Red, green, and blue lanthanum phosphate phosphors obtained via surfactant-control led hydrothermal synthesis

A new solution route for the obtainment of highly pure luminescent rare-earth orthophosphates in hydrothermal conditions was developed. By starting from soluble precursors (lanthanide tripolyphosphato complexes. i.e. with P(3)O(10)(5) as a complexing agent and as in orthophosphate source) and by applying surfactants in a water/toluene medium, the precipitations are confined to reverse micelle structures, thus yielding nanosized and homogeneous orthophosphates The method was employed to obtain lanthanide-activated lanthanum phosphates, which can be applied as red (LaPO(4):Eu(3+)), green (LaPO(4):Ce(3+), Tb(3+)) and blue (LaPO(4):Tm(3+)) phosphors The produced materials were analyzed by powder X-ray diffractometry, scanning electron microscopy, infrared spectroscopy and luminescence spectroscopy (emission, excitation, lifetimes and chromaticity coordinates) (C) 2009 Elsevier B V All rights reserved

The effect of cationic-anionic polyelectrolyte multilayer surface treatment on inkjet ink spreading and print quality

The focus of the work reported in this thesis was to study and to clarify the effect of polyelectrolyte multilayer surface treatment on inkjet ink spreading, absorption and print quality. Surface sizing with a size press, film press with a pilot scale coater, and spray coating, have been used to surface treat uncoated wood-free, experimental wood-free and pigmentcoated substrates. The role of the deposited cationic (polydiallydimethylammonium chloride, PDADMAC) and anionic (sodium carboxymethyl cellulose, NaCMC) polyelectrolyte layers with and without nanosilica, on liquid absorption and spreading was studied in terms of their interaction with water-based pigmented and dye-based inkjet inks. Contact angle measurements were made in attempt to explain the ink spreading and wetting behavior on the substrate. First, it was noticed that multilayer surface treatment decreased the contact angle of water, giving a hydrophilic character to the surface. The results showed that the number of cationic-anionic polyelectrolyte layers or the order of deposition of the polyelectrolytes had a significant effect on the print quality. This was seen for example as a higher print density on layers with a cationic polyelectrolyte in the outermost layer. The number of layers had an influence on the print quality; the print density increased with increasing number of layers, although the increase was strongly dependent on ink formulation and chemistry. The use of nanosilica clearly affected the rate of absorption of polar liquids, which also was seen as a higher density of the black dye-based print. Slightly unexpected, the use of nanosilica increased the tendency for lateral spreading of both the pigmented and dye-based inks. It was shown that the wetting behavior and wicking of the inks on the polyelectrolyte coatings was strongly affected by the hydrophobicity of the substrate, as well as by the composition or structure of the polyelectrolyte layers. Coating only with a cationic polyelectrolyte was not sufficient to improve dye fixation, but it was demonstrated that a cationic-anionic-complex structure led to good water fastness. A threelayered structure gave the same water fastness values as a five-layered structure. Interestingly, the water fastness values were strongly dependent not only on the formed cation-anion polyelectrolyte complexes but also on the tendency of the coating to dissolve during immersion in water. Results showed that by optimizing the chemistry of the layers, the ink-substrate interaction can be optimized.

Syntheses and spectroscopy of diamine complexes of Zn(II) and Cd(II) ethylxanthates and the molecular structures of [M(S2COEt)(2)TMEDA]: formation of US nanoparticles from [Cd(S2COEt)(2)] and [Cd(S2COEt)(2)TMEDA]

The zinc and cadmium ethylxanthate complexes of N,N,N',N'-tetramethylethylenediamine (TMEDA), [M(S2COEt)(2)TMEDA], were synthesized and characterized with infrared, H-1 and C-13 NMR spectroscopy, mass spectrometry and X-ray crystallography. Whereas the cadmium complex has a six-coordinate {CdS4N2} centre with bidentate xanthate ligands, the zinc complex contains four coordinate {ZnS2N2} zinc with two monodentate xanthate groups. The cadmium species [Cd(S2COEt)(2)(diamine)] (where diamine = N,N-dimethylethylenediamine or N,N'-diisopropylethylenediamine) were also synthesized. The surfactant-assisted formation of nanoparticles from [Cd(S2COEt)(2)] and [Cd(S2COEt)(2)TMEDA] was studied with TEM, XRD and XRF techniques. From [Cd(S2COEt)(2)], spherical nanoparticle aggregates 140-200 nm in diameter were obtained but from [Cd(S2COEt)(2)TMEDA], single nanoparticles were produced with estimated diameters in the range of 4-7 nm and almost no aggregation. (C) 2004 Elsevier Ltd. All rights reserved.

