Thesis (MSc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: The aim of this thesis was to study structure-property relationships in porous materials using various adapted analytical techniques and in-house instruments. The thesis is divided into two sections, and the first section of work constitutes the majority of the thesis. The first section of work deals with the theoretical versus experimental classification of sorption selectivity in porous compounds. A transiently porous metallocycle that can adsorb acetylene and carbon dioxide served as a model host for this experiment. A volumetric sorption instrument had to be constructed to carry out sorption with acetylene. Even though the metallocycle should theoretically be selective for acetylene over carbon dioxide based on single-gas sorption isotherms, this was not the case during the sorption of a mixture of the two gases. Furthermore, high-pressure single-crystal diffraction was carried out utilising an in-house environmental gas cell, and structural elucidation indicated that both acetylene and carbon dioxide coexist in a single cavity of the host. Additional complementary techniques are discussed that were used to confirm that both gases are present in a single host cavity. The techniques included infrared spectroscopy as well as high-pressure florescence and Raman spectroscopy, which had to be conducted with a specially designed pressure vessel and with adapted instrumentation. Finally, density functional theory calculations were employed to explain how host-guest and guest-guest interactions lead to the change in adsorption selectivity. It is concluded that researchers need to show experimentally that a compound is selective for the adsorption of a specific gas, because theoretical models are not always accurate. The second part of this work focuses on a fundamental study of the structure-property relationships in a porous hydrogen-bonded organic framework. The section starts off by exploring the activation conditions and thermal stability of the framework. This is followed by an exploration of a possible phase transformation or thermal expansion in the framework, but neither of these occurred. Thereafter, an extended study of the framework’s sorption behaviour with various gases is discussed. Then, a structural study of its solvated phase is used to explain the framework’s stability. Finally, a novel analytical method is introduced, and two examples are used to demonstrate why the instrument is useful in the field of supramolecular chemistry. The chapter is concluded by stating the importance these fundamental studies, as well the development of new analytical techniques. / AFRIKAANSE OPSOMMING: Die doel van hierdie tesis was om die struktuur-afhanklike eienskappe van poreuse materiale te ondersoek. Die studie het gebruik gemaak van verskeie aangepasde analitiese metodes asook instrumente wat spesifiek vir die studie gebou was. Die werk word in twee dele verdeel, en die meerderheid van die tesis word in die eerste deel bevat. In die eerste deel van die tesis word die validiteit van teoretiese- teen eksperimentele adsorpsie selektiwiteit opgeweeg. ʼn Gasheer wat bestaan uit ringvormige koördinasie-verbindings en wat asetileen asook koolstof dioksied kan adsorbeer, dien as ʼn model gasheer vir die studie. ʼn Volumetriese sorpsie instrument was spesiaal vir die studie gebou sodat asetileen sorpsie gedoen kon word. Volgens asetileen en koolstof dioksied se enkel-gas adsorpsie isoterme moet asetileen teoreties met voorkeur geadsorbeer word gedurende ʼn adsorpsie eksperiment waarin beide gasse teenwoordig is, maar eksperimenteel was dit bepaal dat dit nie so is nie, dus is daar ʼn verandering in die gasheer se adsorpsie selektiwiteit. Hierna word strukturele data van die gasheer, onder ʼn hoë druk van die gas mengsel, versamel deur gebruik te maak van enkel-kristal diffraksie en ʼn spesiaal-gemaakde gas sel. Die strukturele data toon dat beide asetileen en koolstof dioksied teenwoordig is binne elke porie van die gasheer. Daar word dan van addisionele analitiese metodes gebruik te maak om die observasie te bevestig. Die analitiese metodes sluit in infrarooi spektroskopie asook hoë-druk fluoressensie en Raman spektroskopie wat geëis het dat ʼn spesiale druk-bestande monster houer gebou moes word en dat analitiese instrumente gemodifiseer moet