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Yes / Measurement of molecular weight is an integral part of macromolecular and polymer characterization which usually has limitations. Herein, we present the use of a bench-top 80 MHz NMR spectrometer for diffusion-ordered spectroscopy as a practical and rapid approach for the determination of molecular weight/size using a novel solvent and polymer-independent universal calibration. / Royal Society. Grant Number: URF∖R1∖180274. Engineering and Physical Sciences Research Council. Grant Numbers: EP/V037943/1, EP/V007688/1, EP/V036211/1

Soluble, thermally stable phosphorus containing polyimides have been synthesized to controlled molecular weights and well-defined phthalimide endgroups via solution imidization. They were characterized by intrinsic viscosity, DSC, TGA, and thermomechanical measurements. Molecular weight control was successful and these polyimides were thermally stable via dynamic TGA up to 500°C. Flame resistance was suggested by the 10-20 % of char yield observed in air at 750°C. Good tensile modulus (500-550 ksi) via stress-strain measurements and excellent adhesion to Ti-6AI-4V substrates through single lap shear tests was demonstrated. Investigations of the effects of molecular weight and end group on thermal and mechanical properties of reactive amine terminated and non-reactive phthalic anhydride terminated PMDA-mBAPPO polyimides were pursued. Polyimides with non-reactive end groups do not crosslink and, hence, were essential for controlled processability. Rheological behavior was investigated with a parallel plate type viscometer and the results confirmed the thermoplastic nature of these systems. Phenyl ethynyl endcapped polyimides were synthesized for a broad based investigation of their processibility and mechanical properties. Thermally stable soluble polyimide oligomers were synthesized via the poly(amic acid) precursor route followed by subsequent solution imidization. These polyimides were successfully crosslinked upon heating, without the evolution of volatile products. The phenyl ethynyl endcapped polymers (T_cure ~ 350-400°C) exhibited a wider processing window above Tg, relative to the unsubstituted acetylene endcapped polymers (T_cure ~ 200°C). Studies of the chemorheological behavior of these polyimides as a function of varying temperatures and times were conducted. This research allows the conclusion that high Tg, thermostable, and solvent resistant new networks suitable for structural adhesives and matrix resins have been identified. This was proven by characterization of these novel networks. Ninety-nine percent gel fraction networks were observed after cure at 380°C for 60 minutes. Thermomechanical properties such as tensile properties, adhesion properties, creep behavior, and heat distortion temperatures have been generated which illustrate the excellent dimensional stability and mechanical properties achievable at optimum crosslink density. Polyarylene ether sulfones were also studied which demonstrated the desirable combination of excellent thermal stability and good mechanical properties. Biphenyl-based polysulfones were synthesized and endcapped with 3-phenyl ethyny] functional groups. High Tg, thermostable, ductile and solvent resistant networks were prepared after curing at 380°C. Thermo-mechanical behavior, including tensile properties and dynamic mechanical analyses have been determined and are reported in this thesis. / Ph. D.