A method of synthesis of silicious inorganic ordered materials (MCM-41-SBA-1) employing polyacrylic acid-C(n)TAB-TEOS nanoassemblies

In this work we describe the synthesis of a variety of MCM-41 type hexagonal and SBA-1 type cubic mesostructures and mesoporous silicious materials employing a novel synthesis concept based on polyacrylic acid (Pac)-C(n)TAB complexes as backbones of the developing structures. The ordered porosity of the solids was established by XRD and TEM techniques. The synthesis concept makes use of Pac-C(n)TAB nanoassemblies as a preformed scaffold, formed by the gradual increase of pH. On this starting matrix the inorganic precursor species SiO2 precipitate via hydrolysis of TEOS under the influence of increasing pH. The molecular weight (MW) of Pac, as well as the length of carbon chain in C,TAB, determine the physical and structural characteristics of the obtained materials. Longer chain surfactants (C(16)TAB) lead to the formation of hexagonal phase, while shorter chain surfactants (C(14)TAB, C(12)TAB) favor the SBA-1 phase. Lower MW of Pac (approximate to2000) leads to better-organized structures compared to higher MW ( 450,000), which leads to worm-like mesostructures. Cell parameters and pore size increase with increasing polyelectrolyte and/or surfactant chain, while at the same time SEM photography reveals that the particle size decreases. Conductivity experiments provide some insight into the proposed self-assembling pathway. (C) 2003 Elsevier Inc. All rights reserved.

Molecular Ordering of Layer-by-Layer Polyelectrolyte Films Studied by Sum-Frequency Vibrational Spectroscopy

The molecular arrangement in organic thin films is crucial for their increasing technological applications. Here, we use vibrational spectroscopy by sum-frequency generation (SFG) to study the ordering of polyelectrolyte layers adsorbed on silica for all steps of layer-by-layer (LbL) self-assembly. In situ measurements during adsorption and rinsing showed that the adsorbed polymer has a disordered conformation and confirmed surface charge overcompensation upon polyelectrolyte adsorption by probing the interfacial electric field. In dry films, the polymer chains acquired a net orientational ordering, which was affected, however, by the adsorption of subsequent layers. Such a detailed characterization may allow the control of LbL film structure and functionality with unprecedented power.

Protein Adsorption onto Polyelectrolyte Layers: Effects of Protein Hydrophobicity and Charge Anisotropy

Ellipsometry was used to investigate the influence of ionic strength (I) and pH on the adsorption of bovine serum albumin (BSA) or beta-lactoglobulin (BLG) onto preabsorbed layers of two polycations: poly(diallyldimethylammonium chloride) (PDADMAC) or poly(4-vinylpyridine bromide) quaternized with linear aliphatic chains of two (QPVP-C2) or five (QPVP-C5) carbons. Comparisons among results for the three polycations reveal hydrophobic interactions, while comparisons between BSA and BLG-proteins of very similar isoelectric points (pI)-indicate the importance of protein charge anisotropy. At pH close to pI, the ionic strength dependence of the adsorbed amount of protein (Gamma) displayed maxima in the range 10 < I < 25 mM corresponding to Debye lengths close to the protein radii. Visualization of protein charge by Delphi suggested that these ionic strength conditions corresponded to suppression of long-range repulsion between polycations and protein positive domains, without diminution of short-range attraction between polycation segments and locally negative protein domains, in a manner similar to the behavior of PE-protein complexes in solution.(1-4) This description was consistent with the disappearance of the maxima at pH either above or below pI. In the former case, Gamma values decrease exponentially with I(1/2), due to screening of attractions, while in the latter case adsorption of both proteins decreased at low I due to strong repulsion. Close to or below pI both proteins adsorbed more strongly onto QPVP-C5 than onto QPVP-C2 or PDADMAC due to hydrophobic interactions with the longer alkyl group. Above pI, the adsorption was more pronounced with PDADMAC because these chains may assume more loosely bound layers due to lower linear charge density.