word. Ten slotte was daar van “density functional theory” gebruik gemaak om te verduidelik dat die interaksie tussen die gasheer en gas sowel as die interaksie tussen twee gasse lei tot die verandering in adsorpsie selektiwiteit. Uit hierdie bevinding word die gevolgtrekking gemaak dat navorsers met meer eksperimentele data vorendag sal moet kom voordat ʼn gevolgtrekking gemaak kan word dat ʼn raamwerk selektief een gas adsorbeer. Die tweede afdeling van die werk fokus op ʼn fundamentele studie van die struktuur-afhanklike eienskappe van ʼn poreuse waterstof-verbinde organies raamwerk. Die afdeling begin deur ʼn ondersoek van die aktivering kondisies sowel as die temperatuur-afhanklike stabiliteit van die raamwerk. Dit word gevolg deur te soek na moontlike fase veranderings of temperatuur-afhanklike uitsetting van die raamwerk, maar nie een van die twee eienskappe word waargeneem nie. Daarna word die deeglike ondersoek van die raamwerk se adsorpsie vermoë met verskeie gasse bespreek. Dit word gevolg deur ʼn strukturele studie van die solvaat van die raamwerk, wat dan gebruik word om die stabiliteit van die raamwerk te verduidelik. Ten slotte word ʼn analitiese metode bekend gestel, en twee voorbeelde word gebruik om te wys hoe nuttig die metode is om ʼn kombinasie van resultate te bekom. Die hoofstuk word saamgevat deur te verduidelik hoekom dit belangrik is om hierdie tipe fundamentele studies te doen asook waarom nuwe analitiese metodes ontwerp moet word.

This study reports on investigation of ways of improving the breeding programme for growth-related traits in common carp in Vietnam. The base population was synthesized following a single pair mating scheme from six carp stocks: (1) 2nd generation of family selection; (2) Hungarian 6th generation of mass selection; (3) Hungarian scaled carp; (4) Indonesian yellow 6th generation of mass selection; (5) Indonesian yellow carp; and (6) Vietnamese 6th generation of mass selection. The next two selected generations were produced using a partial factorial mating scheme, with each family being split and reared using communal early rearing (CER) or separate early rearing (SER) methods. The second generation (G2) was produced from selected fish from the CER G1 group. The total number of selection, control and reference families was 135 in the G1 and 101 in the G2 respectively. The control and reference (Hungarian P33 line) families were produced by single pair mating (reference families with the G2 only). Seven microsatellite loci were used for parentage assignment in the CER groups: 96.8% of the offspring (1284 individuals) and 96.2% offspring (1341 individuals) were unambiguously assigned to 113 families (selection, control) in the G1 and 99 families (selection, control and reference) in the G2 generations, respectively. Restricted maximum likelihood in the individual model was used to estimate phenotypic and genetic parameters. In CER, the estimated heritability values of common carp were from 0.20 ± 0.04 to 0.29 ± 0.05 for both weight and length at final harvest, indicating substantial additive genetic variation for selection on growth-related traits. The overall obtained maternal and common environmental effects were consistently close to zero. The average of direct response to selection for body weight was 15.0% per generation. In SER, the number of families in the G1 and G2 were 135 (selection and control) and 101 (selection, control and reference), respectively. The heritability estimates were from 0.20 ± 0.07 to 0.31 ± 0.08 at final measurement. Common environmental (full-sib family) effect were all lower at tagging and slightly higher at last measurement, ranging from 0.05 to 0.22. The response in each generation of selection as the difference between the selection and control lines was 8.1% on average for weight at final harvest, lower than under CER. The high genetic correlations of growth-related traits between the third (one year old, mature) and second (7 months old) measurements could allow selection to be based on the earlier assessment, reducing handling stress close to spawning. The benefits of using microsatellite markers to ascertain parentage, achieve greater growth rate (close to farming systems), shorten time to maturity and selection, and the overall relative merits of using CER v’s SER in this genetic improvement programme are discussed.

