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Dissertations / Theses on the topic 'Anion'

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Published: 4 June 2021
Last updated: 11 March 2023

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1

Drumright, Ray E. "Radical anion rearrangements. aryl cyclopropyl ketyl anions." Diss., This resource online, 1991. http://scholar.lib.vt.edu/theses/available/etd-07282008-134853/.

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2

Sun, Zhanhu [Verfasser]. "Quinoline-based anion receptors and anion-pi interactions / Zhanhu Sun." Aachen : Hochschulbibliothek der Rheinisch-Westfälischen Technischen Hochschule Aachen, 2013. http://d-nb.info/1042551367/34.

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3

Wang, Zhiming 1958. "Anion Exchange and Competition in Layered Double Hydroxides." Thesis, University of North Texas, 1997. https://digital.library.unt.edu/ark:/67531/metadc332481/.

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Exchange reactions of anions, especially ferrocyanide and carbonate, with layered double hydroxides (LDHs) were investigated in relation to the origin of life on the early Earth. The effect on ferrocyanide exchange of concentration, pH, reaction time and cations are discussed. It was found that there were two different kinds of ferrocyanide species: one was that intercalated into the layered structure, occupying a site of D symmetry within the LDHs, while in the other, the ferrocyanide group retains full O symmetry. In addition, very low concentration, ferrocyanide associated with LDH will change its FTIR absorption shape. Carbonate was much more strongly intercalated than ferrocyanide into the LDHs, probably because of the strong hydrogen bonding.
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4

Andrews, Django H. "Anion photoelectron spectroscopy." Diss., Connect to online resource, 2006. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqdiss&rft_dat=xri:pqdiss:3239380.

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5

Wietek, Jonas. "Anion Conducting Channelrhodopsins." Doctoral thesis, Humboldt-Universität zu Berlin, 2018. http://dx.doi.org/10.18452/19325.

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Seit mehr als 10 Jahren kann biologische Aktivität durch eine Vielzahl photosensorischer Proteine beeinflusst werden. In diesem als Optogenetik bezeichneten Forschungsgebiet, werden Kationen leitende Kanalrhodopsine (CCRs) als lichtinduzierte neuronale Aktivatoren eingesetzt. Diese Arbeit soll zur Vervollständigung von optogenetischen Werkzeugen durch die Entwicklung Anionen leitender Kanalrhodopsine (ACRs) dienen, um die bestehenden Nachteile mikrobieller lichtgetriebener Ionenpumpen zu überwinden, die bislang zur neuronale Inhibition genutzt wurden. Der Austausch von E90 in C. reinhardtii Kanalrhodopsin 2 (CrChR2) durch positiv geladene Aminosäuren führte zu Entwicklung Chlorid leitender ChRs (ChloCs), die jedoch eine Restkationen-permeabilität aufwiesen. Durch Substitution zweier weiterer negativen Ladungen innerhalb des Ionenpermeationsweges, konnte die Kationenleitung vollständig aufgehoben werden. Parallel wurde durch A. Berndt et al. ein inhibitorisches C1C2 (iC1C2), basierend auf der CrChR1/2 Chimäre entwickelt. Wie auch bei den ChloCs, zeigte iC1C2 verbesserungswürdige biophysikalische Eigenschaften. Mutagenesestudien des Ionenpermeationsweges führten zur Entwicklung der verbesserten Nachfolgervariante iC++. Um ausgehend von weiteren CCRs neuartige ACRs zu entwickeln (eACRs), wurden die zuvor angewandten Mutagenesestrategien auf weitere CCRs übertragen. Zwei neue eACRs, Phobos und Aurora, mit jeweils blau- und rotverschobenen Aktionsspektrum konnten generiert werden. Bistabile eACRs wurden erzeugt, die ein lichtgesteuertes Schalten zwischen offenen und geschlossenen Zuständen ermöglichen. Schlussendlich wurde ein natürlich vorkommendes ACR (nACR) aus Proteomonas sulcata (PsACR1) identifiziert und charakterisiert. Die Maximalaktivität von PsACR1 zählt mit 540 nm zu den am stärksten rotverschobenen unter den nACRs. Elektrophysiologische und spektroskopische Untersuchungen ergaben, dass sich der Photozyklus von PsACR1 signifikant von jenen der CCRs unterscheidet.
For more than 10 years, photosensory proteins have developed as powerful tools to manipulate biological activity. In this research field termed optogenetics, cation-conducting channelrhodopsins (CCRs) mainly are utilized as light-induced neural activators. This study aimed at a complementation of the optogenetic tool box by engineering anion-conducting channelrhodopsins (ACRs) to overcome the existing drawbacks of microbial light-driven ion pumps utilized for neural inhibition so far. Replacement of E90 in the cation-conducting C. reinhardtii channelrhodopsin 2 (CrChR2) with positively charged residues reversed the ion selectivity and yielded chloride-conducting ChRs (ChloCs). Applied in neuronal cell culture, ChloCs showed residual cation permeability occasionally leading to excitation instead of the desired inhibition. Further charge elimination within the ion permeation pathway completely abolished cation conduction. In parallel, an inhibitory C1C2 (iC1C2) was developed by A. Berndt et al. based on a CrChR1/2 chimera. Though, iC1C2 displayed unsatisfactory biophysical properties as well. Further mutational modifications of the ion permeation pathway led to the development of the improved successor variant iC++. A systematic transfer of both conversion strategies to other CCRs was conducted to create engineered ACRs (eACRs) with distinct biophysical properties. Two novel eACRs, Phobos and Aurora, with blue- and red-shifted action were obtained. Additionally, step-function mutations greatly enhanced the operational light sensitivity and enabled temporally precise toggling between open and closed states using two different light colors. Finally, a natural ACR (nACR) originating from Proteomonas sulcata (PsACR1) was identified and characterized. With a maximum activation at 540 nm it is one of most red-shifted nACRs. Single turnover electrophysiological measurements and spectroscopic investigations revealed an unusual photocycle compared to that of CCRs.
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6

Calin, Nathalie. "Etude thermique de quelques sels d'hétéropolymolybdates : mise en évidence d'interactions anion-anion et anion-cation à l'état solide." Lille 1, 2001. https://pepite-depot.univ-lille.fr/LIBRE/Th_Num/2001/50376-2001-119.pdf.

