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FABRICATION OF SOL-GEL FILMS BASED ON ELECTROCHEMICALLY ASSISTED DEPOSITION PROCESSINGMehdi, Beata Layla 08 May 2013 (has links)
No description available.
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TRYPTAMINE TERMINATED 1st GENERATION POLYAMIDE DENDRIMER:SYNTHESIS AND DRUG RELEASEKomurcu, Ramazan January 2007 (has links)
No description available.
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POLYMERIC REAGENTS IN SOLID-PHASE SYNTHESES OF SMALL MOLECULES AND DENDRIMERSLu, Yuhua 06 August 2004 (has links)
No description available.
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Intramolecular Communication of Peptide-Dendrimer Hybrids and the Self-Assembly of Polymerizable NDI-Diacetylene Amphiphilic NanotubesBewick, Nicholas Andrew January 2014 (has links)
No description available.
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Effect of localized structural perturbations on dendrimer structureGabriel, Christopher J. 14 September 2006 (has links)
No description available.
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CHIRALITY TRANSFER AND ELECTRON TRANSFER IN DENDRITIC COMPLEXES WITH STABLE SECONDARY STRUCTUREHe, Dian 07 October 2008 (has links)
No description available.
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Molecular modeling of the complexation of proteins with strong anionic polyelectrolytesXu, Xiao 07 May 2018 (has links)
In dieser Arbeit untersuchen wir die elektrostatische Komplexierung zwischen Proteinen und anionischen, linearen bzw. dendritischen Polyelektrolyten mittels Molekulardynamik Simulationen in implizitem Lösungsmittel und mit expliziten Salzen. Die Proteine und Polyelektrolyte werden mit vergröberten Details simuliert. Jedes vergröberte Segment repräsentiert eine Aminosäure oder eine sich wiederholende chemische Untereinheit des Polyelektrolyten. Die Vergöberung ermöglicht Simulationen von großen Proteinen wie Humanalbumin oder dendritischen Polyelektrolyten, ohne dabei die essentiellen elektrostatischen Eigenschaften der Moleküle zu vernachlässigen. Wir validieren unsere Simulationen durch Kalorimetrieexperimente. Zur Interpretation der resultierenden Bindungs-freien Energien schlagen wir Theorien vor, die auf Gegenionen-Kondensation und Ladungs-Renormalisierung basieren. Die Arbeit zeigt die äußerst wichtige Bedeutung der kondensierten Gegenionen auf, die in allen untersuchten Systemen an der elektrostatischen Komplexierung teilhaben. Sowohl bei linearen als auch dendritischen Polyelektrolyten bewirken die kondensierten Gegenionen Ladungsrenormalisierung, die die elektrostatischen Wechselwirkungen in den Systemen abschwächt. Die Bindung wird durch die Freisetzung von Gegenionen bewirkt, was mit einem massiven Anstieg der Entropie einhergeht. Aufgrund der multivalenten Bindung können
unsere Ergebnisse nicht mithilfe des konventionellen Langmuir-Adsorptionsisothermen interpretiert werden. Daher schlagen wir eine neuartige Interpretation der Langmuir-Adsorptionsisothermen vor, die einen sinnvollen Vergleich zwischen Simulationen und Experimenten ermöglicht. / In this thesis, we conducted a comprehensive study of the electrostatic complexation between proteins and anionic linear/dendritic polyelectrolytes, by means of molecular dynamics simulations with implicit solvent and explicit salt. The proteins and polyelectrolytes are both represented in a coarse-grained fashion. Each coarse-gained segment represents either an amino acid residue or the repeating chemical subunit of the polyelectrolyte. This modeling
strategy allows for simulations of big proteins such as human serum albumin and dendritic polyelectrolytes of large generations, while the crucial molecular electrostatic properties are still well retained. Our simulations are validated further by calorimetry experiments. Finally, we propose theories based on counterion condensation and charge renormalization for interpreting the system binding free energies. Regarding all systems investigated here, the thesis demonstrates the crucial and ubiquitous role of condensed counterions which participates in the electrostatic complexation. For both linear and dendritic polyelectrolytes, we find a strong charge renormalization induced by
the condensed counterions, which consequently suppresses electrostatic interactions to an appreciable extent. The resultant binding is governed by the release of those condensed counterions, resulting in a massive entropy gain. Due to the presence of the multivalent binding, we propose a new interpretation of the conventional Langmuir adsorption isotherm, which ensures a meaningful comparison between simulations and experiments.
