Auswahl der wissenschaftlichen Literatur zum Thema „Cationic Cellulose Derivative“

Polymeric multilayer capsules formed by the Layer-by-Layer (LbL) technique are interesting candidates for the purposes of storage, encapsulation, and release of drugs and biomolecules for pharmaceutical and biomedical applications. In the current study, cellulose-based core-shell particles were developed via the LbL technique alternating two cellulose derivatives, anionic carboxymethylcellulose (CMC), and cationic quaternized hydroxyethylcellulose ethoxylate (QHECE), onto a cationic vesicular template made of didodecyldimethylammonium bromide (DDAB). The obtained capsules were characterized by dynamic light scattering (DLS), ζ potential measurements, and high-resolution scanning electron microscopy (HR-SEM). DLS measurements reveal that the size of the particles can be tuned from a hundred nanometers with a low polydispersity index (deposition of 2 layers) up to micrometer scale (deposition of 6 layers). Upon the deposition of each cellulose derivative, the particle charge is reversed, and pH is observed to considerably affect the process thus demonstrating the electrostatic driving force for LbL deposition. The HR-SEM characterization suggests that the shape of the core-shell particles formed is reminiscent of the spherical vesicle template. The development of biobased nano- and micro-containers by the alternating deposition of oppositely charged cellulose derivatives onto a vesicle template offers several advantages, such as simplicity, reproducibility, biocompatibility, low-cost, mild reaction conditions, and high controllability over particle size and composition of the shell.

Cellulose nanomaterials have been widely investigated in the last decade, unveiling attractive properties for emerging applications. The ability of sulfated cellulose nanocrystals (CNCs) to guide the supramolecular organization of amphiphilic fullerene derivatives at the air/water interface has been recently highlighted. Here, we further investigated the assembly of Langmuir hybrid films that are based on the electrostatic interaction between cationic fulleropyrrolidines deposited at the air/water interface and anionic CNCs dispersed in the subphase, assessing the influence of additional negatively charged species that are dissolved in the water phase. By means of isotherm acquisition and spectroscopic measurements, we demonstrated that a tetra-sulfonated porphyrin, which was introduced in the subphase as anionic competitor, strongly inhibited the binding of CNCs to the floating fullerene layer. Nevertheless, despite the strong inhibition by anionic molecules, the mutual interaction between fulleropyrrolidines at the interface and the CNCs led to the assembly of robust hybrid films, which could be efficiently transferred onto solid substrates. Interestingly, ITO-electrodes that were modified with five-layer hybrid films exhibited enhanced electrical capacitance and produced anodic photocurrents at 0.4 V vs Ag/AgCl, whose intensity (230 nA/cm2) proved to be four times higher than the one that was observed with the sole fullerene derivative (60 nA/cm2).

