Dissertations / Theses on the topic 'Self assembly'
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Fox, Michael Jacob. "Stochastic self-assembly." Thesis, Georgia Institute of Technology, 2010. http://hdl.handle.net/1853/34741.
Full textSpanton, Robert. "Stateful self-assembly." Thesis, University of Southampton, 2013. https://eprints.soton.ac.uk/355888/.
Full textChen, Ho-Lin. "Robust self-assembly /." May be available electronically:, 2007. http://proquest.umi.com/login?COPT=REJTPTU1MTUmSU5UPTAmVkVSPTI=&clientId=12498.
Full textDillenback, Lisa M. Keating Christine Dolan. "Self-assembly and controlled assembly of nanoparticles." [University Park, Pa.] : Pennsylvania State University, 2008. http://etda.libraries.psu.edu/theses/approved/WorldWideIndex/ETD-2613/index.html.
Full textWilliams, Richard James. "Enzyme assisted self-assembly." Thesis, University of Manchester, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.496231.
Full textMayans, Tayadella Enric. "Self-assembly of phenylalanine derivatives." Doctoral thesis, Universitat Politècnica de Catalunya, 2017. http://hdl.handle.net/10803/461917.
Full textEn aquesta tesis, nous homooligopèptids derivats de fenilalanina ha estat sintetitzats per tal d'estudiar la seva capacitat d'autoorganització i examinar la influencia de l'estructura química i les condicions externes. Encara que les interaccions NH3+···-OOC cap-a-cua en els homopèptids desprotegits mostren estabilitzar les estructures peptídiques, s'han introduït funcionalitzacions químiques a través de la incorporació de proteccions a N- i C-, com per exemple, grups bloquejadors aromàtics, grups d'acoblament azida-alquí, l'anió trifluoroacetat o un bloc de polilàctide. Diferents capítols estan dedicats a mostrar que la llargada del bloc d'homopèptid també juga un paper rellevant en l'organització supramolecular dels derivats de fenilalanina. Els resultats publicats evidencien no només el control que exerceixen les característiques de l'ambient sinó també del substrat. Les interaccions pèptid··· pèptid, pèptid···superfície i la rugositat superficial han estat assenyalades com a factors clau que defineixen la forma, les dimensions i l'estabilitat de les estructures jerarquitzades.
Vikramaditya, Barmeshwar. "Micromanipulation using self assembly strategies /." Diss., ON-CAMPUS Access For University of Minnesota, Twin Cities Click on "Connect to Digital Dissertations", 2001. http://www.lib.umn.edu/articles/proquest.phtml.
Full textGutzler, Rico. "Surface-Confined Molecular Self-Assembly." Diss., lmu, 2010. http://nbn-resolving.de/urn:nbn:de:bvb:19-127201.
Full textNellis, Michael. "Self assembly of complex structures." [Tampa, Fla.] : University of South Florida, 2007. http://purl.fcla.edu/usf/dc/et/SFE0002280.
Full textYin, Jinsong. "Self-assembly of ordered nanostructures." Diss., Georgia Institute of Technology, 2000. http://hdl.handle.net/1853/19116.
Full textLi, Lin. "Automated self-assembly programming paradigm." Thesis, University of Nottingham, 2008. http://eprints.nottingham.ac.uk/10468/.
Full textChremos, Alexandros. "Self assembly in soft matter." Thesis, University of Edinburgh, 2009. http://hdl.handle.net/1842/4010.
Full textJahn, S. "Polymer-driven colloidal self-assembly." Thesis, University of Cambridge, 2011. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.605018.
Full textSagar, Rajeeve. "Self-assembly via hydrogen bonding." Thesis, University of Warwick, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.247352.
Full textSchergna, Stefano. "Self assembly of interlocked architectures." Thesis, University of Warwick, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.252501.
Full textRazali, Azaima. "Self assembly in gel systems." Thesis, University of Bristol, 2018. http://hdl.handle.net/1983/77bc44c6-4aed-4548-90f6-4c2f6975e522.
Full textFejer, Szilard. "Self-assembly in complex systems." Thesis, University of Cambridge, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.611771.
Full textLeckie, Joy Susan. "Nanopropulsion by biocatalytic self-assembly." Thesis, University of Strathclyde, 2015. http://oleg.lib.strath.ac.uk:80/R/?func=dbin-jump-full&object_id=25502.
