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1
Eryazici, Ibrahim. "SUPRAMOLECULAR CHEMISTRY OF FUNCTIONALIZED TERPYRIDINES." University of Akron / OhioLINK, 2007. http://rave.ohiolink.edu/etdc/view?acc_num=akron1195677178.
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Zhu, Shiying. "Terpyridine-based, Coordination-driven, 2D and 3D Supramolecular Architectures." University of Akron / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=akron1490368620583045.
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Hong, Wei. "Temperature-Dependent Supramolecular Cages Self-Assembled By Tristerpyridine and Transition Metal Ions." University of Akron / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=akron1490352933805703.
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Zheng, Keqin. "Design and Construction of Metallo-Supramolecular Terpyridine Possessing Higher Order Structure." University of Akron / OhioLINK, 2013. http://rave.ohiolink.edu/etdc/view?acc_num=akron1375283764.
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Wu, Xiaolei. "COORDINATION-DRIVEN SELF-ASSEMBLY OF TERPYRIDINE-BASED SUPRAMOLECULES." University of Akron / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=akron1490372164176458.
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Ludlow, James M. III. "Design and Synthesis of Terpyridine based Metallo-Supramolecular Architectures." University of Akron / OhioLINK, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=akron1444989836.
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Yao, Yuchen. "The Construction of Supramolecular Arrays by Coordination Driven Stepwise Self-Assembly of Terpyridine-Based Building Blocks and Transition Metal Ions (Ru2+, Fe2+, Zn2+)." University of Akron / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=akron1490370382150615.
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Yeung, Ching-lam Margaret, and 楊靖琳. "Design and synthesis of luminescent alkynylplatinum (II) terpyridine complexes and their function as optical probes for biomolecules and ions : from self-aggregarion, supramolecular assembly to host-guest chemistry." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2013. http://hdl.handle.net/10722/208590.
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A number of cationic water-soluble alkynylplatinum(II) terpyridine complexes, [Pt(tpy){C≡CCH2OC6H3-(CH2OH)2-3,5}]OTf, [Pt(tBu3tpy){C≡CCH2OC6H3- (CH2OH)2-3,5}]Cl, [Pt(tpy){C≡CCH2OC6H4-(CH2OH)-4}]OTf, [Pt(tpy){C≡CC6H3- (CH2OH)2-3,5}]OTf, [Pt(tpy){C≡CC6H4-(CH2OH)-4}]OTf, [Pt(tpy)(C≡C－C≡CH)]OTf and [Pt(tpy){C≡CC6H4(CH2NMe3)-4}](OTf)2, have been synthesized. Phosphate anion derivatives of polyanionic nature, e.g. adenosine triphosphate and tyrosine-containing phosphopeptide, were employed to investigate the induced supramolecular helical assembly behaviors of several of the water-soluble platinum(II) complexes through the study of their UV-vis absorption, emission and circular dichroism (CD) spectroscopies. The extent of such induced self-aggregation properties has been shown to be dependent on the concentration of substrates and capable of screening their respective structurally similar analogues. Two of the complexes were further explored for their use as label-free detection probes for real-time monitoring of the conversion of these phosphate anion derivatives to their metabolic products catalyzed by several biologically important enzymes. Michaelis-Menten analyses have been performed to determine the kinetic parameters.
Supramolecular self-assembly and disassembly behaviors of water-soluble platinum(II) complexes have also been explored for their sensing applications for biomacromolecules with quantitative analyses based on UV-vis, emission and CD spectral titration studies. Making use of the selective binding affinity of aptamers towards their target substrates, the extent of self-assembly of the platinum(II) complexes in the presence of lysozyme and thrombin, which arose from their electrostatic interactions with the negatively charged aptamers, could be modulated for the quantification of these substrates. The potential applicability of this probing strategy in real biological environment has been assessed. Other than that, CD spectroscopic studies revealed the formation of supramolecular helical assembly of the platinum(II) complexes upon electrostatic interaction with heparin. Such helical conformation of the heparin–complex mixture together with the distribution of the negatively charged functionalities on the heparin have endowed the complex with high differentiating power for screening possible interfering analogues. Insulin has also been employed as a template for inducing the self-assembly of the platinum(II) complex. Changes in negative surface charge distribution on insulin, brought about by its conformational changes upon conversion to insulin amyloid under destabilizing conditions, have resulted in different extent of induced self-assembly of the metal complex. Spectral changes of the platinum(II) complex has provided a convenient monitoring of insulin amyloid formation, with kinetic parameters determined.
A number of platinum(II) complexes with nucleobase-functionalized alkynyl ligands, [Pt(tpy)(C≡CCH2-T-1)]OTf, [Pt(tBu3tpy)(C≡CCH2T-1)]OTf, [Pt(tpy)(C≡C– CH2-A-9)]OTf, [Pt(tpy)(C≡CCH2-C-1)]OTf and [Pt(tpy)(C≡CCH2-G-9)]OTf (T = thymine; A = adenine; C = cytosine; and G = guanine), and amide-functionalized terpyridine ligands, [Pt{tpy–(CONHPh)2}(C≡CPh)]PF6 and [Pt{tpy–(CONHC6H13)2} (C≡CPh)]PF6, have been synthesized. Cation-binding properties of [Pt(tpy)(C≡CCH2-T-1)]OTf have been examined using UV-vis and emission spectroscopies, and ESI-MS. Pronounced selectivity towards Hg2+ ions was obtained due to the formation of thymine–Hg2+–thymine base pair, through which the Pt… Pt interactions were turned on. Such binding mechanism has been confirmed with the use of a control complex [Pt(tBu3tpy)(C≡CCH2T-1)]OTf and resonance light-scattering experiments. Anion-binding properties of the complexes with amide-functionalized terpyridine moieties towards spherical and non-spherical anions have been examined with UV-vis and emission spectral titration studies. Drastic color changes were observed for [Pt{tpy–(CONHC6H13)2} (C≡CPh)]PF6 in acetone upon F– ion addition, which was attributed to the F– ion-induced deprotonation of the amide functionalities.published_or_final_version
Chemistry
Doctoral
Doctor of Philosophy
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Young, Michael Christopher. "Self-Assembly of Functionalized Supramolecular Structures." Thesis, University of California, Riverside, 2014. http://pqdtopen.proquest.com/#viewpdf?dispub=3644049.
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Enzymes 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.
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Iden, Hassan. "From molecular tweezers to metallocavitands : self-assembly and supramolecular chemistry." Thesis, Université Laval, 2014. http://www.theses.ulaval.ca/2014/30840/30840.pdf.