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Les polyoxométallates et plus particulièrement les hétéropolymolybdates sont des composés très recherchés en catalyse, homogène ou hétérogène. A l'état solide, leur comportement réactif dépend de nombreux paramètres dont la nature des contre-ions présents, le type de molécules de solvatation, le système cristallin et leur evolution thermique. Plusieurs sels (sodium, potassium, alkyl(aryl)ammonium) des ions dodécamolybdophosphate (3-), vanadoundécamolybdophosphate (4-) et de structures apparentées (octadécamolybdophosphate (6-)) ont été préparés. Ils ont été étudiés en solution par polarographie et à l'état solide par spectrométries de vibration (infra-rouge, Raman) et spectrométrie RMN de 31P. Leur comportement thermique a été suivi par analyse thermique et les différentes phases décelées étudiées par RPE. Ces mesures ont permis d'identifier plusieurs types d'interactions susceptibles de rendre compte de la réactivité en oxydation sélective. Deux d'entre elles, interactions anion-anion et anion-cation, sont fortement dépendantes des arrangements cristallographiques et de leur évolution thermique. L'interaction anion-anion est attendue augmenter la stabilité de l'anion, alors que l'interaction anion-cation, antagoniste, est attendue la diminuer.
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7

Ferguson, Richard. "Fluorescent Anion Sensing and Anion Templated Assembly of Interpenetrated Molecular Architectures." Thesis, University of Oxford, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.491446.

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The main aim: of this project is to develop novel acyclic and macrocyclic hosts for the binding and fluorescent sensing of anionic guests in solution. In addition the use of these hosts in anion templated interpenetrated architectures was exploited. Chapter One introduces the field of supramolecular chemistry and gives a brief description of the non-covalent forces employed in supramolecular host design. A description of the areas of anion binding and the more sophisticated discipline of anion sensing is given. The Chapter concludes with a discussion of the phenomenon of selfassembly and in particular, details the advances in molecular templation that have revolutionised the synthesis ofmechanically interlocked systems. Chapter Two describes the synthesis of a range of indolo[2,3a]carbazoles through a 'one-pot' Fischer indolisation reaction and their subsequent functionalisation to give acyclic and macrocyclic receptors. Schiff base receptors capable of intramolecular hydrogen bonding were shown to have minimal anion binding. However, a bipodal amino receptor showed very high anion affinity. Chapter Three details the preparation ofnew 'off-on' fluorescent sensors for anions using anthracene PET based receptors. Various neutral and charged anion binding groups were appended to the anthracene including imidazoliums and pyridine bis-amide derivatives. Both the anion binding potential of these receptors and the ability of the anion to effect the fluorescence PET ofthe anthracene were investigated Chapter Four reports the use of fluorescent receptors in Chapters Two and Three as . threads in anion templated [2]-pseudorotaxanes. Sulfate successfully templated the formation of an indolocarbazole pseudorotaxane while chloride was used for the anthracene derivative. Each section culminates in the attempts to permanently interlock the structures as [2]-rotaxanes. Chapter Five reports the synthetic procedures used within the thesis.
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8

Sekizaki, Shuichi. "Development of conducting cation radical salts with flexible organic anions : tetracyanoallyl anion derivatives." 京都大学 (Kyoto University), 2006. http://hdl.handle.net/2433/144214.

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9

Zain, S. A. M. "Novel inorganic anion exchangers." Thesis, University of Salford, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.234769.

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10

Swinburne, Adam Neil. "Induced-fit anion sensing." Thesis, Durham University, 2011. http://etheses.dur.ac.uk/579/.

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Anions have many important roles in biological systems, as well as in the environment and as such there is significant interest in their binding and sensing. In induced-fit anion sensing, the binding of an anion causes a shift in the equilibrium of conformers of the molecule, which in turn may lead to a change in a physical property. In this thesis four experimental chapters describe the synthesis and anion sensing properties of a series of induced-fit anion sensors derived from a hexa-substituted triethylbenzene and diphenylacetylene motif. Chapter one provides an introduction to anion recognition and sensing, whilst Chapter two describes a new synthetic method towards triethylbenzene receptors involving the solvent-drop grinding technique. Facile synthesis of known and novel anion receptors was achieved. Chapter three describes the use of the triethylbenzene motif, functionalised with quinolinium groups to sense anions. The receptor binds anions strongly, with complex binding observed, involving a host dimer, 2:1 host:guest and 1:1 host:guest stoichiometries. The receptor functions as a turn-off fluorescence sensor with selectivity for acetate. Chapter four describes the further functionalisation of the triethylbenzene core with the viologen moiety, leading to a series of tri- and tetrapodal anion receptors. These receptors show a colourimetic response to carboxylates through a charge transfer interaction. These receptors bind several different anions strongly. However a colourimetric response is only observed with carboxylates. Chapter five describes the use of diphenylacetylene derivatives functionalised with urea groups which have also been investigated as induced-fit anion sensors. The receptors show a high degree of preorganisation, except for free rotation around the acetylene bond. The receptors bind a range of anions to varying extents, with strong binding observed with basic anions. Upon the addition of anions, several different fluorescent responses are observed depending on the receptor design. A turn-on fluorescent response is observed with diphenylacetylene and diphenylbutadiyne derivates due to planarisation of the receptor. Fluorescent quenching is also observed with several receptors and can allow for the discrimination of several anions when the receptors are used as part of an array. The diphenylbutadiyne derivative can also be incorporated into a dipstick which shows a turn-off response in the presence of chloride.
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11

Sergeant, Genevieve. "Applications of Anion Binding." Thesis, The University of Sydney, 2022. https://hdl.handle.net/2123/28497.