Full textKwiecinski, James Andrew. "Self-assembly in mechanical systems." Thesis, University of Oxford, 2018. http://ora.ox.ac.uk/objects/uuid:a3b521ad-be4a-4152-aaa6-f9a002060c48.
Full textЮщенко, Ольга Володимирівна, Ольга Владимировна Ющенко, Olha Volodymyrivna Yushchenko, Анна Юріївна Бадалян, Анна Юрьевна Бадалян, Anna Yuriivna Badalian, and S. O. Bratash. "A self-assembly of nanoparticles." Thesis, Sumy State University, 2014. http://essuir.sumdu.edu.ua/handle/123456789/39629.
Full textFalk, Martin Jin-teng. "Self-assembly of biological heteropolymers." Thesis, Massachusetts Institute of Technology, 2020. https://hdl.handle.net/1721.1/128325.
Full textCataloged from PDF version of thesis.
Includes bibliographical references (pages 115-122).
In this thesis, we are primarily concerned with understanding the complicated geometrical and topological structures that polymers can adopt. We first consider this in the context of chromatin, the polymer of DNA and associated proteins. Our experiments and coarse-grained modeling suggest that attractions between heterochromatic regions are central to the separation of the active and inactive genome in nuclei. We adopt a similar strategy of coarse-grained polymer modeling in order to devise a collagen-like scheme for twisting polymers together. We found that such scheme generically includes the presence of defects, which we speculate could be useful in designing hierarchical assemblies of twisted filaments. In order to extend strategies for twisting of filaments to arbitrary braid topologies, we constructed a simple numerical model for a device that manipulates float-attached wires with capillary interactions between the walls of the device and the float. We use this model to rationalize design rules for the device, and to predict the motion of the float in non-trivial geometries. Finally, we study the dynamics of a two-dimensional seven-particle cluster as it relaxes from an extended, polymer-like state. We find that this system rarely reaches its (non-degenerate) global free energy minimum.
by Martin Jin-teng Falk.
Ph. D.
Ph.D. Massachusetts Institute of Technology, Department of Physics
Luhrs, Chris. "Producing reliable nanoscale self-assembly /." May be available electronically:, 2008. http://proquest.umi.com/login?COPT=REJTPTU1MTUmSU5UPTAmVkVSPTI=&clientId=12498.
Full textLi, Xuehe. "Self-assembly, Templation and biomimetics." ScholarWorks@UNO, 2002. http://louisdl.louislibraries.org/u?/NOD,25.
Full textTitle from electronic submission form. Vita. "A dissertation ... in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry"--Dissertation t.p. Includes bibliographical references.
Spiteri, Ludovic. "Self-assembly of dipolar particles." Thesis, Université de Lorraine, 2018. http://www.theses.fr/2018LORR0261/document.
Full textThis thesis covers the self-assembly of dipolar (magnetic/dielectric) particles. These systems are abundant in condensed matter physics (magnetic molecules and nanoparticles, magnetic colloidal particles, magnetotactic bacteria, etc). They also represent a fundamental challenge owing to the both long range and anisotropic nature of the pair interaction. The main objective of this research work is to predict the microstructures of these systems by properly handling the intricate dipole-dipole interaction combined with steric and possibly confinement effects. Understanding and revisiting the interaction of dipolar filaments such as needles or chains made up of dipolar beads is a first important achievement in this thesis. Indeed, the chains are the fundamental building blocks of many dipolar systems especially under applied external magnetic field. Then, the columnar aggregation of dipolar chains is investigated which naturally leads to the study of the bulk dipolar crystals. A new phase is discovered there. The more generic case of helical chains is discussed by considering limiting situations such as straight linear chains and zigzag chains. The association of dipolar chains in two-dimensions forms ribbons then a monolayer with triangular lattice symmetry. The interesting response of such a layer to an imposed perpendicular magnetic is addressed as well. It is demonstrated that rhombicity can be induced that way. Finally, sedimenting paramagnetic particles in a tilted monolayer in presence of a magnetic field are investigated by experiments, theory and simulations. The gravity-mediated ordering is found to be a promising route to elaborate tailored two-dimensional patterns
Spiteri, Ludovic. "Self-assembly of dipolar particles." Electronic Thesis or Diss., Université de Lorraine, 2018. http://www.theses.fr/2018LORR0261.