Gene delivery using dendrimer/pDNA complexes immobilized in electrospun fibers using the layer-by-layer technique

Tissue engineering is an important branch of regenerative medicine that uses cells, materials (scaffolds), and suitable biochemical and physicochemical factors to improve or replace specific biological functions. In particular, the control of cell behavior (namely, of cell adhesion, proliferation and differentiation) is a key aspect for the design of successful therapeutical approaches. In this study, poly(lactic-co-glycolic acid) (PLGA) fiber mats were prepared using the electrospinning technology (the fiber diameters were in the micrometer range). Furthermore, the electrospun fiber mats thus formed were functionalized using the layer-by- layer (LbL) technique with chitosan and alginate (natural and biodegradable polyelectrolytes having opposite charges) as a mean for the immobilization of pDNA/dendrimer complexes. The polyelectrolyte multilayer deposition was confirmed by fluorescence spectroscopy using fluorescent-labeled polyelectrolytes. The electrospun fiber mats coated with chitosan and alginate were successfully loaded with complexes of pDNA and poly(amidoamine) (PAMAM) dendrimers (generation 5) and were able of releasing them in a controlled manner along time. In addition, these mats supported the adhesion and proliferation of NIH 3T3 cells and of human mesenchymal stem cells (hMSCs) in their surface. Transfection experiments using a pDNA encoding for luciferase showed the ability of the electrospun fiber mats to efficiently serve as gene delivery systems. When a pDNA encoding for bone morphogenetic protein-2 (BMP-2) was used, the osteoblastic differentiation of hMSCs cultured on the surface of the mats was promoted. Taken together, the results revealed that merging the electrospinning technique with the LbL technique, can be a suitable methodology for the creation of biological active matrices for bone tissue engineering.

Interação de ácido algínico com surfactantes catiônicos em solução aquosa

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Counter-ion effect on surfactant-DNA gel particles as controlled DNA delivery systems

The ability to entrap drugs within vehicles and subsequently release them has led to new treatments for a number of diseases. Based on an associative phase separation and interfacial diffusion approach, we developed a way to prepare DNA gel particles without adding any kind of cross-linker or organic solvent. Among the various agents studied, cationic surfactants offered particularly efficient control for encapsulation and DNA release from these DNA gel particles. The driving force for this strong association is the electrostatic interaction between the two components, as induced by the entropic increase due to the release of the respective counter-ions. However, little is known about the influence of the respective counter-ions on this surfactant-DNA interaction. Here we examined the effect of different counter-ions on the formation and properties of the DNA gel particles by mixing DNA (either single-(ssDNA) or double-stranded (dsDNA)) with the single chain surfactant dodecyltrimethylammonium (DTA). In particular, we used as counter-ions of this surfactant the hydrogen sulfate and trifluoromethane sulfonate anions and the two halides, chloride and bromide. Effects on the morphology of the particles obtained, the encapsulation of DNA and its release, as well as the haemocompatibility of these particles are presented, using counter-ion structure and DNA conformation as controlling parameters. Analysis of the data indicates that the degree of counter-ion dissociation from the surfactant micelles and the polar/hydrophobic character of the counter-ion are important parameters in the final properties of the particles. The stronger interaction with amphiphiles for ssDNA than for dsDNA suggests the important role of hydrophobic interactions in DNA.