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This thesis describes the development and exploration of chemosensing systems for phosphates and their applications to specific biological challenges. Investigation of the sensing abilities of a peptide-based bis-Zn(DPA) chemosensor, is detailed. Building on existing research aimed at developing selective sensors of phosphate species (PPi, ADP and ATP), the properties of this sensor were thoroughly investigated in a variety of buffered aqueous systems. The chemosensor exhibited a large, selective, turn on in emission in the presence of pyrophosphate but this response was modulated by additives including magnesium(II) and calcium(II) that are commonly found in biological systems. However, a range of conditions were identified that allowed the sensor to be successfully applied to the challenge of monitoring multiple enzymatic reactions. Cross reactive chemosensors are discussed and applied to discriminate between multiple similar phosphate species including inorganic, nucleoside phosphates and phosphorylated amino acids. Using two array-based sensing approaches and two different methods for diversification of array elements, the sensing of phosphates in an array format was investigated. The resultant arrays represent an improvement on the breadth of phosphates previously classified using an array-based sensing approach. Finally, the principles of selective and cross reactive chemosensors are combined to address a diagnostic challenge – diagnosis of rheumatological disease. By targeting pyrophosphate and uric acid, a strategy to diagnose crystal arthritis was developed. Proof of concept studies showed promising results however challenges remain for the analysis of clinical samples. The work in Chapter 4 was affected by the Covid-19 pandemic and details of further planned studies are included.
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12

Gillmore, Jason G. Jr. "Evaluation of 1,1-Dimethyl-5,7-Di-T-Butylspiro[2.5]Octa-4,7-Dien-6-One as a Mechanistic Probe for Single Electron Transfer." Thesis, Virginia Tech, 1998. http://hdl.handle.net/10919/36888.

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Single electron transfer (SET) mechanisms are becoming ubiquitous in modern organic chemistry. However, it is often difficult to distinguish SET mechanisms from polar mechanisms. Kinetics, products and product distributions, and response to perturbation in solvent and substituents are often identical between the two mechanisms. Detection techniques such as EPR, CIDNP, and UV absorption can often detect "blind" pathways and thus cannot provide unambiguous evidence regarding the true mechanism of interest. In recent years mechanistic probes have been developed which can test for single electron transfer in the mechanism of interest in a more unambiguous manner, although a given probe is often applicable to a narrower range of reactions.

In this work 1,1-dimethyl-5,7-di-t-butylspiro[2.5]octa-4,7-dien-6-one (6) is presented as a new "hypersensitive" probe for single electron transfer to conjugated carbonyl compounds. This new probe functions in a rather unique fashion, allowing interpretation of the mechanism at work on the basis of the regiochemistry of spirocyclic ring opening. This "regiodifferentiation" based probe was studied with a variety of nucleophiles (particularly Grignard reagents) and has been found to be effective in differentiating SET from polar processes, although surprising results indicative of polar pathways in the case of reaction of 6 with Grignard reagents other than methyl Grignard were found. Additional insight into the mechanism of the reaction of Grignard reagents with conjugated ketones is also presented.


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13

Busschaert, Nathalie. "Structure-activity relationships in novel small-molecule anion receptors and transmembrane anion transporters." Thesis, University of Southampton, 2014. https://eprints.soton.ac.uk/367100/.

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14

Wells, Debra J. "Extraction of the perrhenate and pertechnetate anions from aqueous solutions using inorganic anion exchangers." Thesis, University of Reading, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.306851.

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15

Brooks, Simon James. "From linear to cyclic anion receptors : high affinity receptors and sensors for oxo-anions." Thesis, University of Southampton, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.438694.

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16

Bradbury, Adam John, and babradbury@optusnet com au. "METAL ION ACTIVATED ANION SENSORS." Flinders University. School of Chemistry Physics and Earth Sciences, 2007. http://catalogue.flinders.edu.au./local/adt/public/adt-SFU20080319.125059.

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A series of new, octadentate, fluorescent, macrocyclic ligands have been prepared with a view to using them to study aromatic anion sequestration. The eight-coordinate Cd(II) complexes of the ligands have been shown capable of acting as receptors for a range of aromatic oxoanions. This has been demonstrated by perturbation of both 1H NMR chemical shift values and the anthracene derived fluorescence emission intensity as the potential guest anion and the host are combined. Non-linear least squares regression analysis of the resulting titration curves leads to the determination of binding constants in 20% aqueous 1,4-dioxane which lie in the range 10^2.3 M-1 (benzoate) to 10^7.5 M-1 (2,6-dihydroxybenzoate). By reference to the X-ray determined structures of related, but non-fluorescent inclusion complexes, the primary anion retention force is known to arise from hydrogen bonding between the anion and four convergent hydroxy groups that exist at the base of a cavity that develops in the complexes as their aromatic groups juxtapose upon coordination. This work reveals significant stability enhancement when hydroxy groups are positioned on the anion at points where O-H...pi hydrogen bonding to the aromatic rings that constitute the walls of the cavity becomes geometrically possible.
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17

Atkinson, Paul. "Chemoselective phospho-anion binding studies." Thesis, Durham University, 2005. http://etheses.dur.ac.uk/2804/.

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An investigation has been carried out, studying the interaction of various bioactive anions, particularly phosphorylated species, with well-defined chiral lanthanide complexes. In each ternary anion adduct, proton NMR analysis revealed a distinctive pattern for the most high frequency shifted resonances. Furthermore, the mean chemical shift of these four resonances can be used to identify the anion adducts present in solution and indicate the binding mode exhibited towards the lanthanide(III) centre. Similar differentiation of anion binding modes is also available from luminescence spectroscopy, via observation of the splitting pattern for the (^7)F(_1) ← (^5)D(_0)transition in europium complexes. Thulium and ytterbium complexes display the greatest affinity towards anions. With 0֊phosphorylated amino acids and peptides, amino acid or N-terminal chelation is a competitive binding mode. In contrast, the corresponding europium complexes display a significant preference towards the phosphate binding mode and such complexes may be considered to function as selective receptors for phosphorylated peptides or proteins. For all the lanthanides, complexes involving an N-methylated ligand show an increase in competition from the chelating binding modes. This effect is most significant for the smaller lanthanide(III) ions. Parallel investigations into the suitability of 1-azaxanthone derivatives as long wavelength sensitisers for europium(III) and terbium(III) emission were performed. The introduction of electron donating groups into the 1-azaxanthone compound led to an increase in the absorption wavelength maximum. However, perturbation of the excited states was accompanied by competitive fluorescence emission and in certain cases quenching of the excited states via intramolecular hydrogen bonding. Formation of the TV-oxide derivative of 1-azaxanthone also led to a significant red shift in the absorption maximum. The related 1 ֊aza-10-thioxanthone compound displayed the greatest potential as a lanthanide(III) sensitiser, and its incorporation into a phosphate selective europium receptor was investigated with the aim of achieving optical detection of low concentration of anions.
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18

McGinnes, D. F. "Anion exchangers for radioisotope storage." Thesis, University of Salford, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.381727.