Interfaces are ubiquitous in our daily life. A good understanding of the interfacial properties between different materials, or a single material in different physical states is of critical importance for us to explore the current world and bring benefits to mankind. In this work, interfacial behavior was investigated with the help of surface analysis techniques, such as quartz crystal microbalance with dissipation monitoring (QCM-D), surface plasmon resonance (SPR) and atomic force microscopy (AFM), in order to gain better understanding on biofuel conversion, gene/drug delivery, and chemical fixation of CO2. Biomimetic chelator-mediated Fenton (CMF) non-enzymatic degradations on cellulose and chitin thin films was studied by liquid-phase QCM-D and AFM. QCM-D is a powerful tool to monitor the kinetics of hydrolysis of regenerated cellulose and chitin model surfaces. Results from QCM-D and AFM showed that the majority of the biomass of the two model surfaces can be hydrolyzed by the CMF system. The initial degradation rates for both model surfaces by the CMF system are faster than that of the corresponding enzyme systems. The CMF system, which is a good non-enzymatic pretreatment agent for cellulose and chitin, may work on a wide variety of polysaccharide systems. Adsorption of cationic cellulose derivatives onto self-assembled monolayer (SAM) surfaces was investigated using liquid-phase SPR. Results from SPR showed that depending upon the cellulose derivative structure, irreversible adsorption ranging from a monolayer to ~1.6 layers of cellulose derivative were formed on the SAM-COOH surface based upon a charge neutralization mechanism. At low salt concentrations, the long-range electrostatic attraction between the cationic cellulose derivatives (6-PyrCA and 6-MeIMCA) and the SAM surfaces facilitates the formation of a 2-dimensional monolayer. While, for TMACE, the energy gained through the hydrophobic interaction between adjacent long polyelectrolyte branches may afford the electrostatic repulsion and chain entropy penalties, resulting in the formation of 3-dimensional adsorbed polyelectrolyte layers. Adsorption of 1,2-epoxybutane gas molecules onto/into VPI-100 metal–organic frameworks (MOFs) was studied by gas-phase QCM-D experiments. Results from QCM-D demonstrated that VPI-100 (Ni) MOFs have higher irreversible adsorption per unit cell (θ) and faster diffusion coefficients (D) than VPI-100 (Cu) MOFs. The presence of bound counter-balancing ions on the metallo-cyclam core was attributed as the cause of the higher θ and faster D through the Ni analogue, which suggests the MOF-epoxide interaction occurs at the metallo-cyclam. This study shed light upon tuning MOF structures for better CO2 sorption and epoxide activation to gain higher catalytic efficiency. Finally, in operando high energy X-ray diffraction (HEXRD) was used to monitor the phase transition of the NaxNi1/3Co1/3Mn1/3O2 cathode material during the sintering process. The first charge/discharge cycle of the NaxNi1/3Co1/3Mn1/3O2 cathode materials in different phases were also studied by in operando HEXRD. It was found that the intergrowth P2/O1/O3 cathode (NCM-Q cathode) can inhibit the irreversible P2–O2 phase transition and simultaneously improve the structural stability of the O3 and O1 phases during cycling. The NCM-Q cathode with triple-phase integration demonstrates highly reversible phase evolution during high voltage cycling, possibly leading to a highly reversible capacity and good cycle stability.
Doctor of Philosophy
Interfaces and surfaces are everywhere. Many critical processes, such as molecular recognition, catalysis, and charge transfer, take place at interfaces. The surfaces of plants and animals provide barriers from pathogens, prevent damage from mechanical impacts, detect external stimuli, etc. Inside the human body, nutrition and oxygen are adsorbed through interactions between substances and cell surfaces. Investigations of interfacial behaviors may help us understand our current world better and bring benefits to mankind. In this dissertation, the interface between bio-renewable natural polymers and biomimetic chelators, the interface between a self-assembled monolayer and cationic cellulose derivatives, and the interface between metal–organic frameworks (MOF) and 1,2-epoxybutane gas molecules, were studied with a quartz crystal microbalance with dissipation monitoring (QCM-D), surface plasmon resonance (SPR) and atomic force microscopy (AFM), to gain insights into biofuel conversion, gene/drug delivery and chemical fixation of CO2, respectively. Additionally, thermally and electrochemically induced phase transitions in sodium-ion battery (SIB) cathode materials were probed via in operando high energy X-ray diffraction (HEXRD). Biomimetic chelator-mediated Fenton (CMF) non-enzymatic degradations of cellulose and chitin thin films were studied by liquid-phase QCM-D and AFM. It was found that the majority of the biomass of the two model surfaces can be degraded by the CMF system. Adsorption of cationic cellulose derivatives onto self-assembled monolayer (SAM) surfaces was investigated using liquid-phase SPR. It was found that both the absorbed layer conformation and the absorbed amount depend upon the interplay between long-range electrostatic interactions and short-range interactions. Adsorption of 1,2-epoxybutane gas molecules onto/into VPI-100 MOFs was studied by gas-phase QCM-D experiments. Data from QCM-D revealed the irreversible gas molecule absorption onto/into MOFs and shed light upon tuning MOF structures for better CO2 sorption and epoxide activation to gain higher catalytic efficiency. Finally, the in operando high energy X-ray diffraction (HEXRD) was used to probe thermally and electrochemically induced phase transitions in sodium-ion battery (SIB) cathode materials. It was found that the NCM-Q cathode with triple-phase integration demonstrates highly reversible phase evolution during high voltage cycling, possibly leading to a highly reversible capacity and good cycle stability.

In an effort to produce new derivatives of cellulose for drug delivery applications, methods were developed to regioselectively modify C-6 halo cellulose esters to produce cationic derivatives via nucleophilic substitution. Reaction of C-6 substituted bromo and iodo cellulose with trialkylated amines and phosphines produced new cationic ammonium and phosphonium cellulose derivatives which can be explored as delivery agents for nucleic acids, proteins and other anionic drug molecules. It was anticipated that these new derivatives would not only be capable of complexing anionic drug molecules but would have greatly improved aqueous solubility compared to their precursors. The phosphonium derivatives described in this work are an obvious example of such improved solubility properties. Given the importance of cellulose derivatives in making amorphous dispersions with critical drugs, it has also been important to analyze commercially available polymers for the potential impact in oral drug delivery formulations. To do so pairwise blends of cellulosics and synthetic polymers commonly used as excipients were tested for miscibility using techniques such as DSC, mDSC, FTIR and film clarity. Miscible combinations highlight the potential to use combinations of polymers currently available commercially to provide drug delivery solutions for specific drug formulations. The use of melt extrusion in processing some of these drug/polymer dispersions provides a means of highlighting the capability for the use of these cellulosics in melt extruded amorphous dispersions. This solvent free, high pressure method significantly reduces cost and time and can be applied on a large scale. The analysis of long chain cellulose esters and ultimately the novel omega carboxy esters for melt processability significantly impacts the possibilities available for use of those excellent drug delivery agents on a much larger scale.
Ph. D.