Full textThis thesis covers the self-assembly of dipolar (magnetic/dielectric) particles. These systems are abundant in condensed matter physics (magnetic molecules and nanoparticles, magnetic colloidal particles, magnetotactic bacteria, etc). They also represent a fundamental challenge owing to the both long range and anisotropic nature of the pair interaction. The main objective of this research work is to predict the microstructures of these systems by properly handling the intricate dipole-dipole interaction combined with steric and possibly confinement effects. Understanding and revisiting the interaction of dipolar filaments such as needles or chains made up of dipolar beads is a first important achievement in this thesis. Indeed, the chains are the fundamental building blocks of many dipolar systems especially under applied external magnetic field. Then, the columnar aggregation of dipolar chains is investigated which naturally leads to the study of the bulk dipolar crystals. A new phase is discovered there. The more generic case of helical chains is discussed by considering limiting situations such as straight linear chains and zigzag chains. The association of dipolar chains in two-dimensions forms ribbons then a monolayer with triangular lattice symmetry. The interesting response of such a layer to an imposed perpendicular magnetic is addressed as well. It is demonstrated that rhombicity can be induced that way. Finally, sedimenting paramagnetic particles in a tilted monolayer in presence of a magnetic field are investigated by experiments, theory and simulations. The gravity-mediated ordering is found to be a promising route to elaborate tailored two-dimensional patterns
Karpenko, Daria. "Self-assembly of Self-similar Structures by Active Tiles." Scholar Commons, 2012. http://scholarcommons.usf.edu/etd/4095.
Full textGuldin, Stefan. "Inorganic nanoarchitectures by organic self assembly." Thesis, University of Cambridge, 2014. https://www.repository.cam.ac.uk/handle/1810/245290.
Full textMontgomery, Caroline Beryl. "The self-assembly of diphenylalanine fibres." Thesis, University of Warwick, 2015. http://wrap.warwick.ac.uk/77370/.
Full textVigier-Carriere, Cécile. "Surface assisted self-assembly of peptides." Thesis, Strasbourg, 2016. http://www.theses.fr/2016STRAE013/document.
Full textSince the middle of the last century, the functionalization of surfaces has emerged as a convenient method to control interactions between a material and its surrounding environment. This recent research field paves the way to the design of surfaces bearing original “smart” functionalities. Herein, we present the design and control of peptide self-assembly taking place exclusively at or near a surface in response to an enzymatic stimulus. The localized enzyme-assisted self-assembly (LEASA) of peptides led to the growth of micrometric hydrogels from the surface. The enzymatic surface was obtained by adsorption of specific enzymes using the layer-by-layer method. In a first strategy, we developed the growth of fibrillary networks resulting from the accumulation of oligopeptides (KL)nOEt produced from a confined enzymatic layer of α-chymotrypsine at the interface. This process of gelation was tuned in time (lag time) by controlling the peptide KLOEt concentration and the enzymatic surface density. In a second strategy, alkaline phosphatase was embedded into a multilayer film to obtain a bioactive surface on which a seed-layer, i.e a poly(acrylic acid) covalently modified with a hydrogelator peptide, was adsorbed. This layer allows to control the self-assembly of the fiber network by changing the peptide density anchored on the seed layer. When this bioactive and seeding film is brought into contact with the peptide substrate, i.e. Fmoc-FFY(PO42-), of alkaline phosphatase, an efficient self-assembly of Fmoc-FFY is obtained leading to nanofibers growing from the surface. We demonstrated that an enzymatic precursor film or a more sophisticated bioactive seeding layer can self-instruct the self-assembly of small peptides sequences and influence buildup of a micrometric hydrogel from the surface
Hall, Jeffrey Ronald. "The self-assembly of metallosupramolecular architectures." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1996. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp04/MQ30907.pdf.
Full textSolomon, Matthew Daniel. "Laterally driven self-assembly of microstructures." Thesis, Imperial College London, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.272242.
Full textCheng, S. "Improved nanofiltration membranes by self-assembly." Thesis, Swansea University, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.636243.
Full textCarew, Daniel B. "Self-assembly of soft nanostructured materials." Thesis, University of Bristol, 2011. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.664972.
Full textYoung, Michael Christopher. "Self-Assembly of Functionalized Supramolecular Structures." Thesis, University of California, Riverside, 2014. http://pqdtopen.proquest.com/#viewpdf?dispub=3644049.