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19

OLIVARI, MARTINA. "Neutral receptors for anion recognition: synthesis, selectivity studies and transport properties." Doctoral thesis, Università degli Studi di Cagliari, 2014. http://hdl.handle.net/11584/266429.

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This thesis reports the synthesis and studies of a new series of compounds containing urea groups that can function as selective anion receptors and efficient anion transmembrane transporters. Two new asymmetric ureidic receptors L1 (1-(1H-indol-7-yl)-3- (quinolin-2-yl)urea) and L2 (1-(quinolin-2-yl)-3-(quinolin-8-yl)urea), shown in Figure 1, have been synthesised and their affinity towards different anions tested in DMSO-d6. L1 adopts both in solution and in the solid state an (E,Z) conformation. A moderate affinity for acetate has been observed with L1 while no interaction has been observed with L2. The different behaviour has been ascribed to the presence/absence of the indole group. In the case of L1 the indole group causes the formation of a peculiar supramolecular architecture with two molecules of the receptor binding the anions in (E,Z) conformation via H-bonds. L2 also adopts an (E,Z) conformation in the solid state. However, the absence of the indole in L2 hampers the formation of the supramolecular assembly with the participation of anionic species. The results are discussed in Chapter 2. In Chapter 3 a new family of bis-ureidic receptors (L3-L8) is reported (Figure 2). The binding properties of L3-L8 towards different anions (acetate, benzoate, glutarate, malonate, dihydrogen phosphate, hydrogen pyrophosphate, triphosphate, AMP and ADP) have been studied by means of 1H-NMR, UV-Vis and fluorescence spectroscopies and a remarkable affinity for HPpi3- has been observed in the case L5 (in DMSO- d6 and DMSO-d6/5% H2O) which also acts as fluorimetric chemosensor, even at naked eye, for this anion. Theoretical calculations helped us to explain the binding properties observed. A series of bis-ureidic receptor L9-L14 (Figure 3) was prepared and the studies of their transmembrane anion transport activity and anion binding properties are described in Chapter 4. Vesicle anion transport assays using ion selective electrodes demonstrate that these compounds function as efficient mobile carriers that are able to transport chloride through lipid bilayer predominantly via anion exchange mechanism including Cl-/NO3- and Cl-/HCO3- antiport. Compound L14 was found to be the most active transporter of the series. As anion receptors, we observed that compounds L10 and L12 demonstrate strong 1:1 binding with TBA fluoride (Ka >104 M-1) and moderate 1:1 binding with TBA dihydrogenphosphate. In Chapter 5, the anion transport efficiency of a series of trisureas L15-L20 (Figure 4) was investigated. The compounds showed a potent transmembrane anion transport activity. The mechanism of transport was extensively investigated using a combination ion selective electrode and fluorescence techniques. It was found that compounds L15-L20 mediate chloride transport via Cl-/NO3- and Cl-/HCO3- antiport and NaCl symport. The tris-urea L15 was found to be a remarkably potent anion carrier at low concentration.
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20

Spooner, Michael. "Anions and the bilayer : structural and mechanistic studies towards synthetic anion carriers for therapeutic applications." Thesis, University of Southampton, 2017. https://eprints.soton.ac.uk/410302/.

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Synthetic transmembrane anion transporters have attracted a great deal of interest due to their potential as therapeutic agents for the treatment of channelopathies such as cystic fibrosis or in the treatment of cancer. Despite a great deal of progress in the field over recent years, there are currently several hurdles that need to be overcome before anionophores become genuine therapeutic candidates. These include knowledge of how carriers behave in more cell-like bilayer systems, what molecular properties govern the rate determining step of the transport process and issues with solubility and deliverability. This thesis aims to explore some of these areas to help overcome some of these future barriers. The effect of lipid environment on the transport ability of a series of alkyl-substituted thioureas was investigated. The series covered a wide range of lipophilicity, to determine whether the optimum lipophilic range varied depending on the composition of the bilayer. Despite the different lipids appearing to modulate the overall transport rate, the relative order of the transporter efficacy appeared unaffected. Data is also presented demonstrating the use of dynamic covalent chemistry to generate an active transporter molecule in situ within the membrane. The compound formed by DCC was observed by measuring its transport response from vesicle experiments after the addition of two precursors (which do not facilitate transport alone) to the membrane. Comparison of the transport ability of the pre-formed compound and the rate of the DCC reaction measured by NMR spectroscopy gave insight into the balance required between these two factors in the design of these compounds. Finally, the effect of the fluorination of alkyl chains in tripodal tris-thiourea receptors was explored. Vesicle assays with and without accompanying protonophores to couple to the transport process were carried out to determine the mechanism of the transport process and discover whether fluorination had any effect on the selectivity of the transporter molecules. The activity of the compounds in FRT-YFP cell assays was also determined and comparison with the vesicle data gave insights into the vesicle tests required to accurately predict the transporters’ efficacy in cell epithelia.
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21

Jones, Graham K. "Expression and anion transport studies on the human erythrocyte anion exchange protein (AE1, band 3)." Thesis, University of Bristol, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.245676.

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22

Brown, Terence D. "Anion exchange at the interfaces of mixed anion III-V heterostructures grown by molecular beam epitaxy." Diss., Available online, Georgia Institute of Technology, 2003:, 2003. http://etd.gatech.edu/theses/available/etd-11182003-014419/unrestricted/brownterenced200312phd.pdf.