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Ce mémoire décrit la synthèse d’hôtes organiques et organométalliques contenant des motifs riches en électrons, particulièrement le tétrathiafulvalène (TTF), pour la complexation supramoléculaire de fullerènes C60 et C70. Le chapitre 1 est une revue de la littérature qui présente les notions de cavitant, de métallocavitant et des hôtes supramoléculaires. Le chapitre 2 présente les méthodes de caractérisation utilisées dans ce travail. Le chapitre 3 est consacré à une nouvelle méthode de synthèse de pinces moléculaires et des récepteurs tripodaux contenant l’unité riche en électrons (TTF). Les pinces triazoles ont été préparées par chimie « clic » entre l'azoture -TTF et des dérivés benzéniques disubstitués en position 1 et 3 par un acétylène. La réaction de l'azoture-TTF et des 1,3, 5-benzènes trisubstitués a donné des récepteurs tripodaux. L'affinité des hôtes avec les fullerènes C60 et C70 a été étudiée par la méthode optique spectroscopique UV-vis dans quatre solvants différents. La constante d’association la plus élevée a été calculée pour l’hôte 4 dans le chlorobenzène. Cependant, le récepteur tripodal n'a pas montré une affinité importante envers les fullerènes. Le chapitre 4 est consacré à la synthèse des nouveaux metallocavitands de zirconium TTF- Zr3 préparés par la méthode d’agrégation. Un seul hôte a été isolé et caractérisé par la méthode spectroscopique. Dans ce chapitre, nous présentons l'étude des interactions supramoléculaires avec les fullerènes en surveillant la réponse UV-vis à l’addition d’une quantité croissante de fullerènes à la solution contenant l’hôte. Le chapitre 5 décrit la synthèse de nouveaux metallocavitants de Zr3 à partir de la réaction de dichlorure de zirconocène sur l'acide carboxylique. Quatre metallocavitants de Zr3 ont été préparés. Les structures cristallographiques, les propriétés photophysiques et leurs utilisations potentielles en tant que matériaux émissifs bleus ont été présentées. Le chapitre 6 est séparé en trois sections. La première section décrit la synthèse et l’affinité de metallocavitant de tantale (V) avec les fullerènes. La deuxième section illustre la tentative de synthèse d’une librairie de Zr3 en utilisant la réaction de couplage croisée. Enfin, la dernière section présente la synthèse du nouveau metallocavitant de Ta3Carbox obtenu par la méthode d’agrégation à partir de la réaction de Cp*TaMe4 avec de l'acide 4 - iodobenzoïque. La structure est étudiée par rayons X.This thesis described the synthesis of organic and organometallic hosts containing electron rich units in particularly tetrathiafulvalene (TFF) to bind fullerenes C60 and C70. Chapter two illustrates the different analysis techniques used in this thesis. Chapter three described new method for the synthesis of tweezers-like TTF and tripodal TTF molecules in addition to their binding affinity towards fullerenes C60 and C70. The tweezers-like TTF were prepared by click chemistry from azide-TTF and 1,3 substituted benzene. Similarly, the reaction of azide-TTF and 1,3, 5 substituted benzene yielded the tripodal-TTF receptor. The affinity toward fullerenes C60 and C70 were studied in four different solvents. The highest binding constant was calculated for host 4 in chlorobenzene toward fullerene C70. Moreover, solvent dependant behavior was observed with the studied host. However, the tripodal receptor did not showed significant affintity towards fullerenes. Chapter four described the synthesis of new TTF-Zr3 metallocavitand by coordination method; two hosts were isolated and characterized. In this chapter we present the binding study toward fullerenes by monitoring the UV-vis response to increasing amount of fullerenes added to the solution of the host. Chapter five described the synthesis of new Zr3 metallocavitand in one pot reaction from the reaction of zirconocene dichloride with carboxylic acid in aqueous media. Four Zr3 metallocavitand were prepared and the crystallography was presented in addition to the photophysical properties and their potential uses as blue emissive materials. The last chapter is separated into three sections. The first section described our early work on tantalum (V) metallocavitand in addition to their hosting capability toward fullerenes. The second section illustrate the tentative has been committed to the design and synthesis of Zr3 library using cross-coupling reaction in addition to the synthesis of extended Zr3-cinnamate metallocavitand. Lastly, the last section illustrates the synthesis of new Ta3-Carbox achieved by aggregation method from reaction of Cp*TaMe4 with 4-iodobenzoic acid. The single X-ray structure revealed a new structure with trimetallic core comparable to the core observed for tantalum metallocavitand.
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Della, Pia Ada. "Using electrostatic interactions to control supramolecular self-assembly at surfaces." Thesis, University of Warwick, 2014. http://wrap.warwick.ac.uk/60286/.
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This thesis is focused on the links between charge transfer (CT) at metalorganic (MO) interfaces, creation of surface dipoles and two-dimensional supra- molecular assembly. Although several examples can be found in the literature where molecular self-assembly on surfaces was in uenced by the formation of interfacial dipoles, only in a few cases were the results fully rationalised and only a posteriori. The MO interface resulting from the deposition of the molecules used for these studies (chosen for their relevance as building blocks for applications in organic opto-electronic, photovoltaic, or proposed organic spintronics devices) is usually very complex. This is mainly due to the chemical structure of these molecules and to their strong interaction with the substrate. A clear identification of the different fundamental processes (such as CT and formation of interfacial dipoles) is thus highly difficult. The approach followed in this thesis is markedly different: specific molecules were rationally designed and subsequently synthesised in order to obtain model systems where the different parameters could be clearly isolated and identified. The presented work is the result of a close collaboration with other two research groups: the organic synthetic chemistry group of Prof. D. Bonifazi and the theoretical group of Prof. A. De Vita. The study was addressed through a complementary multi-disciplinary theoretical and experimental investigation, including the synthesis of new molecules, the analysis of their self-assembly by scanning tunnelling microscopy and spectroscopy and the use of density functional theory calculations and Monte Carlo simulations for the theoretical modelling of the systems. A balance between omnipresent short-range van der Waals attractive forces and long-range repulsive interactions generated by CT at MO interfaces was found to be responsible for the spontaneous formation of novel classes of supramolecular structures. By selecting different metal substrates and by carefully modifying the molecular species through chemical synthesis, the CT was selectively inhibited or enabled. This strategy represents a new paradigm for predicting and controlling the molecular self-assembly at surfaces. Conversely, the appearance of specific molecular linkage patterns is used to reveal the occurrence of CT and provides a novel means for obtaining crucial information on the electronic properties and the energy level alignment of MO interfaces.
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Riddell, Imogen Anne. "Construction and application of new supramolecular architectures using subcomponent self-assembly." Thesis, University of Cambridge, 2013. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.648239.
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Jacobs, Tia. "Self-assembly of new porous materials." Thesis, Stellenbosch : University of Stellenbosch, 2009. http://hdl.handle.net/10019.1/3970.
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Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2009.ENGLISH 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.
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Yamaguchi, Nori. "Supramolecular Assemblies: Dendrimers, Linear Arrays, and Polypseudorotaxanes." Diss., Virginia Tech, 1999. http://hdl.handle.net/10919/28741.
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The chemistry of the non-covalent bond has developed rapidly over the last few decades. In particular, the successful construction of nanoscale assemblies by non-covalent forces has been described more frequently in the recent literature. This significant progress is largely due to transferring of concepts found in the biological systems (e.g., the tobacco mosaic virus and the DNA double helix) to the area of synthetic chemistry. As an example, the architecture of the double helix, perhaps the most well-known biological self-assembling structure, remarkably demonstrates the ability of biological systems to construct large supramolecules by multiple aggregations of relatively simple building blocks by means of hydrogen bonding. Scientists have begun to employ such synthetic strategy adopted in Nature to construct nanoscale systems.
The use of pseudorotaxane assemblies formed between the suitably sized crown ethers and dipyridinium salts (paraquats) or dibenzylammonium ions is a viable synthetic strategy to construct non-covalent systems because of their selectivity and strong hydrogen bonding ability. We describe the syntheses and characterization of non-covalent assemblies of different sizes and shapes via the pseudorotaxane approach.
A series of dendritic pseudorotaxanes were efficiently prepared from self-assembling complimentary building blocks, namely a triply charged ammonium ion and the 1st, 2nd, and 3rd generations of benzyl ether dendrons bearing dibenzo-24-crown-8 moiety. The wholly complexed self-assembling dendrimers were evidenced by 1H NMR spectroscopy and mass spectrometry.
Linear supramolecular pseudorotaxane polymers were formed with reversible chain extension in solution by self-assembly of two complimentary homoditopic molecules with secondary ammonium ion and dibenzo-24-crown-8 moieties. The fraction of the cyclic dimer and the size of the linear suprastructures were determined in solution by 1H NMR spectroscopy as a function of concentration. Viscosity measurements corroborated the presence of aggregates of large hydrodynamic volume at high concentrations. The solid state samples of the supramolecular polymers, prepared by freeze-drying, were analyzed by DSC and optical microscopy and shown to be distinct from the starting materials and the cyclic dimer. Fibers and films were formed from high concentration solutions, corroborating the polymeric nature of the aggregates. Similarly, polymolecular arrays were formed in solution from a heteroditopic self-complimentary molecule, comprising bis-m-phenylene-32-crown-10 and a paraquat unit.
Side-chain polypseudorotaxanes were prepared from spontaneous association of polymethacrylates bearing dibenzo-24-crown-8 and secondary ammonium ions. The complexation behavior in solution was investigated using 1H NMR spectroscopy. The solid state samples of side-chain polypseudorotaxanes, prepared by freeze-drying, showed noticeable changes in thermal behavior and morphology from the individual components.Ph. D.
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Burd, Caroline Glenn. "Supramolecular block and random copolymers in multifunctional assemblies." Diss., Atlanta, Ga. : Georgia Institute of Technology, 2008. http://hdl.handle.net/1853/24627.
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Thesis (Ph.D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009.Committee Chair: Marcus Weck; Committee Member: Bunz, Uwe; Committee Member: Collard, David; Committee Member: Jones, Christopher; Committee Member: Payne, Christine
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Cui, Lu. "Hydrogen Bonding and Cucurbituril Complexation as Self-Assembly Mechanisms." Scholarly Repository, 2009. http://scholarlyrepository.miami.edu/oa_dissertations/450.