L’objectif principal de ce travail est la modification chimique des fibres cellulosiques, afin d'améliorer leurs propriétés interfaciales lors de leur utilisation comme renforts dans des matériaux composites à matrice polymère organique (polystyrène). La synthèse d'un nouvel agent de couplage pour le système cellulose-polystyrène a été entreprise par la voie de copolymérisation cationique. Une caractérisation complète de cet agent de couplage a été faite par ftir, analyse élémentaire, #1h-nmr, calorimétrie différentielle (dsc) et chromatographie par exclusion stérique (ces). La réactivité de ce copolymère a été vérifiée vis-a-vis des oh et des amines primaires par ftir. Les caractéristiques essentielles pour pouvoir l'utiliser comme agent de couplage sont : une bonne miscibilité avec le polystyrène (matrice), de longues chaînes (mn 20000) et la présence des groupements réactifs (isocyanates) sur la chaîne polymère. A titre comparatif, d'autres agents de couplage ayant des structures et des masses différentes ont été utilisés. Deux d'entre eux portent des anhydrides comme fonctions réactives vis-à-vis de la cellulose. La modification chimique des charges cellulosiques a été vérifiée par ftir, analyse élémentaire, microscopie a balayage (meb). De plus, l'énergie de surface des diverses dérives cellulosiques a été mesurée par goniométrie (angle de contact) et chromatographie inverse (igc). L’imperméabilisation des surfaces cellulosiques vis-à-vis des liquides polaires a été vérifiée. L’adhésion (cisaillement interfacial) entre la cellulose et le polystyrène a été mesurée par des techniques micromécaniques sur composites monofilamentaires. Les techniques utilisées ont été la multifragmentation et le déchaussement ('pull-out'). POUR LES COMPOSITES A BASE DE FIBRES CELLULOSIQUES COURTES, L'EFFET DU RENFORCEMENT A ETE VERIFIE A L'AIDE DE LA SPECTROSCOPIE DYNAMIQUE (DMA). LES PARAMETRES SUIVANTS ONT ETE ETUDIES : TAUX DE RENFORT ET FACTEUR DE FORME (LONGUEUR/DIAMETRE). LE MODELE D'HALPIN-KARDOS REPRESENTE CORRECTEMENT LE COMPORTEMENT DE NOS MATERIAUX.

Resumo Em diversas formulações industriais, encontram-se, facilmente, vários exemplos da utilização de biopolímeros derivados de celulose em conjunto com tensoativos. Entretanto, na literatura, há divergências se ocorre realmente uma interação entre um polímero não iônico, como os derivados aquo-solúveis de celulose, em conjunto com tensoativos catiônicos. Desta forma, neste projeto de Mestrado, foram investigadas as interações entre três derivados de celulose (2-hidroxietil celulose, 2-HEC; hidroxipropil celulose, HPC e hidroximetilpropil celulose, HMPC) e três tensoativos catiônicos (cloreto de benzil-hexadecildimetilamônio, CBz; cloreto de fenil-hexadecildimetilamônio, Fenil e cloreto de 2-feniletil hexadecildimetilamônio, 2-Feniletil) obtendo-se informações sobre a estrutura dos agregados formados por este sistema através de medidas de condutividade, fluorescência no estado estacionário e viscosidade. Estas técnicas forneceram os parâmetros de concentração de agregação crítica (cac), concentração micelar crítica (cmc), grau de dissociação micelar e viscosidade das soluções. Em uma segunda etapa, foi investigada a variação da cmc do tensoativo zwitteriônico, coco amido propil betaína (CAPB), em soluções aquosas com diferentes pHs, visando futuros estudos de interação deste compostos com os biopolímeros derivados ou não de celulose.
There are many industrial formulations that are consisted of a biopolymer, such as cellulose derivatives, and surfactants. However, in literature, there are some divergences if there is a cooperative interaction between non-ionic polymers, and cationic surfactants. For this reason, in this project, the interactions between three cellulose derivatives (2- hydroxyethyl cellulose, 2-HEC, hydroxypropyl cellulose, HPC, and hydroxymethylpropyl cellulose, HPMC), and cationic surfactants (benzyl hexadecyldimethylammonium chloride, CBz, phenylhexadecyldimethylammonium chloride, Fenil, and 2-phenylethyl hexadecyl dimethylammonium chloride, 2-Feniletil) were studied through conductivity, steady-state fluorescence and viscosity measurements. The critical aggregation concentration (cac), critical micelle concentration (cmc), micelle dissociation degree, and viscosity were determined for each polymer surfactant system. In addition, the cmc of a zwitterionic surfactant, coco amido propyl betaine (CAPB), was measured in aqueous solutions of different pHs. This last experiment was performed as a preliminary essay to study the interaction of zwitterionic surfactant with several types of biopolymers.