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Thesis (Ph. D.)--Electrical and Computer Engineering, Georgia Institute of Technology, 2004.
May, Gary, Committee Chair; Doolittle, William, Committee Member; Brown, April, Committee Member; Wang, Zhong Lin, Committee Member; Ralph, Stephen, Committee Member. Includes bibliography.
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23

Butson, Jeffery M. "Electron Transfer and Other Reactions Using Atomic Metal Anions." Thèse, Université d'Ottawa / University of Ottawa, 2014. http://hdl.handle.net/10393/30561.

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The atomic metal anions Rb-, Cs-, Cu-, Ag- and Fe- have been generated in the gas phase and reacted with various neutral reactants in a triple quadrupole mass spectrometer. The metal anions were formed via electrospray ionization of the metal-oxalate solutions and form in gas phase between the capillary and the first quadrupole. Neutral gas phase reactants investigated include NO, NO2, SO2, C6F5OH, C6F5NH2, C6F6, E-octafluoro-butene and 1,2,3/1,2,4/1,3,5 trifluoro-benzene. When possible, CBS-4M methods were used to suggest the lowest energy products based on relative energy. Observed reactions of atomic metal anions with the aforementioned neutral species include electron transfer and dissociative electron transfer to the neutral gas phase reactants. In addition, hydrogen abstraction and fluorine abstraction forming a neutral metal hydride or fluoride as well as the formation of multiply substituted metal-oxide/fluoride anions was also observed. Metal-complex anions observed from the gas phase reactions include CuF-,CuF2-,CuO-,CuO2-, FeO-, FeO2-, FeO3-, FeF-, FeF2-, FeF3-, CsF- and CsF2-.
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24

Jagessar, Raymond C. "Anion recognition by novel functionalised porphyrins." Thesis, University of Oxford, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.363767.

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25

Goulden, Alistair John. "Anion recognition by novel calixarene receptors." Thesis, University of Oxford, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.240479.

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26

Parsons, Thomas. "The anion chemistry of manganese perovskites." Thesis, University of Oxford, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.497068.

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27

Lloyd, Gareth Owen. "Anion-tuning of supramolecular gel properties." Thesis, Durham University, 2010. http://etheses.dur.ac.uk/186/.

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Low molecular weight gelators (LMWGs) are a class of compounds that has garnered great interest from material, synthetic, supramolecular and biological chemists. Anion tuning of these supramolecular gels is a burgeoning field of study. Two classes of compounds, chiral bisureas and urea derivatised pyrazoles are studied. The synthesized chiral bisurea compounds act as gelators in a variety of solvents. Addition of anions in the form of tetrabutyl ammonium salts was found to afford break up of the gels. Studies reveal that the rheological characteristics of these materials can be tuned using the simple addition of sub-stoichiometric amounts of anion. Variation in the length of the alkyl chain of the spacer separating the chiral and bisurea moieties affects the gel formation of a series of related compounds. Compounds with even numbered spaced alkyl chains were found to gel, whereas the odd numbered spaced alkyl chain compounds did not. Crystal growth within the gel matrix influences the crystallization processes and the use of anion induced break down of the LMWGs allows for easy recovery of the grown crystals. Drug compounds, bound upon gelation of a solution containing the drugs, were found to be released in a controlled manner from the gel matrix. Urea functionalised pyrazoles were synthesized. Crystallographic determination of the hydrogen bonding of the compounds as well as the coordination chemistry of these compounds was obtained. Anion binding studies, in addition to the crystallographic results, reveal that the urea or thiourea groups form an intramolecular hydrogen bond with the pyrazole group resulting in an anti conformation. This prevents formation of gels except in one case. The gelation of 1-(3-methyl-1H-pyrazol-5-yl)-3-(3-nitrophenyl)urea in acidic water overcomes this problem by protonation of the pyrazole group resulting in a syn conformation of the urea group. Anion tuning of the gel properties is revealed where nitrate and chloride result in precipitation of gels and the rheological characteristics can be tuned by changing the anion’s identity.
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28

Burns, Barry. "Palladium catalysed cyclisation anion capture process." Thesis, Queen's University Belfast, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.334562.

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29

Watson, James David. "Anion and cation binding in proteins." Thesis, University of Glasgow, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.252533.

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30

Murray, Ernest Jonathan. "Metalloporphyrins as hosts for anion transport." Thesis, University of Liverpool, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.263898.

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31

Nowosielski, Andrzej. "Alternative regimes for anion exchange denitrification." Thesis, Cranfield University, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.352928.

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32

Wilson, Thomas Charles. "Coordination chemistry of the pentacyanocyclopentadienide anion." Thesis, University of Cambridge, 2014. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.708033.

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33

Sullivan, Eirin Courtney. "Anion manipulation in perovskite-related materials." Thesis, University of Birmingham, 2009. http://etheses.bham.ac.uk//id/eprint/484/.