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The supramolecular interactions of small organic molecules with different host molecules are investigated in this dissertation. Additionally, the author also describes the self-assembly mechanisms in hydrogen bonding motif. These studies were carried out by many techniques including, NMR, cyclic voltammetry, steady state voltammetry, mass spectroscopy, UV-visible spectroscopy and fluorescence spectroscopy. Chapter 1 introduces the science of supramolecular chemistry and the background of cucurbiturils, one of the most important host molecules studied in this research work. It describes the structures and binding behaviors of each host molecule. Additionally, the selectivity and binding properties in the host-guest interactions involved cucurbiturils are discussed. Chapter 2 compares the electrochemical properties of cationic and neutral ferrocene derivatives upon addition of cucurbiturils. It is observed that the cationic ferrocene compounds bind to cucurbit[7]uril much stronger compared to the neutral ferrocene compounds. The positive charged side chains favor to interact with cucurbit[7]uril portals and thus stabilize the complexes. Besides, the author describes a simple analytical method to determine the binding constants by a competitive binding with a standard reference compound, cobaltocenium, which is reported to bind strongly to cucurbit[7]uril. Chapter 3 described the research of the pH-dependent binding affinity between cucurbit[7]uril and ferrocene guests. The electrochemical behavior of ferrocene moiety in aqueous solution was investigated by cyclic voltammetry in the presence of cucurbit[7]uril in acidic and basic environment respectively. The protonation and deprotonation processes affect the binding behaviors of the ferrocene residues with cucurbit[7]uril. Chapter 4 describes the synthesis and characterization of a new series of 4-phenyl-pyridinium derivatives. These compounds contain a phenyl-pyridinium residue which is favorable to be bound by cucurbit[8]uril. The 1:1 and 1:2 host-guest binding stoichiometries are both observed by UV-visible spectroscopy. These new compounds can be dimerized encapsulated inside the cucurbit[8]uril portals without being electrochemical reduced. Chapter 5 is a brief introduction into the science of hydrogen bonding. This chapter investigates the application of multiple hydrogen-bonding in supramolecular chemistry extensively. Multiple hydrogen bonds with their directionality and reversibility are of great interest and importance in the design and investigations of well-defined supramolecular assemblies. The potential of hydrogen bonding is limitless and is still developing. Chapter 6 describes the synthesis and photochemical behaviors of a series of ureido-pyrimidione derivatives. All of the DDAA derivatives form stable, non-covalent dimers in non-polar solvents. The dimeric molecular assemblies of these hydrogen bonding motifs in their DDAA pyrimidinedione units are investigated by NMR, X-ray crystallography, fluorescence spectroscopy and computations. Additionally, their hetero-dimerization is well studied by fluorescence spectroscopy. The observation and comparison of fluorescence quenching on the photochemical fluorophore for each compound by ferrocene-DDAA and isopropyl-DDAA reveal the electron transfer process through the quadruple hydrogen bonding motifs.
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White, Claire Michelle. "Ruthenium polypyridyl complexes designed for the non-covalent self-assembly of supramolecular systems." Thesis, University of Bristol, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.265497.
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Eghtesadi, Seyed Ali. "SUPRAMOLECULAR ASSEMBLY OF DENDRITIC POLYIONS INTORESPONSIVE NANOSTRUCTURES." University of Akron / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=akron1522527868518926.
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McKinlay, Robert M. "Design and construction of multicomponent spheroidal assemblies on the nano-scale via the self-assembly approach." Diss., Columbia, Mo. : University of Missouri-Columbia, 2006. http://hdl.handle.net/10355/5881.
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Thesis (Ph. D.)--University of Missouri-Columbia, 2006.The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed Aug. 13, 2007). Vita. Includes bibliographical references.
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Meng, Wenjing. "Metal-organic polyhedra : subcomponent self-assembly, structural properties, host-guest behavior and system chemistry." Thesis, University of Cambridge, 2012. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.610719.
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JIANCHENG, LUO. "CONTROLLING SELF-ASSEMBLY OF MACROIONIC SOLUTIONS VIA NON-COVALENT INTERACTIONS: FROM SUPRAMOLECULAR STRUCTURES TO SELF-RECOGNITION." University of Akron / OhioLINK, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=akron1583331502913712.
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Ivasenko, Oleksandr. "Supramolecular design of hydrogen-bonded architectures via surface self-assembly of carboxylic building blocks." Thesis, McGill University, 2011. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=97007.
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Crystal engineering deals with the design of ordered arrays of molecular building blocks and is of high importance in nanotechnology, electronics and in the pharmaceutical industry. While organic synthesis provides access to a wide range of molecules, control over their intermolecular interactions is the major challenge taken on by crystal engineering. This thesis focuses on the surface self-assembly of carboxylic acids, as a convenient model system to study general factors governing self-assembly. It is a step towards the rational design of materials with desired compositions, morphologies and functionalities.Specifically, this thesis presents a systematic investigation of hydrogen-bonded (H-bonded) assemblies of carboxylic building blocks on surfaces (i.e. 2D crystals), complemented by studies of their assemblies in bulk solid state (i.e. 3D crystals). This work provides new insights into the complex relationship between building block structures, H-bonding synthons and self-assembly outcomes using scanning tunneling microscopy (STM), X-ray diffraction crystallography and quantum-mechanical calculations. Consideration of these insights has resulted in the supramolecular design of novel self-assembled molecular networks (SAMNs), described below.To elucidate the effect of building block structure on self-assembly, architectures formed by cyclic homo-dimers of carboxylic groups (i.e. structures containing the R22(8) synthon) are analyzed. Results are given in the form of case-studies covering formation of H-bonded macrocycles, chains, ladders, rotaxanes, catenanes and various 2D and 3D nets. Similar analyses of other H-bonding carboxylic acid assemblies are used to highlight the most important aspects of the carboxylic group's supramolecular reactivity, as well as the applications thereof.A detailed study of the surface co-assembly of trimesic acid (TMA) with n-alcohols is presented. Investigating this single system allows for the observation of a wide variety of phenomena that were previously only studied separately, and on structurally different systems. This enables relevant comparisons between molecular structure and the many factors governing self-assembly at the liquid-solid interface. The periodicity and fine structure of the TMA-alcohol SAMN is conveniently modulated by varying n-alcohol length and parity, representing an important step towards rational molecular nanopatterning of surfaces using the principles of crystal engineering.Relationships between building block structures and the stability of resulting carboxylic homosynthons (viz. the cyclic dimer R22(8), the trimer R33(12) and the hexamer R66(24)) are established through a combination of empirical observations and quantum-chemical calculations. Thus, formation of specific homosynthons is found to depend strongly upon steric intermolecular interactions, as well as upon the relative packing efficiencies of competing polymorphs. These findings allow explanation of the structure and chiral nature of the self-assembly formed by terthienobenzenetricarboxylic acid (TTBTA). Additionally, the rational design of supramolecular networks formed by the R66(24) homosynthon is demonstrated for the first time, using triethynylbenzenetricarboxylic acid (TEBTA).Finally, porous TMA networks are used as host matrices to control and study the self-assembly of new π-functional guest molecules. Specifically, two semiconducting heterocirculenes (sulflower and selenosulflower) are