Yes / This study used sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) analysis and a jar test apparatus to investigate the molecular weight (MW) and turbidity removal potential of Hibiscus seeds. Three Hibiscus species were assessed: okra crude extract (OCE), sabdariffa crude extract (SCE), and kenaf crude extract (KCE). Furthermore, purified versions of each [i.e., purified okra protein (POP), purified sabdariffa protein (PSP), and purified kenaf protein (PKP)] obtained from anionic exchange were evaluated. The results show that whereas the crude extracts had multiple proteins with MW sizes between 11 and 82 kDa, the purified samples consisted of a single coagulant protein band around 39 kDa. In each case, significant turbidity removal was recorded with the purified proteins; POP, PSP and PKP achieved approximately 98%, 94%, and 90% removal, respectively, at a reduced dosage of ≤0.6  mg/L. However, OCE and SCE achieved lower turbidity removal of 86% and 85% using 40-mg/L doses, respectively, whereas KCE recorded only 73% turbidity removal with a 60-mg/L dose. Sludge generation by crude and purified proteins was approximately 25% of sludge produced by aluminum sulfate and had the additional benefit of being biodegradable. Therefore, the coagulant protein in Hibiscus plant seeds has potential applications for improvements to accessing clean water in developing countries.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2008. / This study involved (a) the development and testing of a solution turbidity fractionation analyser (TFA) and (b) the investigation of possible molecular weight effects on solution crystallisation. To investigate the latter highly isotactic polypropylene was polymerised with a C2 symmetric metallocene catalyst. Blends were made of these homopolymers. The homopolymers as well as the blends were fractionated by means of temperature rising elution fractionation (TREF). The fractionated and unfractionated homopolymers as well as the fractionated blends were characterised by 13C NMR, differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). The TFA was successfully developed and helped in explaining the shifting of solution crystallisation temperature that was seen when blending of the homopolymers occurred. This was done performing analyses on the machine of blends of the homopolymers. Fractions, of the homopolymers and blends, obtained from TREF were also done. Subsequent runs of blends made from the fractions obtained from TREF were also done. In the end it was shown that the shift of the solution crystallisation temperature is either due to the tacticity or the molecular weight depending on the sample.

Thesis (PhD)--University of Stellenbosch, 2011. / ENGLISH ABSTRACT: The crystallization of polyolefins is an important parameter in determining the properties of such materials. The crystallization phenomenon generally depends on the molecular symmetry (tacticity) and molecular weight of the material. In this study, a series of polypropylenes was prepared using heterogeneous MgCl2-supported Ziegler catalysts with two different external donors, diphenyldimethoxysilane (DPDMS) and methyl-phenyldimethoxysilane (MPDMS), and two different homogeneous metallocene catalysts, racethylene- bis(indenyl) zirconium dichloride, Et(Ind)2ZrCl2 (EI), and rac-ethylene-bis(4,5,6,7- tetrahydro-1-indenyl) zirconium dichloride, Et(H4Ind)2ZrCl2 (EI(4H)). Molecular hydrogen was used as terminating agent. In order to establish a correlation between the molecular weight and the crystallization of these polymers, fractionation of the materials according to crystallizability was performed by means of temperature rising elution fractionation (TREF). This affords the opportunity of blending materials of different molecular weights but similar symmetry. These materials were characterized using various analytical techniques: differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), 13C nuclear magnetic resonance spectroscopy (13C-NMR), high temperature gel permeation chromatography (HT-GPC) and Fourier-transform infrared spectroscopy (FT-IR). DSC was used to study the bulk crystallization of different polypropylene blends, most of which showed only one melting peak. The latter is usually associated with a high degree of cocrystallization. Turbidity analysis of the different polypropylene polymers, obtained