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Sr\(_2\)Co\(_2\)O\(_5\) with the perovskite-related brownmillerite structure has been synthesised via quenching, with the orthorhombic unit cell parameters \(a\) = 5.4639(3) Å, \(b\) = 15.6486(8) Å and \(c\) = 5.5667(3) Å based on refinement of NPD data collected at 4K. Electron microscopy revealed L R L R intralayer ordering of chain orientations which requires a doubling of the unit cell along the \(c\) parameter, consistent with the assignment of the space group \(Pcmb\). However, on the length scale pertinent to NPD, no long-range order is observed and the disordered space group \(Imma\) appears more appropriate. Low-temperature fluorination of this material and the related brownmillerite phases Sr\(_2\)CoFeO\(_5\) and Sr\(_2\)Fe\(_2\)O\(_5\) has been found to give different products depending on the starting material. Sr\(_2\)Co\(_2\)O\(_5\) and Sr\(_2\)CoFeO\(_5\) are amenable to fluorine insertion reactions with corresponding oxidation of transition metal cations, forming cubic perovskite phases of the nominal compositions SrCoO\(_{2.5}\)F\(_{0.5}\) (\(a\) = 3.8574(3) Å) and SrCo\(_{0.5}\)Fe\(_{0.5}\)O\(_{2.5}\)F\(_{0.5}\) (\(a\) = 3.872(2) Å). Fluorination of Sr\(_2\)Fe\(_2\)O\(_5\), however, results in a 1:1 mixture of two phases that were assigned to SrFeO\(_2\)F (\(a\) = 3.9481(3) Å) and SrFeO\(_{3-δ}\) (\(a\) = 3.8775(3) Å). Fluorine insertion into the oxygen defect superstructure manganite Sr\(_2\)MnO\(_{3.5+x}\) has been shown by TEM to result in two levels of fluorination. In the higher fluorine content sections, the fluorine anions displace oxygen anions from their apical positions into the equatorial vacancies, thus destroying the superstructure and giving a K\(_2\)NiF\(_4\) type structure (\(a\) = 3.8210(1) Å and \(c\) = 12.686(1) Å). Ce\(_2\)MnN\(_3\)F\(_{2-δ}\) with tetragonal symmetry (\(P4/nmm\) \(a\) = 3.8554(4) Å and \(c\) = 13.088(4) Å based on neutron powder diffraction) and a structure related to LaSrMnO\(_4\)F has been synthesised via low-temperature fluorination of the ternary nitride Ce\(_2\)MnN\(_3\). Two F\(^-\) anions are inserted but no F\(^-\)/N3\(^-\) substitution takes place, instead a structural rearrangement whereby one F\(^-\) expands the manganese coordination from four to six occurs and the second F\(^-\) inserts in alternate layers of interstitial sites, in a staged fashion. The effective magnetic moment in Ce\(_2\)MnN\(_3\)F\(_{2-δ}\), μ\(_{eff}\) = 5.38 μ\(_B\), is consistent with an intermediate value between that of Mn\(^{3+}\) (4.9 μ\(_B\)) and Mn\(^{2+}\) (5.9 μ\(_B\)) supporting the proposed stoichiometry, Ce\(_2\)MnN\(_3\)F\(_{2-δ}\).
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34

Hewett, David R. "Mixed anion amides for hydrogen storage." Thesis, University of Birmingham, 2012. http://etheses.bham.ac.uk//id/eprint/3696/.

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Metal hydride materials have attracted much interest for their potential use as hydrogen storage materials. Complex hydrides are amongst the most promising due to their high gravimetric storage capacities and favourable de/rehydrogenation conditions. Here, mixed anion complex hydrides are investigated both through halide doping of LiNH\(_2\) and Li\(_2\)NH, and though a mixed LiNH\(_2\)-LiBH\(_4\) system. The reaction of LiNH\(_2\) and Li\(_2\)NH with lithium or magnesium chloride, bromide and iodide has been shown to form a series of amide- and imide-halide phases. The structures of these phases were investigated through powder diffraction methods as well as Raman spectroscopy. The hydrogen releasing properties of these materials were investigated through reaction with LiH and MgH\(_2\); while the equivalent hydrogenation reactions were also tested. In both cases these materials performed more favourably than the pure LiNH\(_2\)-LiH system. The lithium ion conductivity of these materials was also investigated; it was shown that the most conducting materials were also the quickest to release and uptake hydrogen. The LiNH\(_2\)-LiBH\(_4\) system was studied, with particular focus on the decomposition product, Li\(_3\)BN\(_2\). All three known polymorphs of this compound were shown to be able to form by the reaction of \(_2\)LiNH\(_2\) + LiBH\(_4\) by carefully changing the reaction conditions. Further stages of this system were investigated through reaction of Li\(_2\)NH and Li\(_3\)N with LiBH\(_4\). Here the products from these reactions were studied along with the thermal desorption properties of the systems.
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35

Kilo, Martin, and Thomas Bredow. "Modelling of anion transport in YZrON." Universitätsbibliothek Leipzig, 2016. http://nbn-resolving.de/urn:nbn:de:bsz:15-qucosa-195357.

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36

Wang, Yizhou. "Regulation of guard cell anion channels." Thesis, University of Glasgow, 2013. http://theses.gla.ac.uk/3859/.

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Stomata account for much of the 70% of global water usage associated with agriculture, and have a profound impact on the water and carbon cycles of the world. Anion channels at the plasma membrane of the guard cell are thought to comprise a major pathway for anion efflux essential for driving stomatal closure. The activity of these channels is therefore tightly linked to abscisic acid (ABA)-dependent stomatal movements. Both the inorganic anion Cl- and the organic acid anion malate (Mal) are transported during stomatal movements. The metabolism of organic acids, primarily Mal plays an especially important role in these processes. However, little is known of the regulation of anion channel current (ICl) or its connection with cytosolic Mal and its immediate metabolite oxaloacetate (OAA). Work described here focuses on the relation of ICl and its connections with metabolism and signals controlling other transport at the guard cell plasma membrane. Thus the impact of Mal, OAA and of acetate in Vicia guard cells was examined, and results shown that all three organic acids affect ICl with different characteristics. Most prominent, the suppression of ICl by OAA within the physiological range in vivo indicates a capacity for OAA to co-ordinate organic acid metabolism with ICl through a direct effect of organic acid pool size. In a second set of studies, the ABA pathway that elevates cytosolic free Ca2+ ([Ca2+]i) in order to activate ICl was explored. These studies build on the discovery of PYR/PRL ABA receptors. Previous analysis of the pyr1/pyl1/pyl2/pyl4 mutant suggested that [Ca2+]i increases are suppressed. However, direct evidence had not been forthcoming. Thus a combination of voltage clamp and fluorescent ratio analysis with the Ca2+-sensitive dye Fura2 was used to show that the activity of Ca2+ channels (ICa) at the plasma membrane in the pyr1/pyl1/pyl2/pyl4 mutant is not activated in ABA, with the effect that [Ca2+]i increases were suppressed. Further studies showed that the normal action of ABA in promoting reactive oxygen species (ROS) was impaired, although adding H2O2 was sufficient to activate the ICa and trigger stomatal closure in the mutant. These results offer direct evidence that the PYR/PYL receptor proteins contribute to the activation by ABA of ICa through ROS, thus affecting [Ca2+]i and its regulation of osmotic solute flux for stomatal closure. Finally, the connection between ICl and the K+ channel currents in the slac1 mutant of Arabidopsis was studied. These studies employed systems dynamic modelling to explain the paradoxical suppression of the inward-rectifying K+ channel current, IK,in and slowing of stomatal opening, by mutation that eliminated the SLAC1 anion channel. Experimental results confirmed the model predictions that the abnormal cytosolic pH (pHi) and [Ca2+]i suppresses IK,in in the slac1 mutant, through measuring pHi and [Ca2+]i in vivo, and experimental manipulation of pHi and [Ca2+]i is sufficient to recover IK,in and stomatal opening. These data uncover a previously unrecognised signaling network that minimises the effects of the slac1 mutant on transpiration, and they underscore the importance of H+-coupled anion transport for pHi homeostasis.
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37

Paver, Michael A. "Novel p-block metal anion complexes." Thesis, University of Cambridge, 1995. https://www.repository.cam.ac.uk/handle/1810/271941.