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Elastin-Like Peptide Dendrimers: Design, Synthesis, and ApplicationsZhou, Mingjun 02 July 2019 (has links)
Elastin like peptides (ELPs)—derived from the protein elastin—are widely used as thermoresponsive components in biomaterials due to their LCST (lower critical solution temperature) behavior at a characteristic transition temperature (Tt). While linear ELPs have been well investigated, few reports focused on branched ELPs. Using lysine (Lys, with an additional side-chain amine) as branching units, ELP dendrimers were synthesized by solid-phase peptide synthesis (SPPS) with up to 155 amino acid residues. A secondary structure change with decreasing ratio of random coil and increasing ratio of β-turn upon heating, which is typical of linear ELPs, was confirmed by circular dichroism spectroscopy for all peptides. Conformational change did not show evident dependence on topology, while a higher Tt was observed for dendritic peptides than for their linear control peptides with the same number of GLPGL repeats. Variable-temperature small-angle X-ray scattering (SAXS) measurements showed a size increase and fractal dimension upon heating, even below the Tt. These results were further confirmed by cryogenic transmission electron microscopy (cryo-TEM), and micro differential scanning calorimetry (micro-DSC), revealing the presence of aggregates below the Tt. These results indicated the presence of a pre-coacervation step in the LCST phase transition of the ELP dendrimers.
We further prepared hydrogels by crosslinking hyaluronic acid (HA) with ELP dendrimers. We invesigated their physical properties with scanning electron microscopy (SEM), swelling tests, SAXS, and model drug loading/release experiments. Most of the HA_denELP hydrogels retained transparent upon gelation, but after lyophilization and reswelling remained opaque for days. This reswelling process was carefully investigated with time-course SAXS studies, and was attributed to forming pre-coacervates in the gelation step, which slowly reswelled during rehydration. We then prepared hydrogels with H2S-releasing aroylthiooxime (SATO) groups and showed human neutrophil elastase-responsive H2S-releasing properties with potential applications in treating chronic diseases with recurring inflammation.
Furthermore, we prepared a series of wedge-shaped triblock polyethylene glycol (PEG)-ELP dendrimer-C16 (palmitic acid) conjugate amphiphiles with adjustable Tts. Various techniques were used to investigate their hierarchical structures. The triblock PEG-peptide-C16 conjugate amphiphiles were thermoresponsive and showed a morphology change from small micelles to large aggregates. However, the hydrophilic shell and strong tendency for micelle formation limited the thermoresponsive assembly, leading to slow turbidity change in the LCST transition. The secondary structure was twisted from conventional β-sheet, and the thermoresponsive trend observed in typical ELP systems was not observed, either. Variable temperature NMR showed evidence for coherent dehydration of the PEG and ELP segments, probably due to the relatively short blocks. Utilizing the micelles with hydrophobic cavity, we were able to encapsulate hydrophobic drugs, with promising applications for localized drug release in hyperthermia. / Doctor of Philosophy / Elastin like peptides (ELPs) are similar to the protein elastin in terms of amino acid sequence. They are used widely as thermoresponsive (change in properties at different temperatures) components in biomaterials due to their abnormally lower solubility at higher temperatures. While linear ELPs have been thoroughly investigated, few investigations in ELP dendrimers have been studied. Dendrimers are molecules that branch in a controlled way to achieve sphere-like structures with rich surface functionalities. We synthesized the ELP dendrimers by using lysine amino acids as branching units. A protein secondary structure change, typical of ELPs, was observed for all peptide dendrimers. Secondary structure transitions showed no dependence on the molecular branching/linear structures, but a higher transition temperature (T<sub>t</sub>) was observed for dendritic peptides than for their linear control peptides with the same number of amino acids. Various techniques confirmed the existence of aggregates below the T<sub>t</sub>s, which was never reported before. We further fabricated hydrogels that mimic the native extracellular matrix, by connecting hyaluronic acid (HA) with ELP dendrimers. Interestingly, most of the hydrogels studied retained transparent upon gelation, but after freeze-drying and addition of water remained opaque for days. This phenomenon was attributed to forming of small aggregates in the gelation step, which resulted in slow reswelling. We then prepared hydrogels with H₂S-releasing groups, which showed human neutrophil elastase-responsive H₂S-releasing properties with potential applications in treating chronic diseases with recurring inflammation.
We then prepared a series of wedge-shaped triblock poly (ethylene glycol) (PEG)- ELP dendrimer-alkyl chain molecules. The triblock molecules were thermoresponsive and showed a change from small spheres to large aggregates. However, the hydrophilic shell limited the thermoresponsive assembly, leading to slow turbidity change in the LCST transition. We found evidence of coherent assembly of the PEG and ELP parts, probably due to the relatively short polymer chains. Utilizing the micelles with hydrophobic cavity, we were able to encapsulate hydrophobic drugs, with promising applications for localized drug release for cancer treatment.
