studie tot die gevolgtrekking dat die stadige asetilator fenoen genotipe as 'n genetiese merker vir ouderdoms verwante katarakte beskou moet word. Die vermoe om ‘n individu beide genotipies en fenotipies akkuraat te klassifiseer mag voorts bruikbaar wees in gesondheidsraadgewing. Indien ‘n individu geTdentifiseer is as ‘n stadige asetileerder, kan addisionele voorsorg maatreels getref word soos bv. die voorkoming van blootstelling van die oog aan UV lig sowel as omsigtigheid met die inname van xenobiotika soos kaffei'ene, kleurstowwe, voedsel preserveermiddels en geneesmiddels. Hierdie bevinding moet ook in berekening gebring word in die langtermyn terapeutiese hantering van gloukoom. Die koolsuuranhidrase inhibitore, dikwels gebruik in die behandeling van gloukoom, is sulfonamied-agtige middels en dus totaal afhanklik van die N-asetieltransferase pad vir hulle metabolisme. Hierdie middels kan ophoop in die stadige asetileerder en gegewe genoeg tyd, bes moontlik toksiese intra-okulere effekte tot gevolg he. Die soeke na genetiese en metaboliese meganismes wat mag bydra tot menslike kataraktogenese behoort nagestreef te word met groot entoesiasme. Hierdie strewe mag dalk net vir die 'Wetenskap' bystaan om sy primere mikpunt te bereik, die effek van ‘Tyd’ te neutraliseer en te help om katarakte werklik te voorkom.

published_or_final_version / Anatomy / Doctoral / Doctor of Philosophy

published_or_final_version / Biochemistry / Master / Master of Philosophy

published_or_final_version / Orthopaedics and Traumatology / Master / Master of Philosophy

Geotechnical characterization of crystalline rock is often dependent upon the influence of the rock's fracture system. To test ensemble fracture behavior in situ, a series of cross-hole and single-hole electrical conductivity measurements were made within saturated Oracle granite. The tests were conducted with a point source and a point reference electrode and employed electrode separations ranging from 8 inches to over 100 feet. A volume of rock approximately 50 x 50 x 150 feet was tested (as bounded by the vertical test borings). Analysis of the data in terms of an equivalent homogeneous material showed that the effective electrical conductivity increased with electrode separation. The cross-hole data indicate that the rock can be treated as a non-homogeneous, isotropic material. Further, the spatial variation of measured conductivities along a line can be fit to a fractal model (fractional Brownian motion), implying that the scale-dependence is a result of a fractal process supported by the fracture system. Scale-dependence exists at the upper scale limit of the measurements, hence a classical representative elemental volume was not attained. Two directions were taken to understand the scale-dependence. The rock mass is treated in terms of a disordered material, a continuum with spatially varying conductivity. First, a percolation-based model of a disordered material was examined that relates the conductivity pathways within the rock to the backbone of a critical percolation cluster. Using the field data, a fractal dimension of 2.40 was derived for the dimensionality of the subvolume within the rock that supports current flow. The second approach considers an analytic solution for a non-homogeneous, isotropic material known as the alpha center model (Stefanescu, 1950). This model, an analytic solution for a continuously varying conductivity in three dimensions, is a non-linear transform to Laplace's equation. It is employed over a regular grid of support points as an alternative to spatially discretized (piece-wise continuous) numerical methods. The model is shown to be capable of approximating the scale-dependent behavior of the field tests. Scaling arises as a natural consequence of the disordered electrical structure caused by the fracture system.

Mit wellenlängenabhängigen Messungen der Oberflächenphotospannung (Surface Photovoltage, SPV) lässt sich die Diffusionslänge von Ladungsträgern im Volumen von Siliziumproben messen. Das Ziel der Arbeit war es, mit Hilfe temperatur- und injektionsabhängiger Messungen der Diffusionslänge die Natur rekombinationsaktiver Defekte in kristallinem Silizium zu untersuchen. Im Rahmen der Arbeit wurde eine zu diesem Zwecke geeignete Messanlage sowie die nötigen Mess- und Auswerteprozeduren entwickelt. Die Möglichkeiten und Grenzen der aufgebauten Anlage wurden durch Messungen an gezielt mit Eisen, Kupfer oder Chrom verunreinigten mono- und multikristallinen Siliziumproben bewertet. Es zeigt sich, dass die SPV-Methode in einem jeweils begrenzten Temperatur- und Injektionsbereich bei Vorhandensein dominanter Defekte zur Defekt-Spektroskopie einsetzbar ist. Eine Anwendung fand das Verfahren an industriell relevantem, aufbereitetem metallurgischen Silizium (umg-Si).