Full textEnzymes are capable of exquisite selectivity in catalysis chemical reactions because of a well-evolved mechanism that binds substrates in internal active sites based on size and shape complementarity. The cavities of these enzymes are decorated with organic or inorganic groups which can promote reactivity once the substrate is non-covalently bound. Synthetic molecular hosts to date have been able to bind to substrates in a similar, biomimetic fashion, but functionalized molecular hosts are still virtually unknown.
One convenient way to prepare molecular hosts is by the self-assembly of organic coordinating ligands with suitable metal salts. The reversible dative bonds holding these cage structures together allow incorrect products to break apart and reform, favoring creation of the most thermodynamically stable product. This leads to discrete, solution phase cages that can function as cavity-containing hosts. Some of these hosts have shown efficacy as catalysts for pericyclic reactions due to favorable transition states of the bound substrates. These cages, however, fail to orient reactive functional groups into their interiors. Truly biomimetic cages will require modifying traditional self-assembled targets to incorporate these reactive functionalities.
This work explores the self-assembly of metal-organic cages displaying covalent modifications on their interior. Incorporation of unreactive and poorly reactive groups was found to have a significant impact on the outcome of the self-assembly process. Cages with endohedral alcoholic functionality were found to have different binding properties than unfunctionalized analogs. Cages with introverted alcohol groups were also exploited for their ability to self-catalyze reactions on the interior of the hosts. The metal vertices themselves could also be used as functional groups, and showed the ability to sense neutral analytes in hybrid dative/hydrogen bonded self-assemblies.
Syafitri, Niken. "Self-organising assembly using swarm robots." Thesis, University of Southampton, 2018. https://eprints.soton.ac.uk/418969/.
Full textPinto, Vieira Vânia Margarida. "Orthogonal self-assembly of bioactive hydrogels." Thesis, University of York, 2017. http://etheses.whiterose.ac.uk/19305/.
Full textDo, Hyung Wan. "Computation by block copolymer self-assembly." Thesis, Massachusetts Institute of Technology, 2018. http://hdl.handle.net/1721.1/117840.
Full textThis electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.
Cataloged from student-submitted PDF version of thesis.
Includes bibliographical references.
Unconventional computation is a paradigm of computation that uses novel information tokens from natural systems to perform information processing. Using the complexity of physical systems, unconventional computing systems can efficiently solve problems that are difficult to solve classically. In this thesis, we use block copolymer self-assembly, a well-studied phenomenon in polymer science, to develop a new approach to computing by applying directed self-assembly to implement Ising-model-based computing systems in materials. In the first part of the thesis, we investigate directed self-assembly of block copolymer thin films within templates of different polygonal shapes. We define a two-state system based on the two degenerate alignment orientations of the ladder-shaped block copolymer structures formed inside square confinements, and study properties of the two-state system. In the second part of the thesis, we demonstrate an Ising lattice setup for directed self-assembly of block copolymers defined on two-dimensional arrays of posts. We develop an Ising-model-based simulation method that can perform block copolymer pattern prediction and template design. Finally, we design simple Boolean logic gates as a proof-of-concept demonstration of computation.
by Hyung Wan Do.
Ph. D.
Aimon, Nicolas M. "Templated self-assembly of multiferroic nanocomposites." Thesis, Massachusetts Institute of Technology, 2014. http://hdl.handle.net/1721.1/89948.
Full textCataloged from PDF version of thesis.
Includes bibliographical references (pages 133-150).
