21 |
Interações entre nanocristais semicondutores de CdTe e complexos polipiridínicos de rutênio (ll)Bispo, Thalita Santos 13 May 2016 (has links)
In this work Ru(II) polypyridine complexes were used as redox active molecules to
study interactions with quantum dots (QDs) surface. The synthesis of cadmium
telluride (CdTe) quantum dots passivated with the organic stabilizer mercaptopropionic
acid (MPA) and with stabilizer mixture of MPA and L-cysteine (CYS) was carried out
in aqueous solution via hydrothermal heating, and the synthesis parameters such as
pH and Cd/Te/stabilizer ratio were fixed according to the literature. The colloidal
dispersion was characterized by UV visible absorption spectroscopy, as well as
infrared and photoluminescence. Absorption spectra were broad with a single band
and the emission showed band maxima at 612 nm and 598 nm for CdTe-MPA and
CdTe-MPA/CYS (labelled in this work as CdTe-CYS) respectively (indicating quantum
confinement). Particle diameters were calculated using a cubic empirical formula
based on the maximum absorption wavelength. Cyclic voltammetry showed the
presence of anodic and cathodic peaks corresponding to redox processes of CdTe
QDs. Electrochemical band gaps were estimated from the onset values of oxidation
and reduction peaks, finding a correspondence with the optical band gaps estimated
from absorption and emission spectra. Polypyridine ruthenium(II) complexes
[Ru(bpy)3](PF6)2 and [Ru(Me-bpy)3](PF6)2 (labelled in this work as Ru-1 and Ru-2,
respectively) were synthesized via hydrothermal method for 72 h at 170ºC. The solids
obtained were characterized by UV visible spectroscopy and the main transitions
involved in the polypyrinde complexes were observed. Fluorescence spectroscopy
exhibited a band assigned to the radiative deactivation of the lowest energy excited
state (3MLTC). A redox pair of the complex was observed in the cyclic voltammograms,
assigned to Ru2+/Ru3+ metal center. The possibility of interactions between the
quantum dots and the complexes was evaluated by electrochemical measurements.
Anodic differential pulse voltammograms showed that the redox potentials of QDs were
modified due to the presence of the Ru(II) polypyridine complexes onto the QD’s
surfaces. Oxidation peak from QDs was shifted to more positive values while the
complexes’s redox peaks shifted to less positive values, indicating that the system
shows characteristics of a nanocrystal molecular conjugated. / Neste trabalho utilizou-se complexos polipiridínicos de Ru(II) como molécula
redox ativa no estudo da interação com a superfície dos quantum dots (QDs). A
síntese dos quantum dots de Telureto de Cádmio (CdTe) passivados com o
estabilizante orgânico MPA (ácido mercaptopropiônico), e com a mistura de
estabilizantes MPA e CYS (� – Cisteína) foi realizada em solução aquosa, via
hidrotermal, e os parâmetros de síntese, como pH e relação Cd/Te/estabilizantes
fixados conforme a literatura. A dispersão coloidal foi caracterizada por espectroscopia
de absorção no UV Visível, no infravermelho e de emissão. Os espectros de absorção
se apresentaram largos com apenas uma banda, e de emissão com máximo em 612
e 598 nm, para CdTe-MPA e CdTe-MPA/CYS (nomeado neste trabalho como CdTe-
CYS), respectivamente (indicando confinamento quântico). Os diâmetros das
partículas foram calculados usando-se uma fórmula empírica cúbica, a partir do
comprimento de onda máximo de absorção. A voltametria cíclica mostrou a presença
de picos anódicos e catódicos correspondentes a processos redox dos QDs de CdTe.
Os band gaps eletroquímicos foram estimados pelos valores dos onsets e dos picos
de oxidação e redução e encontrados correspondência com os band gaps ópticos
estimados a partir dos espectros de absorção e emissão. Os complexos polipiridínicos
de rutênio (II), [Ru(bpy)3](PF6)2 e [Ru(Me-bpy)3](PF6)2 (nomeados neste trabalho como
Ru-1 e Ru-2, respectivamente), foram sintetizados através do método de síntese
hidrotermal por 72 h a 170 ºC. O sólido obtido foi caracterizado por espectroscopia de
absorção no UV Visível e principais transições eletrônicas envolvidas nos complexos
polipiridínicos foram observadas, a espectroscopia de fluorescência exibiu a banda
atribuída a desativação radiativa do estado excitado de menor energia (3TCML). Na
voltametria cíclica foi observado um par redox do complexo atribuído ao centro
metálico Ru(II)/(III). A possibilidade de interação entre os quantum dots de CdTe e os
complexos foi avaliada por medidas eletroquímicas. Voltamogramas de pulso
diferencial anódico mostraram que os potenciais redox dos QDs são modificados
devido a presença dos complexos polipiridínicos de Ru(II) na superfície dos QDs. Os
picos de oxidação dos QDs foram deslocados para potenciais mais positivos enquanto
o pico redox dos complexos deslocou para potenciais menos positivos, indicando que
o sistema exibiu características de um conjugado nanocristal-molecular.