Visualization, manipulation and force spectroscopy of cylindrical polymer brushes

The Ph.D. thesis deals with the conformational study of individual cylindrical polymer brush molecules using atomic force microscopy (AFM). Imaging combined with single molecule manipulation has been used to unravel questions concerning conformational changes, desorption behavior and mechanical properties of individual macromolecules and supramolecular structures. In the first part of the thesis (chapter 5) molecular conformations of cylindrical polymer brushes with poly-(N-isopropylacrylamide) (PNIPAM) side chains were studied in various environmental conditions. Also micelle formation of cylindrical brush-coil blockcopolymers with polyacrylic acid side chains and polystyrene coil have been visualized. In chapter 6 the mechanical properties of single cylindrical polymer brushes with (PNIPAM) side chains were investigated. Assuming that the brushes adopt equilibrium conformation on the surface, an average persistence length of lp= (29 ± 3) nm was determined by the end-to-end distance vs. contour length analysis in terms of the wormlike chain (WLC) model. Stretching experiments suggest that an exact determination of the persistence length using force extension curves is impeded by the contribution of the side chains. Modeling the stretching of the bottle brush molecule as extension of a dual spring (side chain and main chain) explains the frequently observed very low persistence length arising from a dominant contribution of the side chain elasticity at small overall contour lengths. It has been shown that it is possible to estimate the “true” persistence length of the bottle brush molecule from the intercept of a linear extrapolation of the inverse square root of the apparent persistence length vs. the inverse contour length plot. By virtue of this procedure a “true” persistence length of 140 nm for the PNIPAM brush molecules is predicted. Chapter 7 and 8 deal with the force-extension behavior of PNIPAM cylindrical brushes studied in poor solvent conditions. The behavior is shown to be qualitatively different from that in a good solvent. Force induced globule-cylinder conformational changes are monitored using “molecule specific force spectroscopy” which is a combined AFM imaging and SMFS technique. An interesting behavior of the unfolding-folding transitions of single collapsed PNIPAM brush molecules has been observed by force spectroscopy using the so called “fly-fishing” mode. A plateau force is observed upon unfolding the collapsed molecule, which is attributed to a phase transition from a collapsed brush to a stretched conformation. Chapter 9 describes the desorption behavior of single cylindrical polyelectrolyte brushes with poly-L-lysine side chains deposited on a mica surface using the “molecule specific force spectroscopy” technique to resolve statistical discrepancies usually observed in SMFS experiments. Imaging of the brushes and inferring the persistence length from a end-to-end distance vs. contour length analysis results in an average persistence length of lp = (25 ± 5) nm assuming that the chains adopt their equilibrium conformation on the surface. Stretching experiments carried out on individual poly-L-lysine brush molecules by force spectroscopy using the “fly-fishing” mode provide a persistence length in the range of 7-23 nm in reasonable accordance with the imaging results. In chapter 10 the conformational behavior of cylindrical poly-L-lysine brush-sodium dodecyl sulfate complexes was studied using AFM imaging. Surfactant induced cylinder to helix like to globule conformational transitions were observed.

Synthesis and characterization of polyelectrolyte brushes

On the pathway to synthesizing synthetic model systems for human cartilage, macroinitiators for the ATRP of styrene sulfonate esters with different chain lengths and initiation site densities from 10 % to 100 % were synthesized. Polymer brushes from styrene sulfonate ethyl ester and styrene sulfonate dodecyl ester with varying grafting density, backbone length and side chain length were synthesized and characterized by 1H-NMR, AUC, AFM, TEM, and in the case of the ethyl esters, GPC-MALLS. Polyelectrolyte brushes from styrene sulfonate were synthesized from the corresponding esters. These brushes were characterized in solution (GPC-MALLS, static and dynamic light scattering, SANS, 1H-NMR) and on solid interfaces (AFM and TEM). It was shown that these brushes may form extended aggregates in solution. The aggregation behavior and the size and shape of the aggregates depend on the side chain length and the degree of saponification. For samples with identical backbone and side chain length, but varying degrees of ester hydrolysis, marked differences in the aggregation behavior were observed. A functionalized ATRP macroinitiator with a positively charged head group was synthesized and employed for the synthesis of a functionalized polyelectrolyte brush. These brushes were found to form complexes with negatively charged latex particles and are thus suitable as proteoglycan models in the proteoglycan-hyaluronic acid complex.