imaged by STM with sub-molecular resolution, enabling the study of adsorption-desorption dynamics, host-guest interactions, and stable π-π stacking architectures. The latter findings open up the possibility to form multilayers of host-guest architectures with high potential for applications in optoelectronic devices.L'ingénierie des cristaux de solides moléculaires est un domaine en plein essor, combinant de nombreux aspects de la chimie des matériaux. Il est d'une grande importance pour l'électronique, la nanotechnologie ainsi que pour l'industrie pharmaceutique, ou il y a grand besoin de concevoir des réseaux ordonnés de molécules. Alors que la synthèse organique donne accès à un grand éventail de molécules, le contrôle des interactions intermoléculaires entre celles-ci est le défi pris en charge par l'ingénierie des cristaux. Cette thèse se concentre sur l'auto-assemblage d'acides carboxyliques en surface, en utilisant ce dernier comme modèle pour étudier les facteurs généraux gouvernant l'auto-assemblage. Cette étude constitue une étape vers la conception rationnelle de matériaux ayant des compositions, morphologies et fonctionnalités tels que souhaitées.Plus précisément, cette thèse présente une étude systématique de l'assemblage de certains blocs carboxyliques en surface (i.e. des cristaux 2D), complétée par des études de leurs assemblées à l'état solide (i.e. des cristaux 3D). Ce travail apporte un nouvel éclairage sur la relation complexe entre la structures des blocs, des synthons liées par des ponts hydrogènes et l'auto-assemblage final. Cette étude met en oeuvre la microscopie à effet tunnel (STM), la cristallographie par diffraction des rayons-X et des calculs a base de mécanique quantique. La nouvelle compréhension établie par cette étude a permis d'aboutir à la conception de nouveaux réseaux moléculaires auto-assemblees (SAMNs), décrit ci-dessous.Pour élucider l'effet de la structure des blocs sur l'auto-assemblage, les architectures formées par des homo-dimères de groupes carboxyliques (c'est-a-dire par des structures contenant le synthon R22(8)) sont analysées. Les résultats sont donnés sous la forme d'études de cas, portant sur la formation de macrocycles (liées par des ponts hydrogènes), de chaînes, d'échelles, de rotaxanes, de caténanes et de divers filets en 2D et en 3D. Des analyses similaires d'autres ensembles d'acides carboxyliques sont utilisés pour mettre en évidence les aspects les plus importants de la réactivité supramoléculaire du groupe carboxylique, ainsi que de l'utilité de celle-ci.Une étude détaillée du co-assemblage de l'acide trimésique (TMA) avec des n-alcools est présenté. La recherche complétée sur ce système permet l'observation d'un grand éventail de phénomènes n'ayant été qu'étudiés séparément. Entre autre, cela permet des comparaisons pertinentes entre structure moléculaire et les nombreux facteurs qui régissent l'auto-assemblage à l'interface liquide-solide. La structure fine et la périodicité du SAMN TMA-alcool est modulée simplement, en faisant varier la longueur et la parité des n-alcools. Ceci représente une étape importante vers la nanostructurisation rationnelle des surfaces avec des molécules, en utilisant les principes de l'ingénierie des cristaux.Les relations entre les structures des blocs et la stabilité des homosynthons carboxyliques qui en resultent (à savoir le dimère cyclique R22(8), le trimère R33(12) et l'hexamère R66(24)) sont établies par une combinaison d'observations empiriques et de calculs émanant de la chimie quantique. Ainsi, la formation d'homosynthons spécifiques se trouve à dépendre fortement des interactions stériques intermoléculaires, ainsi que de l'efficacité relative des polymorphes qui résultent de l'assemblage. Ces résultats permettent l'explication de la structure et de la nature chirale de l'auto-assemblage formé par l'acide terthienobenzenetricarboxylic (TTBTA). En outre, la conception rationnelle des réseaux supramoléculaires formés par l'homosynthon R66(24) est démontré pour la première fois, a l'aide de l'acide triethynylbenzenetricarboxylic (TEBTA).Enfin, les réseaux poreux TMA sont utilisées comme matrices d'accueil pour contrôler et étudier l'auto-assemblage de nouvelles molécules π-fonctionnelles.
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Naidoo, Venthan B. "The supramolecular chemistry of novel synthetic biomacromolecular assemblies." Thesis, Stellenbosch : Stellenbosch University, 2004. http://hdl.handle.net/10019.1/50196.
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Dissertation (PhD)--Stellenbosch University, 2004ENGLISH ABSTRACT: Over the past decade peptide bola-amphiphiles have been the subject of much attention because of their role as potential models of functionalised membranes and as new generation surfactants. In the quest for new surfactants a peptidomimetic-based approach was used to design a library of novel 'hybrid' bola-amphiphilic peptide surfactants derived from sapecin B and a model symmetrical oligo-glycine bola-amphiphile. The library was divided into different series, each one purpose-built; first, to investigate hierarchal supramolecular architecture and, second, to investigate potential antimicrobial activity. The bola-amphiphiles were synthesised using Fmoc-polyamide based solid phase peptide synthesis and purified via high performance liquid chromatography. The peptide hybrids were characterised using electro spray mass spectrometry, nuclear magnetic resonance, different modes of electron microscopy, Fourier-transform infrared spectroscopy and, in some cases, further studies were done using circular dichroism and bioactivity tests. The model bola-amphiphile suberamide(GGh was synthesised using peptide fragment condensation based on solid phase peptide synthesis. The synthesis is bi-directional (N~C and C~N) and versatile, making it possible to synthesis new dicarboxylic oligopeptide bola-amphiphiles and other analogous compounds. The product, suberarnide(GG)2, was purified using its inherent ability to self-assemble in an acidic solution. Novel asymmetrical bola-amphiphiles composed of dipeptide head groups linked via an aliphatic (I)-amino acid, serving as a hydrocarbon spacer, were also synthesized. Two small libraries of bola-amphiphiles were established - the first involved variation in to-amino acid length and the other variation in the C-terminal amino acid. The bolaamphiphiles were self-assembled in either 0.1% trif1uoroacetic acid or 0.1% triethylamine. Electron microscopy revealed the formation of a variety of higher order supramolecular architectures based on ~-sheet self-assembly. FT-IR spectrometry indicated that interlayer and intralayer hydrogen bond networks, together with strong selfassociation, promoted by the hydrophobic effect and, in certain instances, electrostatic interactions, are responsible for the variety of supramolecular architectures. Variations in the higher order structures can be attributed to amino acid composition, specifically length of m-amino acid, nature of the C-terminal amino acid and the optimised solvent conditions used for the self-assembly process. A third library of novel 'hybrid' bola-amphiphilic peptide surfactants, in which a cationic tripeptide motif from antimicrobial peptides was combined in a hybrid molecule containing a oi-amino acid residue, was established. These bola-amphiphiles displayed potent antimicrobial activity against both Gram-positive and Gram-negative bacteria; the analogues were as active or more active than the leader peptides yet, remarkably, displayed little or no appreciable haemolytic activity. These organopeptide bolaamphiphiles thus demonstrated selective toxicity towards bacteria. The hydrophobicity imparted by the co-amino acid has contrasting effects on haemolysis and antimicrobial activity of the peptide analogues. The other unique feature of these peptides and their analogues is the fact they self-assembled into complex supramolecular architectures, composed primarily of ~-sheets. Their self-assembly is primarily governed by hydrophobic interactions together with inter and intralayer hydrogen bonding. Electron microscopy clearly revealed higher order structures for both peptides and analogues. The generation of higher order supramolecular architecture is dependent on optimisation of ~- sheet self-assembly whereas antimicrobial activity is dependent on the balance between net positive charge and optimum hydrophobicity of the peptide hybrids. This study has demonstrated that it is possible to design hybrid peptide surfactants capable of producing higher order supramolecular architecture and improving the antimicrobial activity whilst reducing the haemolytic effect. The study and design of these versatile 'purpose-built' bio-inspired surfactants heralds a novel approach, one that shows tremendous potential.