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38

Kilo, Martin, and Thomas Bredow. "Modelling of anion transport in YZrON." Diffusion fundamentals 2 (2005) 22, S. 1-2, 2005. https://ul.qucosa.de/id/qucosa%3A14352.

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39

Kafy, Ahmed M. L. A. E. "Interactions between oligoamines and superoxide anion." Thesis, Aston University, 1987. http://publications.aston.ac.uk/12556/.

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1- Oligoamines and EDTA inhibited the reduction of cytochrome-C and nitrobule tetrazolium (NBT) induced by the hypoxanthine/xanthine oxidase superoxide anion generating system in the following order of effectiveness: putrescine > diaminopropane > spermidine > EDTA > spermine > cadaverine. 2- Oligoamines and EDTA did not affect the rate of urate formation from the hypoxanthine/xanthine oxidase system. 3- Oligoamines and EDTA inhibited the reduction of cytochrome-C induced by stimulated PMNL's in the same order of effectiveness as mentioned before. 4- Oligoamines and EDTA inhibited luminol dependent stimulated PMNL's chemiluminescence. 5- Oligoamines and EDTA inhibited the aerobic photoreduction of NBT. 6- Oligoamines-copper sulphate complexes inhibited the reduction of cytochrome-C induced by the hypoxanthine/xanthine oxidase system more effectively than oligoamines or copper sulphate individually. 7- Superoxide anion, hydrogen peroxide and hydroxyl radical induced breakdown of isolated intact guinea pig liver lysosomes. 8- Oligoamines and EDTA protected isolated intact guinea pig liver lysosomes from the lytic effect of superoxide anion generated either by the hypoxanthine/xanthine oxidase system or by stimulated PMNL's. 9- Oligoamines and EDTA have no stabilizing effect on isolated intact guinea pig liver lysosomes. 10- The uptake of oligoamines by lysosomes was in the following order: putrescine > spermidine > spermine. 11- Oligoamines were metabolised into aldehyde compounds either by the hypoxanthine/xanthine oxidase system or stimulated PMNL's. 12- Oligoamines and EDTA have no effect on the activities of free lysosomal enzymes (acid phosphatase and -glucosaminidase). 13- Oligoamines and EDTA inhibited lipid peroxidation in guinea pig liver lysosomes induced either by the hypoxanthine/xanthine oxidase or ascorbic acid-ferrous sulphate. 14- Oligoamines and EDTA have no effect on the release of PGE_2 from stimulated peritoneal guinea pig PMNL's. 15- Oligoamines increased the uptake of (^3H)thymidine and (^3H)leucine by stimulated peritoneal guinea pig macrophages in the following order of effectiveness: spermine > spermidine > putrescine > cadaverine. 16- PGE_2, dibutyryl Cyclic AMP, and theophylline inhibited luminol dependent stimulated peritoneal guinea pig PMNL's chemiluminescence.
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40

Smyth, Megan Rebecca. "Chiral hosts for enantioselective anion recognition." Thesis, Queen's University Belfast, 2016. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.709822.

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This research thesis considers the synthesis of a novel library of symmetrical and unsymmetrical 2,2-bipyridine ligands containing both amide functionality and chirality. These ligands were then used to develop either a labile system containing iron(II) or an inert system comprised of ruthenium(II) complexes. The inclusion of chirality in the bipyridine ligand, from the synthesis with a chiral amine, resulted in a diastereomeric excess in the resulting metal complexes, observable using circular dichroism spectroscopy. Further enhancement of this diastereomeric excess was observed in the presence of particular anions. It was found that addition of certain anions would result in the degeneration of the iron(II) bipyridyl complex thus eliminating these anions as potential stimuli to perturb a dynamic iron(II) bipyridyl system. The stability of the iron(II) bipyridyl complex was also found to be affected by solvent, temperature and the counter anion. The use of chiral bipyridine ligands with ruthenium(II) afforded a mixture of isomers dependent on whether the ligand was mono- or difunctionalised. This thesis reports the separation of the ruthenium(II) complexes of unsymmetrical ligands in the respective isomers to afford enantiopure material. The anion binding properties were then studied using 1H NMR spectroscopic titrations with chloride anions. A ruthemum(II) bipyridine metal complex with non-chiral ligands was also synthesised and separated into the four isomers, first by preparative plate chromatography followed by cation-exchange chromatography* on Sephadex SP-C25 to obtain enantiopure material. These diastereomers were investigated using 1H NMR, UV/vis, emisson and CD spectroscopy, with the addition of the enantiopure chiral anion mandelate showing some potential diastereoselectivity.
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41

Qin, Lei. "Squaramide-based Receptors for Anion Recognition." Thesis, The University of Sydney, 2017. http://hdl.handle.net/2123/17808.