In many studies of the side-chain liquid crystalline polymers (SCLCPs) bearing azobenzene mesogens as pendant groups, obtaining the orientation of azobenzene mesogens at a macroscopic scale as well as its control is important, because it impacts many properties related to the cooperative motion characteristic of liquid crystals and the trans-cis photoisomerization of the azobenzene molecules. Various means can be used to align the mesogens in the polymers, including rubbed surface, mechanical stretching or shearing, and electric or magnetic field. In the case of azobenzene-containing SCLCPs, another method consists in using linearly polarized light (LPL) to induce orientation of azobenzene mesogens perpendicular to the polarization direction of the excitation light, and such photoinduced orientation has been the subject of numerous studies. In the first study realized in this thesis (Chapter 1), we carried out the first systematic investigation on the interplay of the mechanically and optically induced orientation of azobenzene mesogens as well as the effect of thermal annealing in a SCLCP and a diblock copolymer comprising two SCLCPs bearing azobenzene and biphenyl mesogens, respectively. Using a supporting-film approach previously developed by our group, a given polymer film can be first stretched in either the nematic or smectic phase to yield orientation of azobenzene mesogens either parallel or perpendicular to the strain direction, then exposed to unpolarized UV light to erase the mechanically induced orientation upon the trans–cis isomerization, followed by linearly polarized visible light for photoinduced reorientation as a result of the cis–trans backisomerization, and finally heated to different LC phases for thermal annealing. Using infrared dichroism to monitor the change in orientation degree, the results of this study have unveiled complex and different orientational behavior and coupling effects for the homopolymer of poly{6-[4-(4-methoxyphenylazo)phenoxy]hexyl methacrylate} (PAzMA) and the diblock copolymer of PAzMA-block- poly{6-[4-(4-cyanophenyl) phenoxy]hexyl methacrylate} (PAzMA-PBiPh). Most notably for the homopolymer, the stretching-induced orientation exerts no memory effect on the photoinduced reorientation, the direction of which is determined by the polarization of the visible light regardless of the mechanically induced orientation direction in the stretched film. Moreover, subsequent thermal annealing in the nematic phase leads to parallel orientation independently of the initial mechanically or photoinduced orientation direction. By contrast, the diblock copolymer displays a strong orientation memory effect. Regardless of the condition used, either for photoinduced reorientation or thermal annealing in the liquid crystalline phase, only the initial stretching-induced perpendicular orientation of azobenzene mesogens can be recovered. The reported findings provide new insight into the different orientation mechanisms, and help understand the important issue of orientation induction and control in azobenzene-containing SCLCPs. The second study presented in this thesis (Chapter 2) deals with supramolecular side-chain liquid crystalline polymers (S-SCLCPs), in which side-group mesogens are linked to the chain backbone through non-covalent interactions such as hydrogen bonding. Little is known about the mechanically induced orientation of mesogens in S-SCLCPs. In contrast to covalent SCLCPs, free-standing, solution-cast thin films of a S-SCLCP, built up with 4-(4’-heptylphenyl) azophenol (7PAP) H-bonded to poly(4-vinyl pyridine) (P4VP), display excellent stretchability. Taking advantage of this finding, we investigated the stretching-induced orientation and the viscoelastic behavior of this S-SCLCP, and the results revealed major differences between supramolecular and covalent SCLCPs. For covalent SCLCPs, the strong coupling between chain backbone and side-group mesogens means that the two constituents can mutually influence each other; the lack of chain entanglements is a manifestation of this coupling effect, which accounts for the difficulty in obtaining freestanding and mechanically stretchable films. Upon elongation of a covalent SCLCP film cast on a supporting film, the mechanical force acts on the coupled polymer backbone and mesogenic side groups, and the latter orients cooperatively and efficiently (high orientation degree), which, in turn, imposes an anisotropic conformation of the chain backbone (low orientation degree). In the case of the S-SCLCP of P4VP-7PAP, the coupling between the side-group mesogens and the chain backbone is much weakened owing to the dynamic dissociation/association of the H-bonds linking the two constituents. The consequence of this decoupling is readily observable from the viscoelastic behavior. The average molecular weight between entanglements is basically unchanged in both the smectic and isotropic phase, and is similar to non-liquid crystalline samples. As a result, the S-SCLCP can easily form freestanding and stretchable films. Furthermore, the stretching induced orientation behavior of P4VP-7PAP is totally different. Stretching in the smectic phase results in a very low degree of orientation of the side-group mesogens even at a large strain (500%), while the orientation of the main chain backbone develops steadily with increasing the strain, much the same way as amorphous polymers. The results imply that upon stretching, the mechanical force is mostly coupled to the polymer backbone and leads to its orientation, while the main chain orientation exerts little effect on orienting the H-bonded mesogenic side groups. This surprising finding is explained by the likelihood that during stretching in the smectic phase (at relatively higher temperatures) the dynamic dissociation of the H-bonds allow the side-group mesogens to be decoupled from the chain backbone and relax quickly. In the third project (Chapter 3), we investigated the shape memory properties of a S-SCLCP prepared by tethering two azobenzene mesogens, namely, 7PAP and 4-(4'-ethoxyphenyl) azophenol (2OPAP), to P4VP through H-bonding. The results revealed that, despite the dynamic nature of the linking H-bonds, the supramolecular SCLCP behaves similarly to covalent SCLCP by exhibiting a two-stage thermally triggered shape recovery process governed by both the glass transition and the LC-isotropic phase transition. The ability for the supramolecular SCLCP to store part of the strain energy above T[subscript g] in the LC phase enables the triple-shape memory property. Moreover, thanks to the azobenzene mesogens used, which can undergo trans-cis photoisomerization, exposure the supramolecular SCLCP to UV light can also trigger the shape recovery process, thus enabling the remote activation and the spatiotemporal control of the shape memory. By measuring the generated contractile force and its removal upon turning on and off the UV light, respectively, on an elongated film under constant strain, it seems that the optically triggered shape recovery stems from a combination of a photothermal effect and an effect of photoplasticization or of an order-disorder phase transition resulting from the trans-cis photoisomerization of azobenzene mesogens.