AFRIKAANSE OPSOMMING: Die afgelope dekade het bola-amfifiliese peptiede baie aandag geniet weens hulle rolle as potensiële modelle van gefunksionaliseerde membrane en as 'n nuwe generasie surfaktante. In die soeke na nuwe surfaktante is 'n peptiedornimetiese benadering gevolg om 'n biblioteek van nuwe "hibried" bola-amfifiliese peptiedsurfaktante van sapesien B en 'n simmetriese oligoglisien bola-amfifil af te lei. Die biblioteek is in verskillende reekse onderverdeel. Elke reeks is doelmatig vervaardig om ondersoek in te stel na twee aspekte, nl. die rangorde van die supramolekulêre strukture en die potensiële antirnikrobiese aktiwiteit. Fmoc-poliamied gebaseerde soliedefase-peptied-sin-tese is aangewend vir die sintese van die bola-amfifile en hulle is met behulp van hoë doeltreffendheid vloeistofchromatografie gesuiwer. Die peptiedhibriede is gekarakteriseer met behulp van elekrosproei massaspektrometrie, kern-magnetiese resonansie, verskillende modusse elektronrnikroskopie, Fourier-transform infrarooispektrometrie en, in sommige gevalle is verdere studies met sirkulêre dichroïsme en bioaktiwiteitstoetsing uitgevoer. Die bola-amfifilsuberamiedtflfij--model is met behulp van peptiedfragment-konden-sasie gesintetiseer gegrond op soliedefase-peptiedsintese. Dit sintese vind in twee rigtings plaas (N~C en C~N) en is veelsydig aangesien dit die sintese van sowel nuwe dikar-boksielbola- amfifile as ander analoë verbindings moontlik maak. Die produk, suber-arnied(GG)2, is gesuiwer met behulp van die verbinding se inherente vermoë tot self-montering in suur oplossings. Nuwe assimetriese bola-amfifile, saamgestel uit dipeptiedkopgroepe, gekoppel via 'n alifatiese ro-aminosuur, wat as koolwaterstofspasieerder dien, is ook gesintetiseer. Twee klein bola-amfifilbiblioteke is saamgestel - die een het variasies in die ro-aminosuur se lengte omvat en die ander een variasies in die C-terrninale aminosuur. Selfmontering van die bola-amfifile het plaasgevind in of 0,1 % trifluorasynsuur Of 0,1 % trietielamien. Elektronrnikroskopie het die bestaan van 'n verskeidenheid hoërorde supramolekulêre strukture, gegrond op p-plaatselfmontering, aangetoon. Uit FT-IR-spektrometrie blyk dit dat inter - en intralaag waterstofbinbdingsnetwerke en sterk selfassosiasie, 19. word bevorder deur die hidrofobiese effek en, in sekere gevalle, elektrostatiese interaksies, is verantwoordelik vir die verskeidenheid supramolekulêre strukture. Variasies in die hoërorde strukture kan toegeskryf word aan aminosuursamestelling, in besonder die lengte van die ro-aminosuur, die aard van die C-terminale aminosuur en die geoptimiseerde oplosmiddelkondisies wat gebruik is vir die selfmonteringsproses. 'n Derde biblioteek nuwe "hibried" bola-amfifiliese peptiedsurfaktante, waarin 'n kationiese tripeptiedmotief uit antimikrobiale peptiede gekombineer is met 'n m-aminosuurresidu, is geskep. Sommige van hierdie bola-amfifile het 'n kragtige antimikrobiese aktiwiteit teenoor sowel Gram-positiewe as Gram-negatiewe bakterieë gertoon. Die analoë strukture was aktief, of selfs meer aktief as die voorste peptiede maar het, verbasend genoeg, nie 'n beduidende hemolitiese aktiwiteit vertoon nie. Hierdie organopeptied bola-amfifil het dus 'n selektiewe toksisiteit teenoor bakterieë vertoon. Die hidrofo-bisiteit, as gevolg van die ui-aminosuur, het 'n resiproke effek op hemolise en die antimikrobiese aktiwiteit van die peptiedanaloë. Die ander uitstaande kenmerk van die peptiede en hulle analoë is die vermoë om te selfmonteer en komplekse supramolekulêre strukture, bestaande hoofsaaklik uit ~-plate, te vorm. Hierdie selfmontering word in hoofsaak beheer deur hidrofobiese interaksies asook inter - en intralaagwaterstofbinding. Elektronmikroskopie het duidelik hoërorde strukture getoon by sowel dié peptiede as hulle analoë. Die ontwikkeling van hoërorde supramolekulêre struktuurvorms is afhanklik van die optimalisering van die ~-plaatselfmontering. Daarteenoor is die antimikro-biese aktiwiteit afhanklik van die balans tussen die netto positiewe lading en die opti-male hidrofobisiteit van die peptiedhibriede. Hierdie studie het getoon dat dit moontlik is om hibriedsurfaktante te ontwerp wat hoërorde supramolekulêre strukture te produseer en om die antimikrobiese aktiwiteit te verbeter terwyl die hemolitiese effek verminder word. Die studie en ontwerp van hier-die veeldoelige, "doelmatig-gesintetiseerde" biogeïnspireerde surfakante stel 'n unieke benadering daar, wat oor groot potensiaal beskik.
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Raeisi, Mersad. "Harnessing the Recognition Properties of Cucurbit[n]urils in Dynamic Supramolecular Polymers." Ohio University / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1565963566821693.
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Adams, Jeramie J. "New classes of bridging and chelating ligand motifs emphasizing: ruthenium(II) molecular squares, ruthenium(II) diphosphino carborane complexes, and acceptor PCP complexes of platinum(II), iridium(I/III), and ruthenium(II)." Laramie, Wyo. : University of Wyoming, 2008. http://proquest.umi.com/pqdweb?did=1663059861&sid=2&Fmt=2&clientId=18949&RQT=309&VName=PQD.
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Chen, Junpeng. "Enzymatic formation of supramolecular hydrogels based on self-assembly of DNA derivatives." Waltham, Mass. : Brandeis University, 2009. http://dcoll.brandeis.edu/handle/10192/23323.
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Clark, Thomas Edward. "Calixarene chemistry en route to nano-fabrication of phosphonated analogues." University of Western Australia. School of Biomedical, Biomolecular and Chemical Sciences, 2008. http://theses.library.uwa.edu.au/adt-WU2008.0052.
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[Truncated abstract] An efficient synthesis of the p-phosphonic acid calix[n]arenes, (n = 4, 5, 6 and 8) in five steps and excellent yield has been developed. This includes the key use of an acetyl protecting group, which is straightforward to introduce and remove using acetic anhydride and potassium hydroxide respectively. The synthesized p-phosphonic acid calixarenes are water-soluble and the hydrogen bonding prowess of the acidic groups dominates its selfassembly processes. For p-phosphonic acid calix[4]arene these include the formation of nano-rafts in the gas phase (≤ 20 molecules) and nano-particles (3.0(3) and 20.0(2) nm) of the calixarene in water using spinning disc processing stabilized by acetonitrile. The larger p-phosphonic acid calix[5,6,8]arenes also show nano-raft formation in both solution and the gas phase. An extensive study of the supramolecular chemistry of calix[5]arene has also been undertaken to better understand its rich structural diversity. This includes the formation of chloromethane inclusion complexes of p-tert-butyl-calix[5]arene and p-H-calix[5]arene with dichloromethane, p-phenyl-calix[5]arene with chloroform and their potential application as gas storage materials. Along with these three investigated inclusion complexes are two sublimates of p-H-calix[5]arene (α and β) with only the β-polymorph active for sorption of carbon dioxide at room temperature and 1 atm. The α-polymorph adopts an inverted cone conformation and forms helical stacks in the extended structure whereas the β-polymorph adopts the usual cone conformation and packs in both 'self included' and 'back-to-back' helical arrangements. ... Complementary to this study involved the p-H-calix[5]arene inclusion complexes with fluoro-, chloro-, bromo- and iodobenzene. All but the iodobenzene complexes are isostructural forming columnar arrays in the extended packing comprised of 'tri-calix[5]arene' segments. Iodobenzene is too large to form the respective 'tri-calix[5]arene' segments and instead forms sheets in the extended packing. To better understand the type and nature of the intermolecular interactions present within the supermolecules and extended structures a detailed Hirshfeld surface analysis was performed. A detailed Hirshfeld surface analysis was also performed on O-octadecyl-calix[6]arene, which crystallizes in the inverted double cone conformation. Three alkyl chains on either side interplay to form one side of hexagon in an hexagonal close packed array of interdigitated alkyl chains. This was the first Hirshfeld surface analysis performed at variable temperatures and enhanced the description of such a large supramolecular system. The related compound O-octadecyl-calix[4]arene was found to crystallize from toluene or benzene as supramolecular bilayers, 32.2(4) and 32.7(2) Å thick respectively. The calixarenes adopt the cone conformation and the alkyl chains interplay to form a continuous hexagonal motif similar to that seen for O-octadecyl-calix[6]arene. The formation of stable bilayers using octadecyl chains leads to the possibility of inserting long chain calixarenes with suitable functionalization into biological membranes. Such functionalization could include upper rim phosphorylation as seen for the p-phosphonic acid calixarenes to produce phospholipid mimics.
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Mathieson, Jennifer Sharon. "Probing the self assembly, reactivity and structure of supramolecular architectures using high resolution mass spectrometry." Thesis, University of Glasgow, 2011. http://theses.gla.ac.uk/2693/.
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Electrospray (ESI-MS) and cryospray mass spectrometry (CSI-MS) techniques were developed to analyse and investigate the self-assembly, reactivity and structure of supramolecular architectures. Using ESI-MS, the complexation reactions of the ligand cis,trans-1,3,5-tris(pyridine-2-carboxaldimino)cyclohexane (ttop) with divalent first row transition metal salts to form complexes with nuclearities 1,2 and 4 were followed. In-situ mass spectrometry was also utilised to show the stepwise formation of the ligand-metal complexes. Mass spectrometry has been used to identify the reactive species in the catalytic oxidation of conventionally hard to activate C-H and C=C moieties. The identity of the reactive species under catalytic conditions has been postulated as Fe(V)=O but direct observation of this species has not been possible before. Using cryospray mass spectrometry, the Fe(V)=O reactive intermediate within the synthetic [FeV(O)(OH)(PyMe2tacn)]+ (PyMe2tacn = 1-(2’-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane) complex at -40 ºC and its reaction with an olefin was observed. Oxygen atom transfer from H2O2 / H2O was followed through Fe(V)=O to the products with isotopic labelling, and the reactivity was probed as a function of temperature. Mass spectrometry has been used as both a qualitative and quantitative tool to deduce the stoichiometry of an anion receptor and the corresponding anion. Job plots of mass spectrometry data have been compared to the conventional 1H NMR job plot data to give corresponding results therefore providing evidence of the use of mass spectrometry as a quantitative and qualitative analytical tool. Mass spectrometry has been used to follow the formation of heterometallic complexes and provide evidence of their building block in solution. The formation of the complexes has been followed using time-resolved mass spectrometry experiments and the building blocks analysed.