|
22 |
Micropartículas produzidas por gelificação iônica recobertas com gelatina de peixe e isolado proteico de soja / Microparticles produced by ionic gelation coated with fish gelatin and isolated soy proteinCosta, Bianca Souza da, 1990- 24 August 2018 (has links)
Orientador: Carlos Raimundo Ferreira Grosso / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-24T10:13:53Z (GMT). No. of bitstreams: 1
Costa_BiancaSouzada_M.pdf: 3645103 bytes, checksum: ee9884c2d54163da7814b0ea032a53c5 (MD5)
Previous issue date: 2014 / Resumo: O objetivo deste trabalho foi produzir partículas de pectina e alginato por gelificação iônica, com posterior recobrimento com isolado proteico de soja (IPS), gelatina de pele de tilápia (GPT) e com a mistura dessas duas proteínas (IPS:GPT), avaliando suas características físico-químicas e seu comportamento frente a diferentes tratamentos. No estudo preliminar foram analisadas as condições que promovessem a carga elétrica livre que otimizassem a interação entre os polissacarídeos e proteínas, formando complexos insolúveis. A partir desses ensaios foram estabelecidas as seguintes proporções de polissacarídeo: proteína e valores de pH: 1:2 em pH4 para recobrimento com gelatina de pele de tilápia, e 1:0,75 em pH3 para interação com o isolado proteico de soja e para a mistura das duas proteínas. Foram testados 4 níveis de proteína em solução ( 1, 2, 4 e 8 %) para recobrimento das partículas de pectina e alginato. As partículas obtidas foram caracterizadas pelo teor de umidade, conteúdo proteico adsorvido e pela sua morfologia. A partir deste estudo preliminar foi selecionada a concentração de 8% de proteína em solução, devido à produção de partículas com alto teor proteico. Estas partículas foram avaliadas com relação à sua estabilidade frente a variações de pH, diferentes concentrações de NaCl e sob simulação das condições gastrointestinais in vitro. Utilizando a concentração de 8% de proteína em solução foram obtidos altos valores de adsorção proteica, resultando no percentual de proteína de 61,87%, 47,61% e 52,06% para as partículas recobertas com GPT, IPS e IPS:GPT, respectivamente. A variação de pH e das concentrações de sal influenciaram na solubilidade da camada proteica, apresentando uma maior solubilidade em condições de extrema acidez (pH 1) e a medida em que aumentava a concentração de sal. Nas faixas de pH (1 a 7) e nas concentrações de NaCl (0 a 584 mM) estudadas, independente do valor da solubilidade proteica obtida, todas as partículas permaneceram íntegras. No ensaio gastroentérico in vitro, as partículas de pectina e alginato (PEC:ALGPart) sem recobrimento e as recobertas com gelatina de pele de tilápia (GPTPart) foram resistentes as condições gástricas e entéricas, permanecendo íntegras. As partículas recobertas com isolado proteico de soja (IPSPart) e com a mistura de proteínas (IPS:GPTPart), foram resistentes às condições gástricas, porém desintegraram-se em meio intestinal, liberando o material encapsulado / Abstract: The aim of this work was to produce particles of pectin and alginate by ionic gelation with subsequent coating with isolated soy protein (IPS), tilapia skin gelatin (GPT), and a mixture of these two proteins (IPS:GPT), evaluating their physico-chemical characteristics and behavior to different treatments. In the preliminary study, the conditions that promote the balance of free electrical charge due the interaction between polysaccharides and proteins were analyzed. From these tests the following proportions of polysaccharide:protein and pH values were established: 1:2 at pH 4 for covering with tilapia skin gelatin, and 1:0.75 at pH3 for interaction with the isolated soybean protein and mixing of the two proteins. Four protein levels were tested (1, 2, 4 and 8%) in solutions for coating the particles of pectin and alginate. The particles obtained were characterized by moisture content, adsorbed protein content and their morphology. From this preliminary study it was selected the concentration of 8% protein solution, due to the production of particles with high protein content. These particles were evaluated for their stability against pH changes, different concentrations of NaCl and simulation under the simulated gastrointestinal conditions. Using a concentration of 8% protein solution