To respond to the growing demand for smart and connected devices, such as smartphones, tablet PCs arid other mobile hardware, while meeting the needs for increased power efficiency, miniaturization and reduced manufacturing costs, new material solutions need to be considered. These should address the shortcomings of incumbent semiconductor-based technologies which provide a limited number of functionalities, suffer from high power consumption and heat dissipation, and whose conventional planar processing is increasingly complex and resource-intensive. Potential replacement materials include complex oxides, which exhibit interesting physical phenomena such as superconductivity, colossal magnetoresistance and multiferroicity. New functionalities are especially found at interfaces between two oxides, including emergent electronic states like two-dimensional electron gases, enhanced ionic transport and magnetoelectric coupling, among many other. In this this thesis, we focus on self-assembled oxide nanocomposites, which elegantly organize into vertical nanostructures via spontaneous phase-separation, naturally forming numerous such heterointerfaces. These provide a rich playground for studying interfacial effects, which could be used in future devices, and the self-assembly promises cheap arid high throughput manufacturing providing it can be integrated into useful architectures. BiFeO₃-CoFe₂O₄ self-assembled nanocomposites, in particular, have been studied for the magnetoelectric coupling that takes place between the ferrimagnetic spinel phase, which forms discrete vertical pillars, arid the ferroelectric perovskite phase, which forms a matrix that surrounds the spinel pillars. Here, after an in-depth study of the mechanisms responsible for the formation of this self-assembled nanostructure, we develop a templating method enabling the precise control over the morphology of the film, resulting in useful structures for potential devices like magnetoelectric memories and logic devices. To study the structural, magnetic and electrical properties of our samples, a set of experimental and theoretical methods is developed, adapted to the unique requirements of these thin film nanostructures with iicron-scale ordering. Using finite element analysis and micromagnetic modeling, the effect of the strain-mediated magnetoelectic coupling on the magnetic switching of the CoFe₂O₄ nanopillars is predicted. Scanning Probe Microscopy is also used to characterize the local ferroelectric and magnetic behavior, and observe, for the first time in these templated composites, electrically-induced magnetic switching of the pillar magnetization. The tools and methods developed in this thesis could pave the way towards a wider use of templated self-assembly to leverage the promising properties of oxide heterointerfaces and enable their use in future devices with low manufacturing costs.
by Nicolas M. Airmon.
Ph. D.
Fujii, Jennifer T. (Jennifer Tomiko) 1972. "Multicellular self-assembly on patterned surfaces." Thesis, Massachusetts Institute of Technology, 2000. http://hdl.handle.net/1721.1/8826.
Full textIncludes bibliographical references.
Controlling the spatial distribution of cells in two and three dimensions may be important in the design of advanced tissue engineering scaffolds and other biomedical applications. In this thesis, the concept of biophysical sorting was applied as a method to control the spatial distribution of cells. This approach relies on a self-assembly process that is dependent, in part, on the intrinsic adhesivity of cells. A model system was developed using a simple patterning technique to prepare surfaces with alternating regions that supported variable cell response. First, the influence of certain biophysical parameters that may govern multicellular assembly of a single cell type on patterned surfaces was quantitatively investigated. For surfaces patterned with small features that allow cells to sample surrounding regions through membrane protrusions, it was found that a dynamic equilibrium distribution of cells correlated with differen~es in cell-substratum adhesion strength. The approach to that distribution, however, could be kinetically limited by the inability of the individual cells to sample adjacent areas of the patterned surface. This kinetic limitation was studied on surfaces with increasingly large feature sizes, and found that a simple diffusion model of migration may not completely describe the present system. Other effects such as contact inhibited motility and an induction time for migration may also influence multicellular assembly. The potential of multicellular assembly to simultaneously control the distribution of two cell types was also investigated. First, the multicellular assembly of each cell type was studied in isolation. Co-culture experiments indicated that, in addition to the factors that govern the assembly of a single cell type, sorting of two cell types depended on cell density. Images of high cell density co-cultures suggest that incomplete biophysical separation was achieved.
by Jennifer T. Fujii.
Ph.D.
Au, Hin Meng 1977. "Solder self-assembly for MEMS fabrication." Thesis, Massachusetts Institute of Technology, 2004. http://hdl.handle.net/1721.1/30304.
Full textIncludes bibliographical references (leaves 99-100).
This thesis examines and demonstrates self-assembly of MEMS components on the 25 micron scale onto substrates using the capillary force of solder. This is an order of magnitude smaller than current solder self-assembly in the literature. This thesis also examines self-assembly of high aspect ratio (2:1) microfabricated structures, which poses a greater challenge in terms of alignment and orientation compared to self-assembly of flat structures. The goal of the assembly is to construct a DEP-based cell trap, which consists of sets of high aspect ratio conducting posts on a Pyrex substrate, along with electrical connections to the posts. The posts and substrates are fabricated separately and then combined together through a self-assembly process. The posts are made of silicon and are 25 Im in diameter and 50 plm tall with a thin gold cap on one end to serve as a wetting site. The substrates are Pyrex wafers which are patterned with arrays of binding sites and electrical connections, and selectively coated with a low melting point bismuth solder alloy on the binding sites. Self-assembly of the posts onto the substrate is then driven by the free surface energy minimization of solder when the gold-capped ends of the silicon posts come into contact with the solder bumps. In this project, self-assembly has been successfully demonstrated with a yield of about 50%.