using solution crystallization analysis by laser light scattering (SCALLS), provided good crystallization information – similar to that provided by crystallization analysis fractionation (CRYSTAF) and TREF. It was also possible to differentiate between polypropylenes with similar chemical structure but different tacticity and molecular weight. SCALLS results also showed that the blends of different isotactic polypropylene polymers were miscible and cocrystallization had occurred, whereas, the blends of syndiotactic polypropylene and different isotactic polypropylenes were not miscible and some interaction between phases had occurred. Optical microcopy (OM) and scanning electronic microscopy (SEM) were used to study the morphological properties of different isotactic polypropylenes. Results revealed a welldefined and large spherulitic morphology of mixed a1 (disordered) and a2 (ordered) crystal form structures. OM and SEM images also clearly showed an effect of molecular weight and tacticity on the crystal structure of the different polypropylene samples. Finally, various homopolymers and blends were studied to investigate the effect of molecular weight on the mechanical properties of these materials. This was done using microhardness testing and dynamic mechanical analysis. / AFRIKAANSE OPSOMMING: Die kristallisasie van poliolefiene is ‘n belangrike faktor wat die eienskappe van hierdie tipe materiale bepaal. In die algemeen hang kristallisasie af van die molekulêre simmetrie (taktisiteit) en molekulêre massa van die materiaal. ‘n Reeks polipropilene is berei deur gebruik te maak van heterogene MgCl2-ondersteunde Ziegler-kataliste met twee verskillende elektron donors, difenieldimetoksisilaan (DPDMS) en metielfenieldimetoksisilaan (MPDMS), en twee verskillende homogene metalloseenkataliste, rac-etileen-bis(indeniel) sirkoniumdichloried, Et(Ind)2ZrCl2 (EI), en rac-etileen-bis(4,5,6,7-tetrahidro-1-indeniel) sirkoniumdichloried, Et(H4Ind)2ZrCl2 (EI(4H)). Molekulêre waterstof is gebruik as termineringssagent. Ten einde ‘n verband te bepaal tussen die molekulêre massa en kristallisasie van hierdie polimere is hulle gefraksioneer op die basis van hulle kristallisseerbaarheid deur gebruik te maak van temperatuurstyging-elueringsfraksionering (TREF). Deur hierdie tegniek verkry ons materiale van verskillende molekulêre massa maar met dieselfde taktisiteit wat ons kan vermeng. Verskeie tegnieke is gebruik om hierdie materiale te karakteriseer: differensiële skandeerkalorometrie (DSC), wyehoek X-straal diffraksie (WAXS), 13C-kernmagnetiese resonansspektroskopie (13C-KMR), hoë-temperatuur gelpermeasiechromotagrafie (HT-GPC) en Fourier-transform-infrarooispektroskopie (FT-IR). DSC is gebruik om die vaste-toestand kristallisasie van verskeie vermengde polipropilene te bestudeer., en net een smeltpunt is in meeste gevalle waargeneem. Laasgenoemde word gewoonlik verbind met ‘n hoë mate van kokristallisasie. Oplossingkristallisasie analise, dmv laserligverstrooiing (SCALLS), is gebruik om die turbiditeit van die verskillende polipropileen kopolimeervermengings te bepaal. Goeie inligting aangaande die kristallisasie in oplossing – soortgelyk aan dié wat dmv die kristallisasie-analise-fraksioneringstegniek (CRYSTAF) en TREF bepaal is, is verkry. Dit was ook moontlik om te onderskei tussen polipropilene met soortgelyke chemiese strukture maar verskillende taktisiteit en molekulêre massas. SCALLS data het ook getoon dat die vermengings van verskeie isotaktiese polipropileen polimere versoenbaar was en dat kokristallisasie plaasgevind het, terwyl vermengings van sindiotaktiese polipropileen en verskeie isotaktiese polipropilene nie versoenbaar was nie en dat ‘n mate van fase-skeiding plaasgevind het. Optiese mikroskopie (OM) en skandeer-elektronmikroskopie (SEM) is gebruik om die morfologiese eienskappe van verskillende isotaktiese polipropilene te bepaal. Goed gedefineerde en groot sferulitiese morfologie van gemengde a1 (onordelike struktuur) en a2 (ordelike struktuur) kristal-strukture is waargeneem. OM en SEM beelde het ook gewys dat molekulêre massa en taktisiteit ‘n effek het op die kristalstruktuur van die verskillende polipropileenmonsters. Laastens is die meganiese eienskappe van ‘n verskeidenheid homopolimere en vermengde materiale bestudeer, deur gebruik te maak van mikro-hardheid metings en dinamiesmeganiese analise (DMA).