high levels of protein adsorption were obtained, resulting in percentage of protein adsorbed of 61.87%, 47.61% and 52.06% for the coated particles GPT, IPS and IPS: GPT, respectively. The variation of pH and salt concentrations influence the solubility of the protein layer having a higher solubility in conditions of extreme acidity (pH 1) and the extent to which increased salt concentration. In the pH ranges and concentrations of NaCl studied, regardless of the amount of protein solubility obtained, all the particles remained intact. In the gastrointestinal assay, pectin and alginate particles (PEC: ALGPart) uncoated and coated particles with tilapia skin gelatin (GPTPart) were resistant to the gastric and enteric conditions, remaining intact. The coated particles with isolated soy protein (IPSPart) and the protein mixture (IPS:GPTPart) were resistant to gastric conditions, but disintegrated in the intestinal environment, releasing the encapsulated material / Mestrado / Nutrição Experimental e de Alimentos / Mestra em Alimentos e Nutrição
|
23 |
Propriétés électrostatiques, mécaniques et chémodynamiques de (bio)interphases molles : analyses en régime d'équilibre et transitoire / Electrostatic, mechanical and chemodynamic properties of soft (bio)interphases : Analyses in equilibrium and transitory regimesMerlin, Jenny 04 June 2012 (has links)
Dans les milieux naturels, la matière solide est essentiellement présente sous la forme de (bio)particules molles perméables aux ions et aux flux hydriques. Ces particules sont sans cesse soumises à des perturbations électriques/mécaniques, de telle sorte que les propriétés physico-chimiques des (bio)interphases qu'elles forment avec le milieu évoluent continûment dans le temps. Les (bio)interphases ne sont donc pas nécessairement à l'équilibre durant les processus interfaciaux (interactions électrostatiques, complexation de métaux). Dans ce contexte, nous avons évalué théoriquement l'énergie d'interaction électrostatique à l'équilibre entre (bio)particules molles multicouches de tailles et de densités de charge arbitraires. Puis nous avons déterminé l'impact de la dynamique hors-équilibre des propriétés électriques de (bio)films mous ligands sur leur capacité à former des complexes avec des métaux. Le dernier modèle théorique élaboré a pour objectif l'analyse de la dynamique de (bio)interphases multicouches hétérogènes en régimes d'équilibre et hors-équilibre. Enfin nous avons analysé à l'équilibre, en alliant l'AFM et l'électrophorèse, les propriétés mécaniques et électriques de bactéries E. coli exprimant spécifiquement (ou non) des structures de surface différentes. Toutes ces études ont montré la nécessité de prendre en compte pour l'analyse de la réactivité de (bio)particules dans leur milieu environnant (i) une représentation fidèle des (bio)particules (mollesse mécanique et hydrodynamique, hétérogénéité spatiale de la structure molle) et (ii) l'impact de la dynamique spatio-temporelle des (bio)interphases sur les processus gouvernant leur réactivité / In natural media, the solid matter is mainly present as soft (bio)particles (bacteria, viruses, humic acids) which are permeable toward ions and hydric fluxes. These (bio)particles are unceasingly exposed to electrical/mechanical perturbations, so that the physicochemical properties of (bio)interphases, developed by (bio)particles with the medium, evolve continuously. (Bio)interphases are thus not necessarily at equilibrium during interfacial processes e.g. electrostatic interactions, complexation with metallic contaminants. Under such a context, we evaluated theoretically at equilibrium the electrostatic interaction energy between soft multilayered (bio)particles with arbitrary sizes and charge densities. We then determined the impact of non- equilibrium electric properties of soft ligand polymeric (bio)films on their ability to form complexes with metals. The aim of the last theoretical model developed here is to analyze the dynamics of multilayered heterogeneous (bio)interphases in both equilibrium and non-equilibrium regimes. Finally we analyzed at equilibrium, by coupling AFM and microelectrophoresis measurements, mechanical and electrical properties of bacterial strains Escherichia coli that specifically express (or not) different surface structures (pili, fimbriae, adhesin Ag43). All these studies highlighted the necessity to integrate for the analysis of (bio)particles reactivity with their surrounding medium (i) a close representation of soft (bio)particles (mechanical and hydrodynamic softness, spatial heterogeneity of the soft material) and (ii) the impact of spatiotemporal dynamics of (bio)interphases on the processes governing their reactivity