Synthese und Charakterisierung von multivalenten kationischen Tensiden und Polymeren

Der Einsatz von den Polyelektrolytkomplexen von DNA / RNA mit Polykationen oder Lipiden in der Gen-Therapie ist für Wissenschaftler von besonderem Interesse, da sie als Träger für den Transport von genetischem Material in lebende Zellen fungieren können. Interessant ist auch die Komplexbildung aus Gadolinium und Polykation, hier können die stabil gebildeten Aggregate als Kontrastmittel zur Anwendung in der Magnetresonanztomographie eingeführt werden. Ziel der vorliegenden Arbeit war es, strukturdefinierte, positiv geladene, polyvalente sperminanaloge Polymere zu synthetisieren. Durch die polyelektrolytische Natur erlauben solche Polymere die Komplexierung von mehr Gadolinium-Polyoxometalaten und wären deshalb sehr gut als Kontrastmittel geeignet. Aufbauend auf den Vorarbeiten, wurde insbesondere die Komplexbildung von kationischem Polymer mit der Green Fluorescent Protein DNA in physiologischem Salzgehalt untersucht. Die Beschreibung der Synthese im Rahmen dieser Arbeit zeigt, dass es mit dem entwickelten Syntheseprinzip, also unter Einsatz von orthogonaler Schutzgruppenchemie und funktionaler Transformation gelungen ist, durch einfache nukleophile Substitution die Kopplung der Elementareinheiten zu komplexeren, auch ionischen Tensiden durchzuführen. Die Komplexierung von Gadolinium-Polyoxometalat mit kationisch geladenem Polymer in reinem Wasser und in physiologischem Salzgehalt hat gezeigt, dass bei einem Ladungsverhältnis von ungefähr 2:1 stabile sphärische Komplexe gebildet werden. HeLa-Zellen zeigen keine hohe Empfindlichkeit gegenüber Polykation-POM-Komplexen, da deren toxische Wirkung nur einen Anteil toter Zellen von maximal 24 % zur Folge hatte. Die Bildqualität einer MRT-Aufnahme der gebildeten Polykation-POM-Komplexe wurde im Vergleich zu den reinen Gadolinium-Polyoxometalat-Lösungen erheblich verbessert. Die Komplexierung von DNA mit dem im Überschuss vorliegenden kationisch geladenen Polymer wurde mittels Rasterkraftmikroskopie, statischer sowie dynamischer Lichtstreuung untersucht. Die Molmasse und Größe der Polykation-DNA-Komplexe geben eindeutige Hinweise darauf, dass sich in physiologischer Salzlösung Multi-Ketten-Komplexe bilden. Neben der Untersuchung der Polymer-Komplexe wurde eine Reihe neuartiger multivalenter kationischer Tenside hergestellt, wobei ihre Eigenschaften beispielsweise mit Tensid B (C12N4), Tensid C (EG8N4) und Tensid F (EG8C12N4) in wässriger Lösung bei verschiedener Salzkonzentration im Vordergrund stehen.

Hydrodynamics and solid dosage form disintegration/dissolution : immediate release tablets and novel in situ polyelectrolyte gastroretentive drug delivery systems