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Polysulfurated aromatic compounds : Préparation and photophysical propertiesFermi, Andrea 17 April 2013 (has links)
Durant mon Doctorat de Sciences Chimiques, effectué en cotutelle entre l'Université de Bologne et l'Université de Aix-Marseille, j'ai pris en charge la synthèse et la caractérisation d'une série de composés aromatiques soufrés qui bénéficient de propriétés photophysiques intéressantes. Ce travail de thèse a été concentré sur deux classes de composés : la première s'apparente à des astérisques moléculaires contenant un coeur benzénique persoufré, fonctionnalisé avec des unités périphériques aromatiques. Dans chaque cas, des groupes stériquement encombrants ont été greffés sur les unités aromatiques situées à la périphérie des molécules. Ces molecules offrent la capacité de fonctionner comme luminophore AIE (Emission Induite par l'Agrégation) à l'état solide ou dans des milieux à haute rigidité. La deuxième famille de molécule est basée sur la même géométrie en astérisque. Cependant, chaque ligand de cette série utilise des unités terpyridyles comme unité périphérique, capables d'interagir avec des métaux de transition comme le fer(III) et le zinc. Suite à la complexation du zinc les propriétés photophysiques peuvent être modulées en fonction de la rigidité du système. Enfin, on a synthetisé un troisième type de système qui a été obtenu par le remplacement du coeur benzénique des astérisques par une fonction pyrene polysoufrée, en conservant les mêmes unités périphériques. Ce composé a montré des propriétés photophysiques intéressantes mais aussi des capacités de coordinations vers les ions métalliques (Fe(III), Zn(II) et le Nd(III)), ce qui a permis la génération d'émission dans le domaine du proche infrarouge. / The aim of this thesis was the synthesis and photophysical characterization of some new polysulfurated aromatic compounds: this class of molecules can offer intriguing properties, potentially useful for the construction of new materials for optoelectronic devices. Two main families of compounds have been synthesized: the first is represented by a series of small molecular asterisks, with peripheral aromatic units, showing luminescence in solid phase or in highly rigid conditions. All compounds with peripheral substituents display an AIE behavior (Aggregation Induced Emission) with radiative deactivation of the triplet states. Taking inspiration from these smaller asterisks, a larger molecule with the same geometry has been designed, decorated with terpyridyl moieties as the outermost units: this compound shows great affinity for the coordination of several transition metal ions, changing luminescence properties after the interaction with zinc ions. With the same intentions, a tetrasulfurated pyrene-core molecule with terpyridyl external units has been synthesized and isolated: this ligand exhibits good coordination capabilities towards transition metal ions, giving rise to luminescent nanoaggregates upon addition of zinc(II), characterized by DLS and AFM microscopy. In addition a NIR emission is recorded after coordination of neodymium(III), showing evidence of an intramolecular energy transfer process.
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Modellering en sintese van alisikliese dendrimeerligande vir alkeenmetatese / Deseré LiebenbergLiebenberg, Deseré January 2010 (has links)
Coupling homogeneous catalysts to dendrimers with rigid nuclei is one possible strategy to recycle
these compounds in an industrial environment. During this study attempts were made to attach the
well-defined ruthenium carbene complex 2 to the alicyclic compound 1A. To achieve this goal
attempts were made to functionalise 1A with anime groups to facilitate the attachment of
phosphine groups. The catalyst 2 would then be attached through a phosphine exchange reaction.
Oximes were used as precursors in attempts to prepare cage amines from 1A. For this purpose,
the dioxime 28 was prepared from 1A. Reduction of 28 was unsuccessful. Molecular modelling
showed that the lobes of the LUMOs of the oxime carbon atoms of 28 do not protrude from the
total electron density of this molecule. This observation indicates that 28 would probably not react
with nucleophiles, such as the hydride ion. Molecular modelling was used to probe the unreactive
nature of oxime 28. The probe revealed that the imide ring deactivates the oxime groups in this
compound.
Based on these results, attempts were made to change the carbon framework of 1A to eliminate
unwanted interaction between the carbonyl groups. Clemmensen reduction of 1A did not yield the
expected ketol 40, but gave a mixture of 62 and 63. Extended reaction times yielded 63 only.
Reduction of 1A with zinc and acetic acid produced a mixture of 62 and 40 that could not be
separated. Consequently, the applicability of 62 as a possible dendrimer nucleus was investigated.
Compound 62 was obtained by oxidisation of the diol 63 with sodium periodate. Attempts to
synthesise the dioxime 69 from 62 failed and only the mono oxime 71 was obtained.
Reduction of 71 with lithium aluminium hydride was unsuccessful. Molecular modelling revealed
that the oxime carbon atom does not have a LUMO and that the carbonyl carbon atom would
probably be unreactive towards nucleophiles. Several other attempts were made at reducing the
oxime 71 to an amine. None of these attempts met with any success. The reason for the
unreactive nature of 71 is less clear than in the case of 28.
Failure to produce a cage amine from 1A or derivatives of 1A meant failure in functionalising the
cage system with phosphine groups and coupling the Grubbs-I catalyst. It seems that cage compounds based on 1A are generally not suitable as starting materials for amine-functionalised
dendrimer nuclei. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2011.
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