Heparin is a complex mixture of sulfated polysaccharides derived from animals and one of the oldest drugs in use. While an efficacious anticoagulant, heparin is beset by side effects and pharmacokinetic difficulties. Low molecular weight heparins (LMWH) are made by depolymerizing unfractionated heparin (UFH) and present improvements in these areas. However, they still retain a phenomenally high level of complexity due to their polydispersity and the introduction of non-native structural features. This makes the structural characterization LMWHs a daunting task. This work details the development of a novel capillary electrophoretic (CE) method for fingerprinting LMWHs. Since their complexity normally results in a nearly featureless electropherogram, polyalkylamines were used as a resolving agents to yield highly resolved and reproducible fingerprints characteristic of the LMWH being investigated. Linear polyamines of resolved LMWH in a manner dependent on chain length and charge density, while cyclic polyamines were incapable of resolution. Longer length glycosaminoglycans such as UFH and chondroitin sulfate were not successfully fingerprinted as they lacked run to run consistency. Further investigation into the mode of polyamine binding showed that they bound to LMWH via a two site binding model, indicating the presence of specific sites on LMWH that tightly bind polyamines. Upon the saturation of these sites, the polyamines continue to interact via general electrostatic binding. Pentaethylenehexamine was also able to separate the known contaminant oversulfated chondroitin sulfate from UFH. In July of 2010, the US food and drug administration approved a generic for the widely used LMWH enoxaparin, a questionable move due to the difficulties of proving the equivalence of such a complex mixture. A comparison of the brand and generic batches of enoxaparin using the fingerprinting method revealed striking similarities, bolstering the generic’s claim of equivalency and providing a protocol for the evaluation of other biosimilar LMWHs. This is the first work utilizing CE in developing high resolution fingerprints of LMWH. It presents a noteworthy method for quality assessment of LMWH and provides the basis for designing other small molecule probes for the analysis of complex glycosaminoglycans.

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.

Ph.D.,Dept. of Orthopaedic Surgery, Faculty of Health Sciences, University of the Witwatersrand, 2009. / Total hip replacement (THR) is an effective method of treatment for patients with hip disability. The procedure is capable of providing long-term functional improvement with excellent control of pain and restoration of function. Sir J Charnley developed a concept of low friction arthroplasty, which was based on use of ultra-high molecular weight polyethylene acetabular and stainless steel femoral components. The components were attached to bone with the use of polymethylmethacrylate (PMMA) bone cement. This concept has been very successful, and is considered the gold standard of THR. Aseptic loosening of the prosthetic components remains the single most important reason for failure of THRs. Wear to the ultra high molecular weight polyethylene (UHMWPE) acetabular cup is a well-known cause of osteolysis and aseptic loosening of the components. Thus, substantial improvement to the wear resistance of UHMWPE could extend the clinical life span of total hip replacements. In an attempt to reduce polyethylene wear and subsequent osteolysis, a method was developed in the early seventies in South Africa to improve polyethylene quality by means of gamma ray cross-linking. The acetabular cup was irradiated with 100 Kilogray in an acetylene environment, which was used as a cross-linking gas material, resulting in improvement of UHMWPE wear resistance. Influenced by the world trend and with the advent of a ceramic bearing surface, the Project of cross-linking was, to a certain extent, forgotten. Patients followed up in the late 1990s, showed minimal or total absence of wear after 15 years or longer. 3 Based on my preliminary studies, and anticipating the world trend of acceptance of cross- link UHMWPE, the aim of this research is to consolidate the results from the largest long term group of patients with acetylene cross-link UHMWPE, to study polyethylene gamma irradiated in the presence of a cross-linking acetiylene gas and the effects of it, in vitro, using a hip simulator. I was planning to communicate with as many patients as possible from the group operated on from 1977 until 1983 in whom cross-link UHMWPE was used. This group of over thousand patients represents the largest group of patients with cross-linked UHMWPE acetabular components in the world, with the longest clinical follow up of over 20 years on average. The first part of the research is a retrospective study: The goal was to contact as many patients as possible who were operated on during the period 1977 to 1983 when cross-linked polyethylene was used. To qualified for the study each patient had to have an early postoperative and the latest follow up radiograph. The radiological study consisted of the radiological measurement of wear. For this purpose the Hip Analysis Suite program was used. This is a software program designed by Dr John M. Martell from the University of Chicago, which is widely used and internationally accepted for that purpose. Image analysis offers significant improvements in reproducibility and accuracy when compared to manual analysis. 