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Dong, Xuehui. "Giant Molecular Shape Amphiphiles: Click Synthesis, Supramolecular Assembly, and Beyond." University of Akron / OhioLINK, 2013. http://rave.ohiolink.edu/etdc/view?acc_num=akron1384774671.
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Thom, James Andrew. "Self-assembly and anion recognition with binuclear lanthanide complexes." Thesis, University of Oxford, 2014. http://ora.ox.ac.uk/objects/uuid:20de876d-0a52-4f11-82b7-922fc3e2ee45.
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This work describes an investigation into the solution-phase binding of anionic guests by bimacrocyclic lanthanide complexes. It outlines the preparation of different classes of complexes bearing two metallic domains, and the effects of association on both the complex and the guest. Chapter one provides a cursory introduction to the fundamental properties of the lanthanides with a focus on luminescence. A brief literature review is given on the use of emissive lanthanide probes for the sensing of analytes. Chapter two concerns the preparation and properties of a series of binuclear complexes in which the two centres are linked with a short spacer group, with the aim of selectively sequestering small anions such as the halides in solution. The concept of luminescence titration will be introduced and then used to assess the binding parameters of a selection of guests. Chapter three describes a related class of ditopic lanthanide complexes in which the two metal centres are separated by a semi-rigid butyne linking group. Luminescence studies are again used to evaluate the binding constants of homologous series of dianions to ascertain how the size, geometry and functionalization of the anionic guest impacts on binding. Chapter four explores the coordination of phosphate species and assesses the ability to bind biologically significant phosphates of some of the complexes from Chapter 3. Chapter five details an investigation into the effects on guest-selectivity of further lengthening the linking unit which separates the two macrocyclic binding domains. Chapter six summarises the work done throughout the thesis and draws some overarching conclusions, as well as highlighting areas for further study. Chapter seven describes the experimental procedures.
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Seidenkranz, Daniel. "Barbiturates and Modified Hamilton Receptors for Supramolecular Catalysis, Sensing, and Materials Applications." Thesis, University of Oregon, 2019. http://hdl.handle.net/1794/24194.
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Supramolecular chemistry (chemistry beyond the molecule) is the study and synthesis of complex molecular architectures from simple subunits using non-covalent interactions. The types of non-covalent interactions that are used for the self-assembly of these complex molecular architectures include electrostatic interactions (e.g. ionic, halogen, and hydrogen bonding), π-effects, van der Waals interactions, metal coordination, and hydrophobic effects. While these interactions are often used in concert, some of the most
successful and ubiquitous approaches for the design and construction of new host–guest architectures are the incorporation of hydrogen bonding motifs. A popular class of molecules capable of making strong, highly directional hydrogen bonds is barbiturates.
Barbiturates have a well-known reputation as potent hypnotics, anticonvulsants, and anxiolytics but recent years have seen a renewed interest in these molecules due to their unique, symmetric acceptor-donor-acceptor hydrogen bonding motif. In addition, receptors with complementary hydrogen bonding motifs capable of binding barbiturates have also been reported, namely those based on the work of Hamilton et al. Collectively, barbiturates and their receptors have seen widespread use in a variety of applications including sensing, optoelectronics, catalysis, and the design of soft materials.
The work presented in this dissertation describes the development of novel Hamilton receptors for supramolecular catalysis and barbiturate sensing, as well as the design of new synthetic barbiturates. Together this body of research aims to extend the utility of these types of host–guest systems as well as continue to develop and refine the
supramolecular design principles that govern the binding interactions between barbiturates and a variety of Hamilton-type receptors.
This dissertation includes both previously published/unpublished and co-authored material.
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Fletcher, Amy L. "Thermodynamically Driven (Reversible) End-Capping of Pseudorotaxanes to Produce Rotaxanes." Thesis, Virginia Tech, 2003. http://hdl.handle.net/10919/30864.
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Rotaxanes can be synthesized using a thermodynamically driven approach of self-assembly. The thermodynamically driven approach is an efficient method to provide a better controlled synthesis of specific structures. This synthetic approach takes advantage of a labile bond between the guest molecule and the end stopper group. The reversibility of this bond allows for threading by the host molecule via chemical equilibrium. Intramolecular interactions such as hydrogen bonding and π-π stacking facilitate threading to form the pseudorotaxane which is endcapped to form the thermodynamically stable rotaxane. In this work, the synthesis and characterization of rotaxanes using a thermodynamically driven approach is reported. New OH-functionalized secondary dibenzyl ammonium hexafluorophosphate and tetrafluoroborate salts were synthesized and complexed with dibenzo-24-crown-8. The complexation between the salts and dibenzo-24-crown-8 was observed using 1D and 2D 1H NMR spectroscopy. An association constant of 110 M-1 was determined by integration for the pseudorotaxane from the ammonium hexafluorophospate salt and dibenzo-24-crown-8. The new guest species were endcapped in situ as trityl ethers to form new thermodynamically stable rotaxanes. Further work to pursue would include synthesis of rotaxanes using functionalized crown ethers for polymerization to make polyrotaxanes and synthesis of self-assembled polymers using this synthetic method.
Master of Science
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Valkov, Eugene. "Design and analysis of self-assembling protein systems." Thesis, University of Oxford, 2007. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.670100.
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Yoshii, Tatsuyuki. "Development of functional biomaterials by self-assembled nanostructures." 京都大学 (Kyoto University), 2014. http://hdl.handle.net/2433/192195.
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Zhang, Wenbin. "Soft Fullerene Materials: Click Chemistry and Supramolecular Assemblies." University of Akron / OhioLINK, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=akron1272303673.
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Monemian, Seyedali. "Tuning Mechanics of Bio-Inspired Polymeric Materials through Supramolecular Chemistry." Case Western Reserve University School of Graduate Studies / OhioLINK, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=case1467882025.
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Heck, James Arthur. "Self-assembly of tubular supramolecular architectures via a combination of endo- and exo-recognition processes." Case Western Reserve University School of Graduate Studies / OhioLINK, 1995. http://rave.ohiolink.edu/etdc/view?acc_num=case1058210556.
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Hallale, Oren. "Progressive design and self-assembly of supramolecular architectures : based on metallamacrocyclic nickel(II) complexes with bipodal tetra-alkylaroylbis (thioureas)." Doctoral thesis, University of Cape Town, 2004. http://hdl.handle.net/11427/6310.
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Includes bibliographical references.Rationally designed bipodal3,3,3',3'-tetraalkyl-l,1'-benzoylbis(thioureas) are used as pre-programmed cheiating ligands to form metallamacrocyclic square planar nickel(ll) complexes via self-assembly. Metal : ligand stoichiometries of either 2:2 or 3:3 can be achieved by using meta- or para- substituted ligands. The metallamacrocyclic complexes are subsequently converted into octahedral adducts via the addition of monodentate nitrogen donor ligands. Metallamacrocycles are further employed as secondary building units in the self-assembly of I-dimensional double- or tripleconnected coordination polymers. The synthesis of these polymers is achieved with the use of exo-bidentate nitrogen donor ligands.
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Groombridge, Alexander S. "Aqueous self-assembly with cucurbit[n]urils : from solution to emulsion." Thesis, University of Cambridge, 2018. https://www.repository.cam.ac.uk/handle/1810/271800.