This thesis proposes a metallic hole array of a rectangular converging-diverging channel (RCDC) shape with extraordinary transmission. We use a three-dimensional (3D) finite element method to analyze the transmission characteristics of two-dimensional metallic hole arrays (2D-MHA) with RCDC. For a straight channel MHA, when the aperture size is reduced, the transmission peaks have a blue-shift. The same result is observed for a smaller gap throat for the RCDC structure. For the rectangular holes with a high length-width ratio, a similar blue-shift in the transmission peaks as well as a narrower full width at half maximum (FWHM) are observed. The asymmetry from the rectangular shape gives this structure high selectivity for light with different polarizations. Furthermore, the RCDC shape gives extra degrees of geometrical variables to 2D-MHA for tuning the location of the transmission peak and FWHM. The tunable transmission property of this structure shows promise for applications in tunable filters, photonic circuits, and biosensors. / text

A promising approach investigated here is to utilize thin film multilayer structures where the thickness of a catalyst layer at an exposed edge of photolithographically defined pattern determines the diameter of the nanotubes/nanowires grown from it. This can in turn be incorporated into photolithographically defined post structures resulting in an array of suspended nanowires for line-of-site shadow lithography. Success of the diameter control approach has been shown by selectively growing carbon nanotubes (CNTs) from narrow lines (12-60 nm) of SiO2, Fe, Ni, Co on micron-scale patterned substrates in a ferrocene or nonferrocene catalyzed CVD process. In addition, the concept has been extended to VS growth of CuO nanowires and VLS growth of ZnO nanowires from an exposed edge in a Al2O3/Cu(40-100 nm)/Al2O3 and Al2O3/Au(10 nm)/Al2O3 thin film multilayer structures. The exposed middle layer of patterned thin-film multilayer acts as a nm-scale wide selective growth area. The resultant CNT/nanowire diameter is directly related to the catalyst/catalyst support size. Growth kinetic studies of CuO nanowires from a thin film multilayer structure indicate diffusion controlled process. Dispersion of CNTs between lithographically defined trenches of width of 200 nm and depth of 500 nm when coupled with line-of-site deposition resulted in nm-scale line underneath the suspended CNT. The width of the resulting shadow is nearly a simple function of CNT/nanowire diameter, incident evaporation angle, and height of CNT above the substrate in a line-of-site evaporation geometry. Another promising approach to control the placement of nanotubes/nanowires is the selective functionalization of only their tips followed by selfassembly onto chemically patterned substrates. Towards this goal, arrays of aligned CNTs were impregnated with polystyrene to form aligned CNT membranes. These CNT membranes were also studied for gas and ionic transport studies. Different functionalization chemistry was performed on each side of the membrane. After dissolution of polymer matrix, a suspension of CNTs with different functionality at each tip was formed, allowing for sophisticated selfassembled architectures.

The current project examined the ability of a novel series of guandine and amidine-containing nicotine analogs to interact with several native and recombinantlyexpressed mammalian neuronal nicotinic-acetylcholine receptor (nAChR) subtypes. Rational drug design methods and parallel organic synthesis was used to generate a library of guanidine-containing nicotine (NIC) analogs (AH compounds). A smaller series of amidine-containing nicotine analogs (JC compounds) were also synthesized. In total, >150 compounds were examined. Compounds were first assayed for affinity in a high-throughput [3H]epibatidine radioligand-binding screen. Lead compounds were evaluated in subtype-selective binding experiments to probe for affinity at the α4β2* and α7* neuronal nAChRs. Several compounds were identified which possess affinity and selectivity for the α4β2* subtype [AH-132 (Ki=27nm) and JC-3-9 (Ki=11nM)]. Schild analysis of binding suggests a complex one-site binding interaction at the desensitized high-affinity nAChR. Whole-cell functional fluorescence (FLIPR) assays revealed mixed subtype pharmacology. AH-compounds were identified which act as activators and inhibitors at nAChR subtypes, while lead JC-compounds were found which possess full agonist activity at α4β2* and α3β4* subtypes. Compounds were identified as partial agonists, full agonists and inhibitors of multiple nAChR subtypes. Several SAR-based, ligand-receptor pharmacophore models were developed to guide future ligand design. Second-generation lead compounds were identified.