|
24 |
Production and characterisation of self-crosslinked chitosan-carrageenan polyelectrolyte complexesAl-Zebari, Nawar January 2017 (has links)
Macromolecular biomaterials often require covalent crosslinking to achieve adequate stability and mechanical strength for their given application. However, the use of auxiliary chemicals may be associated with long-term toxicity in the body. Oppositely-charged polyelectrolytes (PEs) have the advantage that they can self-crosslink electrostatically and those derived from marine organisms are an inexpensive alternative to glycosaminoglycans present in the extracellular matrix of human tissues. A range of different combinations of PEs and preparation conditions have been reported in the literature. However, although there has been some work on complex formation between chitosan (CS) and carrageenan (CRG), much of the work undertaken has ignored the effect of pH on the consequent physicochemical properties of self-crosslinked polyelectrolyte complex (PEC) gels, films and scaffolds. Chitosan is a positively-charged polysaccharide with NH3+ side groups derived from shrimp shells and, carrageenan is a negatively-charged polysaccharide with OSO3- side groups derived from red seaweed. These abundant polysaccharides possess advantageous properties such as biodegradability and low toxicity. However, at present, there is no clear consensus on the cell binding properties of CS and CRG or CS-CRG PEC materials. The aim of this study was to explore the properties of crosslinker-free PEC gels, solvent-cast PEC films and freeze-dried PEC scaffolds based on CS and CRG precursors for medical applications. The objective was to characterise the effect of pH of the production conditions on the physicochemical and biological properties of CS-CRG PECs. Experimental work focused on the interaction between PEs, the composition of PECs, the rheological properties of PEC gels and the mechanical properties of PEC films and scaffolds. In addition, cell and protein attachment to the PEC films was assessed to determine their interactions in a biological environment. For biomedical applications, these materials should ideally be stable when produced such that they can be processed to form either a film or a scaffold and have mechanical properties comparable to those of collagenous soft tissues. FTIR was used to confirm PEC formation. Zeta potential measurements indicated that the PECs produced at pH 2-6 had a high strength of electrostatic interaction with the highest occurring at pH 4-5. This resulted in stronger intra-crosslinking in the PEC gels which led to the formation of higher yield, solid content, viscosity and fibre content in PEC gels. The weaker interaction at pH 7-12 resulted in higher levels of CS incorporated into the complex and the formation of inter-crosslinking through entanglements between PEC units. This resulted in the production of strong and stiff PEC films and scaffolds appropriate for soft tissue implants. The PECs prepared at pH 7.4 and 9 also exhibited low swelling and mass loss, which was thought to be due to the high CS content and entanglements. From the range of samples tested, the PECs produced at pH 7.4 appeared to show the optimum combination of yield, stability and homogeneity for soft tissue implants. Biological studies were performed on CS, CRG and PECs prepared at pH 3, 5, 7.4 and 9. All of the PE and PEC films were found to be non-cytotoxic. When the response of three different cell types and a high binding affinity protein (tropoelastin) was evaluated; it was found that the CS-CRG PEC films displayed anti-adhesive properties. Based on these experimental observations and previous studies, a mechanistic model of the anti-adhesive behaviour of PEC surfaces was proposed. It was therefore concluded that the CS-CRG PECs produced might be suitable for non-biofouling applications.