(cont.) However, it also becomes increasingly difficult to control component placement and orientation at these small size scales, because deviations in components and sites from their ideal geometries become relatively pronounced as feature size is reduced. It is observed that post concentration, agitation, and solder wetting of the substrate and posts binding sites are critical for successful assembly. Solder de-wetting, and the peeling of gold caps due to prolonged HF exposure, also limits the yield and the orientation of the assembled posts.
by Hin Meng Au.
S.M.
Bayne, Christopher D. "New directions in dimeric self-assembly." Thesis, Massachusetts Institute of Technology, 1996. http://hdl.handle.net/1721.1/38398.
Full textJacobs, Tia. "Self-assembly of new porous materials." Thesis, Stellenbosch : University of Stellenbosch, 2009. http://hdl.handle.net/10019.1/3970.
Full textENGLISH ABSTRACT: The primary objective of the work was to prepare and investigate new porous materials using the principles of crystal engineering. Both organic and metal-organic systems were studied and the work can best be divided into two separate sections: 1. The crystal engineering of Dianin’s Compound, a well-known organic host. 2. The design and synthesis of a series of related porous coordination compounds consisting of discrete, dinuclear metallocycles. The first section discusses the synthetic modification of Dianin’s compound in order to engineer a new clathrate host with an altered aperture size. Although this study ultimately failed to isolate the host material in its porous guest-free form, the work led to the discovery of a chiral host framework that aligns guest molecules in a polar fashion, and consequently displays non-linear optical properties. These findings are unprecedented in the long history of crystal engineering of Dianin’s compound and its analogues. This section also describes desorption studies of the new inclusion compound, as well as the known thiol analogue of Dianin’s compound. Systematic characterisation of these desorbed phases has raised interesting fundamental questions about desolvation processes in general. The second section constitutes the major portion of the work. A series of related isostructural coordination metallocycles were synthesised and their structure-property relationships were investigated using a variety of complementary techniques. These metallocyclic compounds all crystallise as solvates in their as-synthesised forms, and different results are obtained upon desolvation of the materials. In each case, desolvation occurs as a single-crystal to single-crystal transformation and three new “seemingly nonporous” porous materials were obtained. A single-crystal diffraction study under various pressures of acetylene and carbon dioxide was conducted for one of the porous metallocycles. This enabled the systematic study of the host deformation with increasing equilibrium pressure (i.e. with increasing guest occupancy). The observed differences in the sorption behaviour for acetylene and carbon dioxide are discussed and rationalised. Gravimetric gas sorption isotherms were also recorded for the three different porous materials and the diffusion of bulkier molecules through the host was also investigated structurally. Finally, a possible gas transport mechanism is postulated for this type of porous material (i.e. seemingly nonporous), and this is supported by thermodynamic and kinetic studies, as well as molecular mechanics and statistical mechanics simulations.
AFRIKAANSE OPSOMMING: Die primêre doel van die werk was om nuwe poreuse materiale te berei en deur die toepassing van beginsels van kristalmanipulasie (E. crystal engineering) te ondersoek. Beide organiese- en metaal-organiese sisteme is bestudeer en die werk kan in twee kategorieë verdeel word: 1. Die kristalmanipulasie van Dianin se verbinding, ’n bekende organiese gasheer. 2. Die ontwerp en sintese van ’n reeks verwante poreuse koördinasieverbindings wat uit diskrete, binukleêre metallosiklieseverbindings bestaan. Die eerste deel handel oor die sintetiese verandering van Dianin se verbinding om ’n nuwe klatraatgasheer met ’n veranderde spleetgrootte te vorm. Alhoewel hierdie studie nie daarin geslaag het om die gasheer in sy poreuse “gas(E. guest)-vrye” vorm te isoleer nie, het die werk ’n nuwe chirale gasheerraamwerk aan die lig gebring. Die chirale gasheerraamwerk rig gas(E. guest)molekules in eendimensionele kolomme op ’n polêre wyse en gevolglik vertoon die materiaal nie-linieêre optiese eienskappe. Hierdie resultaat is ongekend in die lang geskiedenis