Nitrogen oxides (NOx) are atmospheric pollutants that pose a serious threat to both the environment and human health. Although catalytic deNOx technologies for engines working under stoichiometric air-to-fuel ratios (i.e., most gasoline engines) are already available, their performance is unsatisfactory under excess air conditions like those under which diesel engines operate. The selective catalytic reduction of NOx with hydrocarbon reductants (HC-SCR) is a potential deNOxsolution for diesel engines, whose operating temperatures are 150-500 ºC. Given that is unlikely for a single catalyst to show acceptable activity throughout this entire temperature span, the use of two catalysts is proposed in this dissertation. Whereas several catalysts active at high temperatures (>300 ºC) are already available, a catalyst showing an acceptable performance at low temperatures (<300 ºC) is yet to be found. Platinum group metals (PGMs) supported on activated carbon have been identified as promising low temperature HC-SCR catalysts. However, these materials show three main drawbacks: 1) the propensity of the carbon support to undergo combustion in an oxidizing environment, 2) a narrow temperature window of operation; and 3) a high selectivity towards N2O (as opposed to N2). To address the first limitation, the use of multi-walled carbon nanotubes (MWCNTs) as the support has been investigated and found to yield catalysts displaying a higher resistance to oxidation. Further, the acid activation of MWCNTs prior to their use as catalyst support has been explored, following reports than link carrier acidity with improved catalyst performance. In turn, the use of PGM alloys as the active phase has been examined as a means to improve catalyst activity and selectivity. Additionally, kinetic, spectroscopic and mechanistic studies have been performed in an attempt to probe structure-activity relationships in the MWCNTs-based formulations showing the best deNOx performance. The fundamental insights gained through these studies may inform further improvements to HC-SCR catalysts. Finally, the synthesis of the most promising formulations has been scaled-up using commercial metal monoliths as the catalyst substrate and the resulting monolithic catalysts have been tested in a diesel engine for activity in the HC-SCR reaction.

One means by which inhibitory control in selective attention may be studied is with the negative priming (NP) procedure. It is widely assumed that children are characterised by reduced capacity for inhibition (Diamond, 2002) and that inhibitory dysfunction is a key characteristic of children and adolescents with ADHD (Barkley, 1997). This should translate into reduced NP effects for these populations. In this dissertation, four studies using the NP procedure find no evidence for reduced inhibitory function in typical children or in adolescents with ADHD. Study 1 examined the magnitude of NP in children compared with adults. An important line of support for the idea that children suffer an inhibitory decrement has been based an empirical report suggesting that conceptual (identity or semantic) NP effects, assumed to reflect the by-product of distractor inhibition, while consistently found in adults are lacking in children (Tipper, Bourque, Anderson, & Brehaut, 1989). In Study 1, the opposite result was found. Study 2 compared NP effects between 7-year-old children and adults while replicating the respective methodologies of the only two studies to explore conceptual NP effects in developmental populations to date (Pritchard & Neumann, 2004, vs. Tipper et al., 1989) to determine the nature of the divergent results between these studies. In Study 2, it was found that distractor inhibition effects are comparable between children and adults when a NP task contains trials in which the distractor stimulus is consistently incongruent with the target stimulus, but that children may be more susceptible than adults to divide attention between target and distractor when a NP task contains a number of trials in which target selection difficulty is reduced. These are critical new findings, highlighting that reduced NP may often relate to methodological artifacts, and when considered in the light of current theories of NP, are also problematic for anti-inhibitory accounts of NP. Having distinguished more definitively the role of inhibition in developmental NP effects, Studies 3 and 4 explored whether the inhibitory process underpinning NP was implicated in young persons with ADHD. To date, evidence for NP in ADHD populations is equivocal. Study 3 found no evidence for a reduced NP effect in ADHD devoid of a corresponding diagnosis. Study 4 found that conduct and oppositional defiant disorders had the potential to confound the evaluation of NP in ADHD. Taken together, results in Studies 1 - 4 parallel very recent results in the literature on NP in older adults and adult psychopathology where presumed reductions of NP in these populations may also be accounted for by methodological artifacts (Buchner & Mayr, in press). It is concluded that NP may reflect a primitive and robust form of inhibitory processing, one that develops early and one that is often the last to deteriorate.