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Making use of the non-covalent bond to make materials is of great interest in many fields of research. This PhD thesis describes a variety of highly interdisciplinary research undertaken at the interface between chemistry, materials science, physics and engineering. Chapter 1 is an introductory chapter into the core concepts underlying this thesis. Supramolecular chemistry as a broad research field is briefly reviewed, followed by a focus on host-guest chemistry. The macrocyclic cucurbit[n]urils (CB[n]s) in particular are highlighted with a discussion on their recent applications since their discovery. Emulsions and their controlled generation with microfluidic techniques are then reviewed, as they have been used as templates for self-assembly processes throughout this thesis. A study into the synthesis of extended polymer networks composed entirely from small molecules held together by non-covalent interactions is described in Chapter 2. These highly dynamic and responsive supramolecular polymer networks have not yet been constructed with CB[n] host-guest chemistry. The ability of the larger CB[8] macrocycle to encapsulate multiple guest molecules in a stepwise fashion was taken advantage on in designing the synthesis of branching monomers. The monomers had two (A$_2$) or three (B$_3$) terminal guest moieties for CB[8], which upon combination formed branching supramolecular polymers that were multi-stimuli responsive. However, the polymers precipitated from solution at high concentrations rather than form a cross-linked network, due to competing intra-chain cyclisation and the limited water solubility of CB[8]. By confining these polymers to microfluidic droplets, directed assembly to the liquid-liquid interface could drive polymerisation to form an interfacial cross-linked gel that was both elastic and self-healing. Chapter 3 follows on from these results, describing attempts into constructing hyperbranched supramolecular polymers from an AB$_2$ guest molecule and CB[8] that would form globular polymers. Intramolecular complexation dominated with the guest molecules synthesised (A and B complexing within the molecule), evidenced by a variety of characterisation. Compared to previous works that relied on linear molecules to form a folded conformation for intramolecular complexes, these molecules were pre-organised with a unique cooperative complexation pathway. The stimuli-responsiveness of the complexes was probed, and the formation of self-sorting mixtures was demonstrated with multiple CB[n] and additional guest molecules. Controlling the self-assembly of semi-conducting nanocrystals with CB[7] is detailed in Chapter 4, a process that typically requires harsh conditions or extensive time-scales. Semi-conducting nanocrystals could be assembled instantaneously from water into extended networks that were highly porous with excess CB[7], retaining their nanoscale properties. Limiting quantities of CB[7] could then form nanoscale aggregates that remained in solution. Confinement of these assemblies within microfluidic droplets allowed the synthesis of dense microparticles, that retained their shape after re-dispersal in water. By simply including metallic nanocrystals as a minor component, mixed aggregates could be synthesised analogously. Finally, Chapter 5 draws overall conclusions from the results of this thesis, looking broadly at the potential for future prospects in these areas of research.
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Gao, Min. "Structural and Dynamic Studies of Supramolecular Assemblies by Solid State NMR Spectroscopy." The Ohio State University, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=osu1385135235.
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Auffray, Morgan. "Cyclophanes, a bridge between photophysics and supramolecular chemistry." Thesis, Paris 6, 2017. http://www.theses.fr/2017PA066285/document.
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Dans ce travail, des derivés du dithia[3.3]paracyclophane sont étudiés pour des applications en nanostructuration de surfaces et comme nouveaux fluorophores. Dans un premier temps, l'auto-assemblage supramoléculaire de molécules est utilisé pour créer des réseaux 2D sur surface. Cependant, l'utilisation de tels substrats a tendance à annihiler les propriétés électroniques des composés adsorbés. Par conséquent, des dérivés 3D du dithia[3.3]paracyclophane sont employées afin d'éloigner le composant actif de la surface. Dans cet optique, de nouvelles molécules à base de groupements pyridine ont été conçues pour s'auto-assembler sur différents substrats. Les caractérisations préliminaires ont été effectuées afin d'étudier les propriétés d'auto-assemblage de telles molécules seules ou co-adsorbées, et les premières images de réseaux 2D auto-organisés sur graphite et or ont été obtenues par microscopie à sonde locale. Dans un second temps, de nouveaux composés sont actuellement étudiés pour électroluminescence à haute rendement à partir de la fluorescence retardée à activation thermique (TADF). Ce phénomène est généralement observé pour des molécules montrant un faible gap électronique entre ses états excités singulet et triplet, lié au faible recouvrement des orbitales HOMO et LUMO localisées sur le donneur et l'accepteur, respectivement. Dans ce contexte, nous proposons un nouveau design de molécules de type donneur-accepteur où HOMO (donneur) et LUMO (accepteur) sont séparées par un cœur cyclophane. Nous avons synthétisé deux émetteurs et leurs propriétés photo-physiques ont été étudiées en solution et à l'état solideIn this work and due to their unique electronic properties, 3D-dithia[3.3]paracyclophane-based molecules have been studied for surface nanostructuration applications and as new fluorophore. First, the supramolecular self-assembly of molecules is used to create well-organised 2D-networks on conducting surfaces. However, the use of such substrates tends to quench any electronic properties of the adsorbed molecules. In this context, 3D-dithia[3.3]paracyclophane-based molecules were employed to lift up the active moiety from the surface. In this work, new pyridyl end-capped molecules were designed to self-assemble on any substrate. Preliminary characterisations were performed to study the supramolecular self-assembly of such molecules alone or with co-adsorbers, and the first images of organised 2D-networks on graphite and gold have been obtained by scanning probe microscopy. Second, the design of new and efficient emitter is a hot topic for the fabrication of OLED devices. A new type of compounds is currently investigated for their high electroluminescence efficiency due to thermally activated delayed fluorescence (TADF). This phenomenon is expected from molecules showing low electronic gap between singlet and triplet excited states, which is related to a low overlap of the HOMO and LUMO, localised on the electron-door and acceptor moieties of the molecule, respectively. In this sense, we propose a new design of donor-acceptor molecules where the HOMO (donor) and LUMO (acceptor) are separated by a cyclophane core. We synthesised a couple of emitters and their photophysics properties were studied in solution and in solid state
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Forbes, Safiyyah. "Hydrogen-bond driven supramolecular chemistry for modulating physical properties of pharmaceutical compounds." Diss., Manhattan, Kan. : Kansas State University, 2010. http://hdl.handle.net/2097/3756.
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Jin, Lun. "Synthesis and Self-assembly of Planar Giant Molecules Based on Polyhedral Oligomeric Silsesquioxanes(POSS)." University of Akron / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=akron1490653139392999.
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Osypenko, Artem. "Supramolecular self-assemblies of triarylamines : fundamental studies and applications." Thesis, Strasbourg, 2016. http://www.theses.fr/2016STRAF062/document.
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Dans cette thèse, nous avons étudié le mécanisme fondamental du processus d'auto-assemblage thermoréversible des trisamides triarylamines chiraux. Nous avons ensuite étudié les utilisations possibles de dérivés de triarylamine dans différents domaines de recherche liés à la science des matériaux. Premièrement, en utilisant une approche biocatalytique, nous avons réussi à contrôler l'auto-assemblage d’amphiphiles à base de TAA-peptide conjugués dans l'eau. Deuxièmement, de nouveaux dérivés de triarylamine ont été incorporés avec succès en tant que couches conductrices de trous dans des cellules solaires de type pérovskite. Troisièmement, nous avons démontré la possibilité de déclencher électrochimiquement l'auto-assemblage de triarylamines pour la construction anisotrope contrôlée de nanofils conducteurs. Enfin, nous avons développé une technique qui permet l'alignement hautement ordonné de nanoparticules d'or sur une couche de nanofils de triarylamines à l'interface liquide-liquideIn this thesis, we have explored the fundamental mechanism of the thermally initiated self-assembly process of chiral triarylamine trisamides. The results demonstrate a cooperative nucleation and growth mechanism with well-defined thermal hysteresis and memory effect. We have then studied the possible implementations of triarylamine derivatives in various fields of material sciences. First, by taking advantage of a biocatalytic approach, we managed to control the self-assembly of TAA-peptide amphiphiles in water. Second, new triarylamine derivatives were successfully inserted as hole transporting layers in perovskite solar cells. Third, the self-assembly of triarylamines was triggered electrochemically, leading to an anisotropic construction of conducting nanowires. Finally, we developed a technique that allows for the highly ordered alignment of gold nanoparticles over a layer of triarylamine nanowires at the liquid-liquid interface by simple centrifugation of a biphasic mixture
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Sprafke, Johannes Klaus. "Supramolecular control of synthesis and electronic structure of porphyrin oligomers." Thesis, University of Oxford, 2011. http://ora.ox.ac.uk/objects/uuid:520bfa69-8cd5-4615-96fb-487651dd557a.