4 The final results were compared with results of polyethylene wear in patients in whom conventional UHMWPE was used. For this comparison only patients with acetabular components made from the same UHMWPE material and from the same supplier were used. The conventional UHMWPE is a component of the gold standard of hip replacement surgery. World-wide published follow up studies of 15 years and longer using conventional UHMWPE were compared to the cross-link UHMWPE group. If revision surgery was indicated for whatever reason in patients in with cross-linked UHMWPE acetabular components, the retrieved prosthesis was analyzed. The analysis consisted of examination of the articular surface of the cross-linked acetabular component for micro wear phenomena using a Scanning Electron Microscope (SEM). In order to perform an objective analysis of the retrieved components, two independent laboratories were used, namely: Peterson Tribology Laboratory, Loma Linda University, California, and Biomechanical Laboratory, Faculty of Engineering, University of Pretoria. The analyses were possible thanks to collaboration with Dr Ian Clark from Peterson Tribology Laboratory and Dr NDL Burger in charge of the Biomechanical Laboratory at the Department of Engineering, University of Pretoria

O polietileno de ultra alto peso molecular (UHMWPE) é um plástico de engenharia que tem várias aplicações atualmente, mormente em áreas específicas da indústria e da medicina. O UHMWPE pode ser utilizado ainda em outras aplicações: defensas portuárias; guias de corrente; revestimentos de caçambas, silos e calhas; engrenagens; buchas; guias de correias e próteses cirúrgicas. Esta gama de aplicações se deve ao fato das excelentes características técnicas que este material possui, como: alta resistência a abrasão, elevada resistência ao impacto, anti-aderência, atóxico, excelente resistência química, baixo peso específico, fácil usinagem e alta resistência a fadiga. Os tipos de polietileno de ultra alto peso molecular (UHMWPE) utilizados neste trabalho foram o UTEC 3041 e UTEC 6541 da Braskem. A reciclabilidade do UHMWPE ganhou interesse, porque a utilização desta matéria-prima na última década cresceu mais de 600%, tornando-se um dos plásticos de engenharia mais utilizados para obtenção de peças usinadas depois da poliamida. Com o crescimento na utilização deste polímero na confecção de peças para maquinários, o seu desperdício tem sido muito grande, porque o resto deste material é desprezado, geralmente não sendo reaproveitado. Este trabalho tem como objetivo reciclar o UHMWPE UTEC 3041 e estudar as propriedades deste material virgem e reciclado e comparar os resultados entre si e com o UHMWPE UTEC 6541, e com estes materiais submetidos a diferentes doses de radiação. / Ultra High Molecular Weight Polyethylene (UHMWPE) is an engineering plastic which has several applications, chiefly, in specific areas of the industry and medicine. UHMWPE can be even for other applications such as: port fenders, current guide, bucket coating, silos and gutters, plugs, pulleys and surgical prosthesis. This range of applications is due to the excellent technical characteristics that this material owns, such as; high resistance to wear, high resistance to impact, anti-adherence, non toxic, excellent chemical resistance, low specific weight, easy mill processing, and high resistance to fatigue. The UHMWPE type used in this work were UTEC 3041 and UTEC 6541 of the Braskem. The recycling process of UHMWPE raised much interest, because the utilization of this rawmaterial grew over 600% in the last decade, becoming one of the most used engineering plastics for attainment of mill processed parts after polyamide. As the utilization of this polymer in the manufacturing of parts for machinery has grown, its waste is very big, because the rest of this material is thrown out, usually not being reused. The goal of this work is to recycle the UHMWPE UTEC 3041 and study the properties of this recycled and virgin material and compare the results between both with these materials submitted to different radiation dose.