The purpose of this study is to review the lives of three immigrant women from the town of Doctor Mora, Guanajuato, Mexico. The following questions were used to gather and analyze the data: 1) How were their lives prior to migrating to the U.S.? 2) What was their experience crossing the border? 3) What are their life experiences in the U.S.? This study is intended to analyze the history and path of acculturation of these three immigrant women. This study analyzes Alejandro Portes's theory of selective acculturation, concept of funds of knowledge, Gordon's classical theory of assimilation, and the concepts of cultural and social capital. Selective acculturation theory is applied as a basis for analysis of the case studies. These studies were conducted using observational, audio-taped and open ended interviews. This study took place in Tucson, Arizona. Interviews took place in Spanish, the interviews were transcribed, translated, verified and analyzed. Findings show the persistence of these participants to become part of American society through education and involvement in the host society, utilizing their inherent cultural and social capital and supporting the theory of selective acculturation path. The next section gives a more detailed introduction of this study.

Three areas related to Polymer Membrane Ion-Selective Electrodes were investigated. The first two concered (1) their application to analysis of organic cations and pharmaceuticals, and (2) the use of electrochemically polymerized films for potentiometric sensors. The third area focused on the development of a computer controlled data acquisition system for studying Ion Transport at the Interface of Two Immiscible Electrolyte Solutions (ITTIES). Coated wire Polymer Membrane Ion-Selective Electrodes (PMISEs) based on dinonylnapthalenesulfonic acid (DNNS) were prepared for several alkylammonium ions and pharmaceuticals. Selectivity coefficients and other operational characteristics were predictable from calculated distribution constants. Specifically, Log k ᵖᵒᵗ(i)(j) values increased linearly with carbon number in a homologous series of alkylammonium ions. Among cations of the same carbon number, interference increased tenfold with each additional substitution in going from quaternary, tertiary, secondary and primary alkylammonium ions. Addition of hydrophilic subtituent groups to cyclohexylammonium interferents further diminished electrode response. Electrodes for several important pharmaceuticals, namely cocaine, methamphetamine, methadone, protriptyline, cimetidine, lidoflazine, verapamil, acebutalol, diltiazem, and nicardipine, displayed nearly theoretical response down to micromolar concentrations. Their selectivity was consistent with calculated distribution constants. Selectivity was independent of sensitivity, suggesting that the magnitude of each was determined by the distribution of both the free cation and the association complex of this cation with DNNS. The polymerization of phenol derivatives onto copper rendered the resulting films responsive to counter-ions of the electroactive species present in the polymerization medium. Those incorporating Aliquat 336 (tricaprylmethylammonium chloride) showed response to various anions, while others prepared using a sulfonated phenol derivative (m-hydroxybenzenesulfonic acid) responded to tributylammonium. The films had short lifetimes due to poor adhesion to the copper substrate. Construction of a computer controlled data acquisition system provided a rapid method for obtaining electrocapillary data simultaneously with the current-scan polarogram. The system was evaluated by observation of ion-transfer of a variety of alkylammonium ions.