|
25 |
Partitioning of Drugs and Lignin Precursor Models into Artificial MembranesBoija, Elisabet January 2006 (has links)
<p>The main aim of this thesis was to characterize membrane-solute interactions using artificial membranes in immobilized liposome chromatography or capillary electrophoresis. The partitioning of a solute into a cell membrane is an essential step in diffusion across the membrane. It is a valid parameter in drug research and can be linked to the permeability as well as the absorption of drugs. Immobilized liposome chromatography was also used to study partitioning of lignin precursor models. Lignin precursors are synthesized within plant cells and need to pass the membrane to be incorporated into lignin in the cell wall.</p><p>In immobilized liposome chromatography, liposomes or lipid bilayer disks were immobilized in gel beads and the partitioning of solutes was determined. Capillary electrophoresis using disks as a pseudostationary phase was introduced as a new approach in drug partitioning studies. In addition, octanol/water partitioning was used to determine the hydrophobicity of the lignin precursor models.</p><p>Electrostatic interactions occurred between bilayers and charged drugs, whereas neutral drugs were less affected. However, neutral lignin precursor models exhibited polar interactions. Moreover, upon changing the buffer ionic strength or the buffer ions, the interactions between charged drugs and neutral liposomes were affected. Hydrophobic interactions were also revealed by including a fatty acid or a neutral detergent into the bilayer or by using a buffer with a high salt concentration. The bilayer manipulation had only a moderate effect on drug partitioning, but the high salt concentration had a large impact on partitioning of lignin precursor models.</p><p>Upon comparing the partitioning into liposomes and disks, the latter showed a more pronounced partitioning due to the larger fraction of lipids readily available for interaction. Finally, bilayer disk capillary electrophoresis was successfully introduced for partitioning studies of charged drugs. This application will be evaluated further as an analytical partitioning method and separation technique.</p>
|
26 |
Statistical thermodynamics of virus assemblyLee, Se Il 06 April 2010 (has links)
Experiments show that MgSO4 salt has a non-monotonic effect as a function of MgSO4 concentration
on the ejection of DNA from bacteriophage lambda.
There is a concentration, N0, at which the minimum amount of DNA is ejected.
At lower or higher concentrations, more DNA is ejected. We propose that this non-monotonic behavior
is due to the overcharging of DNA at high concentration of Mg⁺² counterions.
As the Mg⁺² concentration increases from zero, the net charge of ejected DNA changes its sign from negative to positive.
N0 corresponds to the concentration at which DNA is neutral.
Our theory fits experimental data well.
The DNA-DNA electrostatic attraction is found to be -0.004 kBT/nucleotide.
Simulations of DNA-DNA interaction of a hexagonal DNA bundle support our theory.
They also show the non-monotonic DNA-DNA interaction and reentrant behavior of DNA condensation by divalent counterions.
Three problems in understanding the capsid assembly for a retrovirus are studied:
First, the way in which the viral membrane affects the structure of in vivo assembled HIV-1 capsid is studied.
We show that conical and cylindrical capsids have similar energy at high surface tension of the viral membrane,
which leads to the various shapes of HIV-1 capsids. Secondly, the problem of RNA genome packaging inside spherical viruses
is studied using RNA condensation theory. For weak adsorption strength of capsid protein, most RNA genomes are located at the center
of the capsid. For strong adsorption strength, RNA genomes peak near the capsid surface and the amount of RNA packaged is proportional to the capsid area instead its volume. Theory fits experimental data reasonably well.
Thirdly, the condensation of RNA molecules by nucleocapsid (NC) protein is studied.
The interaction between RNA molecules and NC proteins is important for the reverse transcription of viral RNA which relates to the viral infectivity.
For strong adsorption strength of the NC protein, there is a screening effect by RNA molecules around a single NC protein.
|
27 |
Partitioning of Drugs and Lignin Precursor Models into Artificial MembranesBoija, Elisabet January 2006 (has links)
The main aim of this thesis was to characterize membrane-solute interactions using artificial membranes in immobilized liposome chromatography or capillary electrophoresis. The partitioning of a solute into a cell membrane is an essential step in diffusion across the membrane. It is a valid parameter in drug research and can be linked to the permeability as well as the absorption of drugs. Immobilized liposome chromatography was also used to study partitioning of lignin precursor models. Lignin precursors are synthesized within plant cells and need to pass the membrane to be incorporated into lignin in the cell wall. In immobilized liposome chromatography, liposomes or lipid bilayer disks were immobilized in gel beads and the partitioning of solutes was determined. Capillary electrophoresis using disks as a pseudostationary phase was introduced as a new approach in drug partitioning studies. In addition, octanol/water partitioning was used to determine the hydrophobicity of the lignin precursor models. Electrostatic interactions occurred between bilayers and charged drugs, whereas neutral drugs were less affected. However, neutral lignin precursor models exhibited polar interactions. Moreover, upon changing the buffer ionic strength or the buffer ions, the interactions between charged drugs and neutral liposomes were affected. Hydrophobic interactions were also revealed by including a fatty acid or a neutral detergent into the bilayer or by using a buffer with a high salt concentration. The bilayer manipulation had only a moderate effect on drug partitioning, but the high salt concentration had a large impact on partitioning of lignin precursor models. Upon comparing the partitioning into liposomes and disks, the latter showed a more pronounced partitioning due to the larger fraction of lipids readily available for interaction. Finally, bilayer disk capillary electrophoresis was successfully introduced for partitioning studies of charged drugs. This application will be evaluated further as an analytical partitioning method and separation technique.