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A series of squaramide based receptors bearing benzene and pyridine linkers was developed, ranging from simple alkyl-substituted mono-squaramides to macrocyclic tri-squaramides by altering the number of squaramide binding sites, adjusting the geometries of compounds and appending different solubilizing groups. These receptors were studied via host-guest 1H NMR titrations with a range of anions in DMSO-d6 and water. In this work, the successful trial of aqueous soluble, macrocyclic squaramide receptors (MSQs) were synthesized that bind sulfate with high affinity and selectivity over other tetrahedral divalent anions in aqueous media up to 50% v/v H2O/DMSO-d6. In mixtures of anions mimicking the composition of either nuclear waste or plasma, the MSQs were still able to bind sulfate ions with high affinity. Encouraged by these results, another library of MSQs was synthesized for sulfate extraction and transport by appending alkyl chains to the macrocycles. According to the sulfate concentration monitored by ion chromatography, MSQs are able to extract approximately 15% sulfate from aqueous solutions under the experimental conditions used. Sulfate transport experiments monitored by ICP-OES suggests that approximately 0.4% of sulfate was carried across a bulk chloroform membrane after 15 days. Furthermore, in order to investigate more complicated structures for anion recognition, a small family of (thio)urea and (thio)squaramide based anion receptors and their corresponding rotaxanes were developed in collaboration with Prof. Steve Goldup at the University of Southampton. According to anion titrations experiments with a range of anions in CDCl3, CD3CN, the thread and rotaxane behave differently, as the thread is an anion binder whereas the rotaxane switch binds ion-pairs with a charge separated binding mode (i.e., a heteroditopic receptor). Meanwhile, the thread and rotaxane also exhibit different selectivities for anions.
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42

Groenewald, Ferdinand George. "Computational study of anion-anion intermolecular interactions between I3-ions in the gas phase, solution and solid state." Thesis, Stellenbosch : Stellenbosch University, 2012. http://hdl.handle.net/10019.1/71786.

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43

Lane, Jakob. "Dual Hydrogen Bond Donors for Anion Recognition." Thesis, The University of Sydney, 2021. https://hdl.handle.net/2123/27262.

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Anions are important in many biological and chemical processes, therefore the development of receptors for binding, sensing and extraction is necessary for a range of potential applications, including in medicine and the environment. This thesis details both the development of novel dual hydrogen bonding receptors for anions, and work towards anion sensing and extraction using dual hydrogen bonding motifs. Chapter 2 describes the synthesis and anion binding investigations into the dual hydrogen bond donating motifs diaminomethylenemalononitriles and diaminomethyleneindanediones. Two novel series of compounds were synthesised and anion affinity and selectivity determined in organic solvent via 1H NMR titrations, crystallographic and computational analysis. Anion binding properties are compared to the widely researched thiourea motif. In Chapter 3, the powerful dual H-bond donating squaramide moiety is appended with fluorophores either directly or through a methylene spacer to produce a library of novel fluorogenic squaramide receptors. The acidity of these squaramides substituents was determined experimentally in order to understand their behaviour in DMSO. UV-Vis and fluorescence anion screens and titrations were performed, which indicate that ratiometric anion sensing can take place in DMSO, induced by aggregation/disaggregation mechanisms upon interaction with anions. Selectivity was observed for interaction with sulfate, acetate and dihydrogen phosphate, with interaction with sulfate resulting in the greatest fluorescence response for all receptors. Chapter 4 describes the development of squaramide-functionalised polymers for anion sensing and extraction. Water soluble polyethylene glycol methyl methacrylate based polymers were functionalised with squaramides and anion binding investigated by UV-Vis and fluorescence screens, and by 1H NMR titration. When dissolved in water, the squaramide appended polymer undergoes a phase transition upon heating. This is exploited to lead to anion extraction that offers selectivity for sulfate and dihydrogen phosphate over anions that are bound less strongly by the squaramide moiety.
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44

Cook, Gabriel Allen. "Structural studies of anion channel forming peptides /." Search for this dissertation online, 2005. http://wwwlib.umi.com/cr/ksu/main.

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45

Crowhurst, Karin Ann. "Refurbishing alamethicin, a path to anion selectivity." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1997. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp04/mq29222.pdf.

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46

Cormode, David. "Porphyrin and gold surface based anion receptors." Thesis, University of Oxford, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.432558.

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47

Tiwari, Laxmikant. "Design and synthesis of novel anion receptors." Thesis, University of Oxford, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.312677.

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48

Rutt, Oliver J. "The synthesis of novel mixed anion solids." Thesis, University of Oxford, 2007. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.442960.

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49

Kingston, Justine E. "Redox-active host molecules for anion recognition." Thesis, University of Oxford, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.320669.

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50

Hancock, Laura M. "Anion-templated synthesis of functional interlocked architectures." Thesis, University of Oxford, 2011. http://ora.ox.ac.uk/objects/uuid:d4f141f6-fd44-49cc-b14b-0dec22679c75.

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This thesis explores the use of anions in the design and construction of interlocked architectures for applications in anion recognition and sensing, and to function as molecular machines upon a given stimulus. Chapter One introduces the field of anionic supramolecular chemistry focusing on host-guest chemistry and directed self-assembly. A review of the recognition and sensing of anionic guest species is given before strategies for the construction of interlocked architectures are discussed, and the potential functions of these structures considered. Chapter Two details the development of a novel anion-templation route for the synthesis of macrocycles and rotaxanes. The versatility of this route in constructing new [2]rotaxanes is explored by varying several features of the macrocyclic component, with emphasis on creating the most powerful anion complexant. Proton NMR spectroscopy is used to probe the anion binding properties of the rotaxanes, and X-ray crystallography and MD simulations are used to rationalize anion binding trends. The possibility of synthesizing catenanes for anion recognition via this new synthetic route is also investigated. Chapter Three investigates the appendage of transition metal complexes to rotaxanes to create interlocked host architectures capable of sensing anions via luminescence spectroscopy. The incorporation of rhenium(I) and ruthenium(II) polypyridyl complexes into the macrocyclic and axle component of [2]rotaxanes are described, before the anion binding studies of these structures using ¹H NMR and luminescence spectroscopy are reported. Chapter Four describes the strategic synthesis of [2]rotaxanes designed to undergo molecular motion upon a given stimulus. Initially, the possibility of exploiting anions to stimulate the macrocyclic component of the [2]rotaxanes to translocate to a second station on the axle is investigated. The use of pyridine N-oxide as an integrated template for rotaxane formation is reported before the ability of these rotaxanes to undergo anion and pH driven molecular motion is explored. This chapter concludes with the construction of a calix[4]diquinone N-oxide containing [2]rotaxane capable of undergoing sodium- and barium-induced molecular pirouetting. Chapter Five provides synthetic procedures and characterisation details for compounds listed in this thesis. Chapter Six reports supplementary experimental information including titration protocols, X-ray crystal structures and MD simulations.
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