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The work described in this thesis demonstrates the use of supramolecular chemistry in the template-directed synthesis of porphyrin nanorings and as a tool to control conformation and topology of π-conjugated porphyrin oligomers. Particular emphasis is placed on changes to the electronic structure of these oligomers depending on their conformation. Chapter 1 gives an overview of π-conjugated porphyrin oligomers and conjugated macrocycles in general, followed by an introduction into supramolecular cooperativity and small angle X-ray scattering in solution. Chapter 2 describes advances in the synthesis, solution structure elucidation and optoelectronic properties of a fully conjugated cyclic porphyrin hexamer. The high rigidity and symmetry of this nanoring as well as its bent π-system lead to a significant decrease in its HOMO-LUMO gap. The resulting near-infrared emission was exploited in the fabrication of light emitting diodes, demonstrating the use of a bent topology for minimizing aggregation in thin films. The synthesis of a [12]porphyrin nanoring using a hexadentate template is presented in Chapter 3. The concept of Vernier templating is introduced as a general strategy for the synthesis of large monodisperse macrocycles. The nanoring is characterized and its cooperative binding to two template molecules is studied. In Chapter 4 a bidentate ligand is used in the cooperative formation of a sandwich complex beween two nanorings. Chapter 5 provides an analysis of the rigidity of the butadiyne linked porphyrin oligomers used throughout this thesis. A linear chain is significantly more flexible in solution than on a surface where it is confined within two dimensions. Analysis of the persistence length indicates that a porphyrin nanoring with more than around 20 units would not be significantly strained. The supramolecular binding of linear porphyrin oligomers to carbon nanotubes is analyzed in Chapter 6. The binding strength increases sharply with oligomer length and binding is strongest with (8,6) and (7,5) tubes. The energy level alignment in these porphyrin CNT complexes appears to be favorable for an application in photovoltaics. In Chapter 7 bisamidine-carboxylate salt bridges together with zinc-nitrogen coordination chemistry are used to access a variety of topologies in assemblies based on carboxylic acid functionalized porphyrin dimers.
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Cougnon, Fabien B. L. "Dynamic combinatorial synthesis of donor-acceptor catenanes." Thesis, University of Cambridge, 2012. https://www.repository.cam.ac.uk/handle/1810/241659.
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Dynamic combinatorial chemistry (DCC) is a powerful method for synthesising complex molecules and identifying unexpected receptors. Chapter 1 gives an overview of the concept of DCC and its applications, and discusses its evolution to date. Chapter 2 describes the discovery of a new generation of donor-acceptor [2]catenanes in aqueous dynamic combinatorial systems. The assembly of these [2]catenanes is promoted by a high salt concentration (1 M NaNO3), which raises the ionic strength and encourages hydrophobic association. More importantly, a mechanism that explains and predicts the structures formed is proposed, giving a fundamental insight into the role played by hydrophobic effect and donor-acceptor interactions in this process. Building on these results, Chapter 3 describes the assembly in high salt aqueous libraries of a larger structure: a [3]catenane. Remarkably, the [3]catenane exhibits strong binding interactions with a biologically relevant target - spermine - in water under near-physiological conditions. Its synthesis is improved if the salt is replaced by a sub-mM concentration of spermine, acting as a template. Chapter 4 explores in further detail how subtle variations in the building block design influence the selective formation of either [2] or [3]catenanes. This last section underlines both the advantages and the limitations of the method developed in Chapter 3. After a short conclusion (Chapter 5), Chapter 6 gives experimental details.
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Perman, Jason Alexander. "Solid-State Synthesis of Imide Ligands for the Self-Assembly of Metal-Organic Materials." Scholar Commons, 2011. http://scholarcommons.usf.edu/etd/3747.
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In this research project, reduction or complete elimination of organic solvents is explored in the synthesis of cyclic imides using a technique that brings reagents into favorable position to react. Cocrystal Controlled Solid-State Synthesis (C3Sy3), takes advantage of supramolecular interactions such as hydrogen bonding and π-π stacking to form a cocrystal which can sequential be heated to complete the condensation reaction and produce a desirable product. Twenty-five successful condensation reactions result in high and clean yield.
C3Sy3 of cyclic imides with auxiliary hydrogen bonding moieties like carboxylic acid, carboxylate or pyridyl groups are amenable to form additional solid-state materials. These moieties are useful in forming coordinate covalent bonds with metal cations. Using these C3Sy3 synthesized molecules as ligands, various Metal-Organic Materials (MOMs) are self-assembled. These MOMs offer unique qualities owing to the properties of the cyclic imides. With the addition of accessible carbonyl groups, they may participate as hydrogen bond acceptors or hydrophilic groups. Various degrees of rotation of N-phenyl substituents around the imide plane allow for structural flexibility as a route to supramolecular isomers in MOMs. The ease in imide synthesis may allow the fast scale-up of these ligands for industrial application. Similar ligands are generally synthesized by cross-coupling or substitution reactions that require expensive catalyst and various organic solvents.
Metal-organic materials are a class of compounds amenable to crystal engineering owing to the directional coordinate covalent bonds between metal or metal clusters and organic ligands. They are characterized by X-ray diffraction, spectroscopy, volumetric and gravimetric analysis. The C3Sy3 imides were used to construct various MOMs, from discrete nanostructures to extended 3-periodic frameworks that possess viable internal space for applications pertaining to porous materials. Structural characterization by single crystal X-ray diffraction and structure-function relations are addressed. Gas sorption experiments show that many of these materials are structurally robust and retain crystallinity after evacuation. Ion exchange and guest uptake experiments using the synthesized materials demonstrate their potential as agents for sequestration.
The bottom-up synthesis of metal-organics materials is leading the field of crystal engineering with built-in properties, showing promise by combining attributes from both inorganic and organic components.
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Nishitani, Nobuhiko. "Design and Control of Cooperative Self-Assembly Processes at Liquid/Solid Interfaces by Tuning Supramolecular Interactions." Kyoto University, 2019. http://hdl.handle.net/2433/242536.
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付記する学位プログラム名: 充実した健康長寿社会を築く総合医療開発リーダー育成プログラムKyoto University (京都大学)
0048
新制・課程博士
博士(工学)
甲第21798号
工博第4615号
新制||工||1719(附属図書館)
京都大学大学院工学研究科合成・生物化学専攻
(主査)教授 松田 建児, 教授 杉野目 道紀, 教授 浜地 格
学位規則第4条第1項該当
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Rota, Martir Diego. "Chiral iridium(III) and ruthenium(II) complexes as phosphorescent scaffolds for heterometallic supramolecular self-assembly." Thesis, University of St Andrews, 2018. http://hdl.handle.net/10023/14555.
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This thesis explores the design, synthesis and optoelectronic properties of supramolecular photoactive materials based on chiral iridium(III) and ruthenium(II) metalloligands. Our design strategies aim to create a high concentration of chromophoric units that, when self-assembled in well-defined geometrical arrangements, exhibit emergent photophysical properties.
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Carter, Timothy Glen 1976. "New supramolecular assemblies of toxic metal coordination complexes." Thesis, University of Oregon, 2010. http://hdl.handle.net/1794/10562.
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xvii, 147 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number.Supramolecular chemistry is a relatively new and exciting field offering chemists simplistic approaches to generating complex assemblies through strategically designed ligands. Much like the many spectacular examples of supramolecular assemblies in nature, so too are chemists able to construct large, elegant assemblies with carefully designed ligands which bind preferentially to target metal ions of choice. An important concept of supramolecular chemistry, often subtle and overlooked, is secondary bonding interactions (SBIs) which in some cases, act as the glue to hold supramolecular assemblies together. This dissertation examines SBIs in a number of systems involving the pnictogen elements of arsenic and antimony as well as aromatic interactions in self-assembled monolayers. The first half of this dissertation is an introduction to the concepts of supramolecular chemistry and secondary bonding interactions and how they are used in the self-assembly process in the Darren Johnson laboratory. Chapter I describes how secondary bonding interactions between arsenic and aryl ring systems and antimony and aryl ring systems assist with the assembly process. Chapter II is a continuation of the discussion of SBIs but focuses on the interactions between arsenic and heteroatoms. The second half of this dissertation will describe work performed in collaboration with Pacific Northwest National Laboratory (PNNL) in Richland, WA. This work was performed under the guidance of Dr. R. Shane Addleman in conjunction with Professor Darren W. Johnson of the University of Oregon. This portion describes novel systems for use in heavy metal ion remediation from natural and unnatural water sources. Chapters III-V describe functionalized mesoporous silica for use in heavy metal uptake from contaminated water sources. Chapter V describes a new technology invented during this internship at PNNL which utilizes weak bonding interactions between aryl ring systems to produce regenerable green materials for toxic metal binding. This work is ongoing in the Darren Johnson lab. This dissertation includes my previously published and co-authored material.
Committee in charge: Michael Haley, Chairperson, Chemistry; Darren Johnson, Member, Chemistry; Shih-Yuan Liu, Member, Chemistry; James Hutchison, Member, Chemistry; Eric Johnson, Outside Member, Biology