|
28 |
Zur Anwendung des Skalarprodukts von Kraft und Weg auf reversible Prozesse (Druck-Volumen-Änderung, Dehnung, Elektrostatische Wechselwirkung, Hub) : die Verwendung äußerer oder systemimmanenter Kräfte / To the application of the scalar product of force and displacement to reversible processes (pressure-volume change, elongation, electrostatic interaction, raising) : the use of external or system-immanent forcesSchmidt, Joachim, Bechmann, Wolfgang January 2014 (has links)
Wir schlagen einen allgemein anwendbaren Algorithmus vor, der unter Verwendung des Skalarprodukts von Kraft und Weg zum richtigen Vorzeichen in den Gleichungen für die Arbeit und die Potentielle Energie bei reversiblen Prozessen (Druck-Volumen-Änderung, Dehnung, Elektrostatische Wechselwirkung, Hub)führt. Wir zeigen, dass es dabei möglich ist, systemimmanente oder externe Kräfte zu benutzen. Wir zeigen, dass bei Verwendung von systemimmanenten Kräften das Skalarprodukt mit negativem Vorzeichen anzusetzen ist. Zudem ist es sehr wichtig, nötige Vorzeichenwechsel bei den einzelnen Schritten zu beachten. Wir betonen dies, weil gelegentlich übersehen wird, dass ein Vorzeichenwechsel nötig ist, wenn das Wegdifferential ds durch das Höhendifferential dh beziehungsweise durch das Abstandsdifferential dx oder dr ersetzt werden muss.
|
29 |
Τροποποίηση νανοσωλήνων άνθρακα με πολυμερή που παρουσιάζουν βιοστατικές ιδιότητεςΚορομηλάς, Νικόλαος 01 October 2012 (has links)
Οι νανοσωλήνες άνθρακα, από τη στιγμή της ανακάλυψής τους, έχουν προσελκύσει το ενδιαφέρον της επιστημονικής κοινότητας, λόγω της ευρείας εφαρμογής τους σε πολλά επιστημονικά και τεχνολογικά πεδία, ως συνέπεια των μοναδικών ιδιοτήτων τους. Σημαντική είναι η χρησιμοποίηση των νανοσωλήνων άνθρακα με σκοπό την ανάπτυξη μιας καινοτόμου μεμβράνης υψηλών αποδόσεων, για χρήση στην τεχνολογία Βιοαντιδραστήρα Μεμβρανών (Membrane Bioreactors, MBRs). Στην παρούσα εργασία, πραγματοποιήθηκε χημική τροποποίηση των νανοσωλήνων άνθρακα με πολυμερικές αλυσίδες. Η τροποποίηση των νανοσωλήνων μπορεί όχι μόνο να αυξήσει τη διαλυτότητά τους, αλλά να βελτιώσει την επεξεργασιμότητά τους και να τους προσδώσει νέες ιδιότητες, ανάλογα με τη φύση των μορίων της τροποποίησης. H τροποποίηση των νανοσωλήνων άνθρακα μπορεί να επιτευχθεί με την επισύναψη λειτουργικών ομάδων στην επιφάνειά τους, είτε μέσω ομοιοπολικού είτε μέσω μη ομοιοπολικού δεσμού. Η ομοιοπολική σύνδεση επιτυγχάνεται με δύο μεθόδους: τον “εμβολιασμό προς” και τον “εμβολιασμό από”. Στον “εμβολιασμό προς” το συντεθειμένο πολυμερές προσδένεται απευθείας στην επιφάνεια του νανοσωλήνα, ενώ στον “εμβολιασμό από” η πολυμερική αλυσίδα αναπτύσσεται πάνω στην επιφάνεια του νανοσωλήνα.