Solid oral dosage form disintegration in the human stomach is a highly complex process dependent on physicochemical properties of the stomach contents as well as on physical variables such as hydrodynamics and mechanical stress. Understanding the role of hydrodynamics and forces in disintegration of oral solid dosage forms can help to improve in vitro disintegration testing and the predictive power of the in vitro test. The aim of this work was to obtain a deep understanding of the influence of changing hydrodynamic conditions on solid oral dosage form performance. Therefore, the hydrodynamic conditions and forces present in the compendial PhEur/USP disintegration test device were characterized using a computational fluid dynamics (CFD) approach. Furthermore, a modified device was developed and the hydrodynamic conditions present were simulated using CFD. This modified device was applied in two case studies comprising immediate release (IR) tablets and gastroretentive drug delivery systems (GRDDS). Due to the description of movement provided in the PhEur, the movement velocity of the basket-rack assembly follows a sinusoidal profile. Therefore, hydrodynamic conditions are changing continually throughout the movement cycle. CFD simulations revealed that the dosage form is exposed to a wide range of fluid velocities and shear forces during the test. The hydrodynamic conditions in the compendial device are highly variable and cannot be controlled. A new, modified disintegration test device based on computerized numerical control (CNC) technique was developed. The modified device can be moved in all three dimensions and radial movement is also possible. Simple and complex moving profiles can be developed and the influence of the hydrodynamic conditions on oral solid dosage form performance can be evaluated. Furthermore, a modified basket was designed that allows two-sided fluid flow. CFD simulations of the hydrodynamics and forces in the modified device revealed significant differences in the fluid flow field and forces when compared to the compendial device. Due to the CNC technique moving velocity and direction are arbitrary and hydrodynamics become controllable. The modified disintegration test device was utilized to examine the influence of moving velocity on disintegration times of IR tablets. Insights into the influence of moving speed, medium viscosity and basket design on disintegration times were obtained. An exponential relationship between moving velocity of the modified basket and disintegration times was established in simulated gastric fluid. The same relationship was found between the disintegration times and the CFD predicted average shear stress on the tablet surface. Furthermore, a GRDDS was developed based on the approach of an in situ polyelectrolyte complex (PEC). Different complexes composed of different grades of chitosan and carrageenan and different ratios of those were investigated for their swelling behavior, mechanical stability, and in vitro drug release. With an optimized formulation the influence of changing hydrodynamic conditions on the swelling behavior and the drug release profile was demonstrated using the modified disintegration test device. Both, swelling behavior and drug release, were largely dependent on the hydrodynamic conditions. Concluding, it has been shown within this thesis that the application of the modified disintegration test device allows for detailed insights into the influence of hydrodynamic conditions on solid oral dosage form disintegration and dissolution. By the application of appropriate test conditions, the predictive power of in vitro disintegration testing can be improved using the modified disintegration test device. Furthermore, CFD has proven a powerful tool to examine the hydrodynamics and forces in the compendial as well as in the modified disintegration test device. rn

Metal-complex ionosilicas: Cationic mesoporus silica with Ni(II) and Cu(II) complexes in their framework

Metal-complex ionosilicas with cationic complexes into the mesoporous silica framework were prepared using anionic surfactants. The electrostatic interaction between the anionic surfactant and the cationic metal complexes incorporated in the silica framework allows for the fine tuning of the mesoporous structure. The gentle procedure of synthesis developed and mild ion-exchange extraction of the surfactant, allowed a cleaner route for the immobilization of homogeneous cationic catalysts in mesoporous silica, while protecting the structural and chemical integrity of the metal complexes.

Novel tear film supplements:a potential application for synthetic protein-phospholipid complexes

Purpose: Surfactant proteins A, B, C and D complex with (phospho)lipids to produce surfactants which provide low interfacial tensions. It is likely that similar complexation occurs in the tear film and contributes to its low surface tension. Synthetic protein-phospholipid complexes, with styrene maleic anhydrides (SMAs) as the protein analogue, have been shown to have similarly low surface tensions. This study investigates the potential of modified SMAs and/or SMA-phospholipid complexes, which form under physiological conditions, to supplement natural tear film surfactants. Method: SMAs were modified to provide structural variants which can form complexes under varying conditions. Infrared spectroscopy and Nuclear Magnetic Resonance were used to confirm SMA structure. Interfacial behaviour of the SMA and SMA-phospholipid complexes was studied using Langmuir trough, du Nûoy ring and pulsating bubblemethods. Factors which affect SMA-phospholipid complex formation, such as temperature and pH, were also investigated. Results: Structural manipulation of SMAs allows control over complex formation, including under physiological conditions (e.g. partial SMAesterfication allowed complexation with dimyristoylphosphatidylcholine, at pH7). The low surface tensions of the SMAs (42mN/m for static (du Nûoy ring) and 34mN/m for dynamic (Langmuir) techniques) demonstrate their surface activity at the air-aqueous interface. SMA-phospholipid complexes provide even lower surface tensions (~2 mN/m), approaching that of lung surfactant, as measured by the pulsating bubblemethod. Conclusions: Design of the molecular architecture of SMAs allows control over their surfactant properties. These SMAs could be used as novel tear films supplements, either alone to complex with native tear film phospholipids or delivered as synthetic protein-phospholipid complexes.