隨著網路的進步與發展，許多新興的資訊服務，如影音資訊，在網路上傳輸時並未要求封包都送達，不同的封包有不同的重要性，例如 MPEG的關鍵畫面(I -Frame)就比其他畫面重要。常用的傳輸層通訊協定中，UDP與TCP都對所有的封包一視同仁，前者不做任何保證，而後者雖可保證所有封包的送達，但效率較差。 本研究提出一個新的TCP，”Partial-Reliable TCP”，使用選擇性重傳機制，配合應用程式的需求，對指定的封包提供遞送保護。當封包遺失時，只重傳保護的封包，可減少額外的網路資源消耗，並提升服務的品質。 此外，我們提出Single-Side的版本，接收端可以使用一般的 TCP，在封包傳送時，讓接收端以為封包都是無誤傳達的，在server-client架構的網路服務中，只有伺服器端必須使用我們的Partial-Reliable TCP，大幅提高本通訊協定的可行性。 最後我們利用網路模擬工具NS-2來模擬實際網路環境，將我們的方法與現行的通訊協定在可解畫面封包數、PSNR值及額外耗用的網路資源三個參數做比較。我們使用兩個 Video 影像作為傳輸標的，在高遺失率的有線與無線網路的環境中進行實驗。當傳輸時間限制很短時，（例如影像會議的應用），在有線的環境中， Basic PR-TCP比TCP Reno、TFRC最少增加約18%的可解畫面封包數，比UDP、TFRC及TCP Reno的PSNR值最少高出約15%，比TCP Reno及TFRC最少節省了12%的頻寬資源，Single-Side PR-TCP比Basic PR-TCP的PSNR值約低了11%，額外耗用的頻寬約多出10%。在無線的環境中，Basic PR-TCP比TCP Reno、TFRC最少增加約19%的可解畫面封包數，比UDP、TFRC及TCP Reno的PSNR值最少高出約20%，比Single-Side PR-TCP、TCP Reno及TFRC最少節省了15%的頻寬資源，Single-Side PR-TCP比Basic PR-TCP的PSNR值約低了14%。當傳輸時間限制較充裕時 (例如VoD應用)，Basic PR-TCP雖然比TCP Reno及TFRC降低了約3%的PSNR值，但是最少能節省8%的頻寬耗費，Single-Side PR-TCP的PSNR值跟Basic PR-TCP相近，但是額外耗用約5%的頻寬資源。 / With the advance of computer and communication networks, many new information services over IP-based networks such as video streaming and VoIP (Voice over IP) are growing rapidly. These services can tolerate some packets lost in transmission without too much damage to their quality. The content carried in the packets of these services is not equally important in their replay processes. For example, key frames (e.g. I-Frames) of a video encoded in MPEG format are more important than others. The loss of I-frames may have a large impact to the quality of the transmitted video, while the loss of other types of frames may only have nominal damage. Unfortunately, the two most popular transport protocols, UDP and TCP, treat all packets equally without any discrimination. TCP guarantees the delivery of all packets, while UDP doesn't. TCP may waste too much resource to guarantee the delivery of unimportant packets, while UDP may fail to deliver too many important packets. This thesis proposes a new TCP protocol, named Partial-Reliable TCP (PR-TCP), which applies selective retransmission strategy to provide delivery guarantee to the selected packets designated by the application programs. In this way, we can save bandwidth consumption and reduce the average delivery time without significant quality degradation. In fact, if the delivery of an object requires a stringent delivery time, the reduction of average delivery time may also lead to the reduction of abandoned packets at the receiver end. We propose two different versions of PR-TCP, Basic PR-TCP and Single-Side PR-TCP. Basic PR-TCP requires both ends of a connection to adopt PR-TCP while Single-Side PR-TCP only requires the sender end to adopt it. It is much easier to deploy Single-Side PR-TCP on the client-server systems where only servers need to use PR-TCP. Finally, we use NS-2 network simulator to evaluate our PR-TCP against TCP Reno, TFRC and UDP. Two video stream samples are used for video sources. Three quality parameters are evaluated: wasted bandwidth consumption, PSNR, and the number of packets in decodable frames. Under heavy loaded wired network and short delay bound (<0.8 sec.), the simulation shows that Basic PR-TCP can outperform TCP Reno and TFRC in the number of packets in decodable frames by at least 18%. It can outperform TCP Reno, TFRC, and UDP in PSNR by at least 12%. The performance of Single-Side PR-TCP is less then Basic PR-TCP in terms of PSNR by 10%, and it consumes larger bandwidth by 8%. Under wireless environments where error rate is high, the simulation shows that Basic PR-TCP can outperform TCP Reno and TFRC in the number of packets in decodable frames by at least 19% as well as wasted transmission overhead by at least 15%. It can also outperform TCP Reno, TFRC, and UDP in PSNR by at least 20%. The performance of Single-Side PR-TCP is less then Basic PR-TCP in terms of PSNR by 14%, and it consumes larger bandwidth by 10%. Under large delay bound (>8 sec.), the quality (PSNR) of the video transmitted using Basic PR-TCP is downgraded by only 3%, while it can save network bandwidth by 8%. The performance of Single-Side PR-TCP is about the same as Basic PR-TCP in terms of PSNR, but it consumes slightly larger bandwidth by 5%.