Στη συγκεκριμένη εργασία, λεπτοί νανοσωλήνες άνθρακα πολλαπλού τοιχώματος (Thin MWCNTs) και νανοσωλήνες άνθρακα πολλαπλού τοιχώματος (MWCNTs) τροποποιήθηκαν ομοιοπολικά και με τις δύο μεθόδους με πολυμερή, τα οποία μπορούν να ενσωματώσουν είτε ομοιοπολικά είτε ηλεκτροστατικά ομάδες τεταρτοταγούς αζώτου και φωσφoνίου, οι οποίες παρουσιάζουν βιοστατικές ιδιότητες.
Ειδικότερα, έγιναν προσπάθειες ομοιοπολικής πρόσδεσης των βιοστατικών ομάδων μέσω πολυμερισμού κατάλληλων μονομερών ή με πολυμερισμό των μονομερών και κατάλληλη χημική τροποποίησή τους στην επιφάνεια των νανοσωλήνων άνθρακα. Τα μονομερή ήταν ο 2-(διμεθυλάμινο) μεθακρυλικός αιθυλεστέρας (DMAEMA) και το τεταρτοταγές DMAEMA για τους MWCNTs, ενώ μια επιπλέον προσπάθεια πραγματοποιήθηκε για πολυμερισμό του Ν,Ν-[(διμεθυλάμινο)πρόπυλο]μεθακρυλαμιδίου (MADAP) στους Thin MWCNTs. Επειδή οι προσπάθειες δεν προχώρησαν σε σημαντικό βαθμό, συντέθηκε το στατιστικό συμπολυμερές P(AA12-co-VBCHAM) με συμπολυμερισμό του ακρυλικού οξέος (ΑΑ) και του 4-βινυλοβένζυλο χλωριδίου (VBC) σε ποσοστό 12% και 88% αντίστοιχα και εισαγωγή της N,N-διμεθυλοδεκαεξυλαμίνης, το οποίο στη συνέχεια εισήχθη στους τροποποιημένους, με ομάδες φαινόλης, νανοσωλήνες άνθρακα (CNTs-PhOH).
Επίσης, επετεύχθη εισαγωγή των βιοστατικών ομάδων αμμωνίου και φωσφονίου μέσω ηλεκτροστατικής αλληλεπίδρασης ως αντισταθμιστικά ιόντα στον αρνητικά φορτισμένο πολυηλεκτρολύτη πολυ(στυρενοσουλφονικό νάτριο) (PSSNa), που είχε προσδεθεί στους τροποποιημένους, με ομάδες εκκινητή ATRP, (πολυμερισμός ελευθέρων ριζών μέσω μεταφοράς ατόμου) λεπτούς νανοσωλήνες άνθρακα πολλαπλού τοιχώματος (Τhin MWCNTs-Ph-INIT). Η ίδια διαδικασία πραγματοποιήθηκε για την εισαγωγή ομάδων αμμωνίου στο PSSNa που είχε προσδεθεί στους τροποποιημένους, με ομάδες εκκινητή ATRP, νανοσωλήνες άνθρακα πολλαπλού τοιχώματος (MWCNTs-Ph-INIT).
Τα συντεθειμένα βιοστατικά υλικά μπορούν να χρησιμοποιηθούν σε πολλές εφαρμογές, μεταξύ των οποίων είναι και ο καθαρισμός του νερού. / Since their discovery, carbon nanotubes, have attracted the interest of the scientific community, because of their wide application in a numerous scientific and technological fields, as a consequence of their unique properties. The use of carbon nanotubes is of great importance to the field of Membrane Bioreactors (MBRs) for the development of innovative membranes of high performance. The modification of carbon nanotubes can not only increase their solubility, but improve their processability and give them new properties, depending on the nature of the molecules of modification. In this work, the chemical modification of carbon nanotubes with polymer chains is investigated. Modification of carbon nanotubes can be achieved with the attachment of functional groups in their surface, through covalent or non covalent bond. The covalent bond is achieved with two methods: “grafting to” and “grafting from”. In the “grafting to” method, the synthesized polymer is attached directly on the surface of carbon nanotube, while in the “grafting from” method, the polymer chain is developed from the surface of the carbon nanotube.
In the present work, thin multi-walled carbon nanotubes (Thin MWCNTs) and multi-walled carbon nanotubes (MWCNTs) were modified covalently with both methods with polymers, that can incorporate either covalently or electrostatically, quartenary ammonium and phosphonium groups that present antifouling properties.