van kristalmanipulasie van Dianin se verbindings en sy analoë. Hierdie afdeling beskryf ook die desorpsiestudies van die nuwe gasheer, en die tiol-afgeleide van Dianin se verbinding. Die sistematiese karakterisering van hierdie fases na desorpsie het fundamentale vrae na vore gebring oor desorpsieprosesse oor die algmeen. Die tweede afdeling maak die grootste gedeelte van die werk uit. ’n Reeks verwante isostrukturele ringvormige koördinasieverbindings is gesintetiseer en hul struktuureienskap verhoudings is deur ’n verskeidenheid komplementêre tegnieke ondersoek. Hierdie metallosiklieseverbindings kristalliseer almal in gesolveerde toestand vanaf sintese en verskillende resultate word verkry wanneer die verbinding desorpsie ondergaan. In alle gevalle vind gas(E. guest)desorpsie as enkel-kristal na enkel-kristal omsettings plaas en drie nuwe ‘oënskynlik nie-poreuse’ poreuse materiale is bekom. ’n Enkelkristal diffraksiestudie onder verskeie gasdrukke is met asetileen en koolstofdioksied uitgevoer vir een van die poreuse metallosiklieseverbindings. Dit het die geleentheid geskep om die mate waartoe die gasheer as gevolg van verhoogde ewewigsdruk vervorm (en dus toename in gasheerbesetting), sistematies te bestudeer. Die waargenome verskille in sorpsie-optrede vir asetileen en koolstofdioksied word bespreek en verklaar. Gravimetriese gassorpsie isoterme is ook vir die drie poreuse materiale verkry en die diffusie van groter molekules deur die gasheer is struktureel ondersoek. Laastens word ’n moontlike gasoordragmeganisme vir hierdie tipe poreuse (i.e. oënskynlik nie-poreuse) materiale gepostuleer. Hierdie bespreking word deur termodinamiese en kinetiese studies aangevul, sowel as molekulêre-meganika en statisties-meganiese studies.
Van, Schalkwyk Welmarie. "Self-assembly of amphiphilic discotic materials." Thesis, Stellenbosch : Stellenbosch University, 2013. http://hdl.handle.net/10019.1/79799.
Full textENGLISH ABSTRACT: The creation of nanometer-scale (nanoscale) materials has fascinated and inspired the scientific community for more than a quarter of a century because of the wide range of applications of these materials, e.g. applications in drug delivery, medicine, tissue engineering, memory storage, display and audio devices, semiconductors, etc. π-Conjugated dendrimers have a proposed flat packing arrangement. An alternating phenyl isoxazole dendrimer system was developed to investigate this phenomenon. The synthesis of this dendritic system was attempted by divergent and convergent approaches. Preparation of the second generation failed because some functional groups inhibited the monomers to react to the first generation. Other examples of nano materials that have attracted a vast amount of interest are the so-called discotic amphiphiles. Discotic amphiphilic molecules have the potential to self-assemble into helical architectures. Discotic systems bearing chiral polar side chains (one and three respectively) were developed. Their self-assembly was investigated in variable concentration and variable solvent composition experiments. These systems did show signs of aggregation in UV-vis and CD spectroscopy experiments. Thread-like helical structures were observed with transmission electron microscopy.
AFRIKAANSE OPSOMMING: Nanometer-skaal materiale inspireer en fassineer wetenskaplikes al vir meer as 25 jaar as gevolg van hulle wye verskeidenheid toepassings bv.: die vervoer van geneesmiddels, weefsel ontwerp, geheue stoorspasie, digitale skerms, klank toerusting, geleiers, ens. π-Gekonjugeerde dendrimere het 'n plat drie dimmensionele rangskikking. 'n Afwisselende feniel isoxazole dendrimer stelsel was ontwikkel om hierdie verskynsel te ondersoek. Die sintese van hierdie dendritiese stelsel is aangepak deur divergerende en konvergerende benaderings. Sintese van die tweede generasie het misluk omdat sommige funksionele groepe die monomere geïnhibeer het om te reageer met die eerste generasie. Ander interessante voorbeelde van nano materiale, is die sogenaamde skyfvormige amphiphiles. Skyfvormige amphiphiles het die potensiaal om spontaan te versamel in heliese strukture. Skyfvormige molekules met chirale polêre sykettings (een en drie onderskeidelik) is ontwikkel. Hulle potensiaal om spontaan te versamel is ondersoek met wisselende konsentrasie en wisselende oplosmiddel samestelling eksperimente. Hierdie stelsels het tekens van versameling gewys in UV-vis en CD-spektroskopiese eksperimente. Staaf-vormige heliese strukture is waargeneem met transmissie-elektronmikroskopie.
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