Doctor of Philosophy / Department of Grain Science and Industry / Yong-Cheng Shi / Starch is the most important source of food energy. However, the information about the metabolic quality of starchy foods is scarce. It is well known that native starches with a B-type X-ray diffraction pattern are more resistant to alpha-amylase digestion than those starches with an A-type X-ray pattern, but the underlying mechanism is not well understood. It is not clear whether the enzyme resistance of B-type starch is due to its B-type crystalline structure or the other structural features in starch granules. The objective of this study was to compare the structure and enzyme digestibility of highly pure A- and B-type starch crystals, and understand the roles of crystalline types in starch digestibility. Highly pure A- and B-type starch crystals were prepared from short linear α-glucans (short-chain amylose) generated from completely debranched waxy starches by manipulating the processing conditions such as starch solids concentration, crystallization temperature and chain length. High concentration, high temperature and short chain length favored the formation of the A-type structure, whereas reverse conditions resulted in the B-type polymorph. Digestion results using a mixture of α-amylase and glucoamylase showed that A-type crystals were more resistant to enzyme digestion than B-type crystals. The A-type crystalline product obtained upon debranching 25% waxy maize starch at 50ºC for 24 h gave 16.6% digestion after 3 h, whereas B-type crystals produced by debranching 5% waxy maize starch at 50ºC for 24 h followed by holding at 25ºC for another 24 h had 38.9% digested after 3 h. The A-type crystals had a higher melting temperature than the B-type crystals as determined by differential scanning calorimetry. Annealing increased the peak melting temperature of the B-type crystals, making it similar to that of the A-type crystals, but did not improve the enzyme resistance. The possible reason for these results was due to more condense packing pattern of double helices in A-type crystallites. It seems that the crystalline types are not the key factor that controls the digestibility of native starch granules. The resistance of native starches with B-type X-ray diffraction pattern is probably attributed to the other structural features in starch granules.