More specifically, efforts were made in covalent attachment of antifouling groups via polymerization of suitable monomers or with polymerization of monomers and appropriate subsequent chemical modification in the surface of carbon nanotubes. The monomers were the 2-(Dimethylamino)ethyl methacrylate (DMAEMA) and quaternized DMAEMA for MWCNTs, while an additional effort was made in polymerization of N,N-[(dimethylamino)propyl]methacrylamide (MADAP) in Thin MWCNTs. Because the efforts were not successful, the random copolymer P(AA12-co-VBCHAM) was prepared, with copolymerization of acrylic acid (AA) and 4-vinylbenzyl chloride (VBC) in 12% and 88% percentage respectively and introduction of N,N-Dimethylhexadecylamine, which afterwards was introduced into modified, with phenol groups, carbon nanotubes (CNTs-PhOH).
Furthermore, successful introduction of antifouling ammonium and phosphonium groups via electostatical interaction as counter ions in the negatively charged polyelectrolyte poly(sodium styrene sulfonate) (PPSNa) was accomplished. The polyelectrolyte was grafted onto modified, with ATRP (atom transfer radical polymerization) initiator groups, thin multi-walled carbon nanotubes (Thin MWCNTs-Ph-INIT). The same process was followed for the introduction of ammonium groups in PSSNa, which was grafted onto modified, with ATRP initiator groups, multi-walled carbon nanotubes (MWCNTs-Ph-INIT).
The composed antifouling materials can be used in a lot of applications, including the water purification.
|
30 |
Modélisation des propriétés électrostatiques des complexes macromoléculaires à partir des données de diffraction des rayons X à très haute résolution / Modeling of electrostatic properties in macromolecular complexes using X-ray diffraction data at ultra-high resolutionFournier, Bertrand 06 July 2010 (has links)
La diffraction des rayons X permet d’obtenir des informations sur la structure atomique et même sur la distribution de charges de composés sous forme cristalline, ce qui est d’une importance fondamentale pour la compréhension de leurs propriétés. Accéder expérimentalement à une description de la distribution de charges de systèmes macromoléculaires reste rarement possible malgré les améliorations techniques. Pour pallier cette limite, la transférabilité des paramètres de distributions de charges est un moyen fiable d’obtenir pour ces systèmes un modèle estimé et d’en déduire leurs propriétés électrostatiques. Les résultats présentés dans ce travail de thèse s’intègrent dans une dynamique visant à étendre les méthodes initialement réservées pour l’étude des petites molécules aux systèmes macromoléculaires. Il s’articule autour du développement de la suite de logiciels MoPro et de la banque de données ELMAM (Experimental Library of Multipolar Atom Model) pour l’étude des énergies des interactions électrostatiques au sein du site actif de complexes enzyme-inhibiteur. L’étude du fidarestat, un inhibiteur de l’holoenzyme aldose réductase, réalisée à partir de données obtenues à très haute résolution, est exposée dans ce manuscrit et a servi notamment à l’amélioration de la banque ELMAM en vue de l’étude des complexes holoenzymes aldo-keto réductase. A cette occasion, la légitimité du recours aux modèles transférés de distribution de charges a été discutée pour la première fois par une estimation statistique des incertitudes sur les énergies d’interaction électrostatique entre enzyme et inhibiteur / X-ray diffraction allows to obtain information about atomic structure and charge density distribution of crystal-state compounds, which is of main interest for the understanding of their properties. Reaching experimentally charge density distribution description of macromolecular systems is rarely possible despite technical improvements. To get around this limit, the transferability of charge density distribution parameters is a reliable way to obtain for these systems estimated model and to deduce their electrostatic properties. Works introduced in this PhD thesis manuscript take part in the will of extending methods initially for study of small molecules to macromolecular systems. It is centered on the development of the MoPro software suite and of ELMAM database (Experimental Library of Multipolar Atom Model) for the study of electrostatic interaction energies in enzyme-inhibitor complexes’ active site. The study of fidarestat, an inhibitor of aldose reductase holoenzyme, performed using ultra-high resolution data, is exposed in this manuscript and allowed to improve ELMAM database for the study of electrostatic interaction in aldo-keto reductase holoenzyme complexes. Moreover, the legitimacy of using transferred charge density distribution models was discussed for the first time, thanks to statistical estimation of uncertainties on electrostatic interaction energies between enzyme and inhibitor
|
Page generated in 0.165 seconds