APTES-Modified RE2O3:Eu3+ Luminescent Beads: Structure and Properties

Europium-doped lanthanide oxide RE2O3:Eu3+ (RE = Y or Gd) luminescent beads, with a spherical shape and a diameter of 150 +/- 15 nm, have been modified by reaction with 3-aminopropyltriethoxysilane (APTES), in order to introduce reactive amine groups at their surfaces. The direct silanation has resulted in the formation of a nanometric layer at the surface of the beads, with an optimum grafting rate of 0.055 +/- 0.005 mol APTES/mol RE2O3. Fourier transform infrared (FTIR) and X-ray photoelectron (XPS) spectroscopies confirmed the condensation of an organosilane layer, made of cross-linked -O-Si-O-Si- and of groups -O-Si-R (with R = (CH2)(3)NH2 or O-Et). Titration of the accessible amine groups has been performed by simultaneously measuring the luminescence of grafted fluorescein isothiocyanate and that of core particles: there are about 2.3 X 10(4) (2.8 X 10(4)) -NH2 per Y2O3:Eu3+ (Gd2O3:Eu3+) bead. The isoelectronic point was shifted by one pH unit after APTES modification. The surface modification by APTES at least preserved (for Gd2O3:Eu3+) or improved (for Y2O3:Eu3+) the red emission of the beads.

Identification of Novel Interaction between ADAM17 (a Disintegrin and Metalloprotease 17) and Thioredoxin-1

ADAM17, which is also known as TNF alpha-converting enzyme, is the major sheddase for the EGF receptor ligands and is considered to be one of the main proteases responsible for the ectodomain shedding of surface proteins. How a membrane-anchored proteinase with an extracellular catalytic domain can be activated by inside-out regulation is not completely understood. We characterized thioredoxin-1 (Trx-1) as a partner of the ADAM17 cytoplasmic domain that could be involved in the regulation of ADAM17 activity. We induced the overexpression of the ADAM17 cytoplasmic domain in HEK293 cells, and ligands able to bind this domain were identified by MS after protein immunoprecipitation. Trx-1 was also validated as a ligand of the ADAM17 cytoplasmic domain and full-length ADAM17 recombinant proteins by immunoblotting, immunolocalization, and solid phase binding assay. In addition, using nuclear magnetic resonance, it was shown in vitro that the titration of the ADAM17 cytoplasmic domain promotes changes in the conformation of Trx-1. The MS analysis of the cross-linked complexes showed cross-linking between the two proteins by lysine residues. To further evaluate the functional role of Trx-1, we used a heparin-binding EGF shedding cell model and observed that the overexpression of Trx-1 in HEK293 cells could decrease the activity of ADAM17, activated by either phorbol 12-myristate 13-acetate or EGF. This study identifies Trx-1 as a novel interaction partner of the ADAM17 cytoplasmic domain and suggests that Trx-1 is a potential candidate that could be involved in ADAM17 activity regulation.

Do patients with osteogenesis imperfecta need individualized nutritional support?

Objective: Information regarding nutrition and body composition in patients diagnosed with osteogenesis imperfecta (OI) is scarce. In the present study, nutritional status, bone mineral density, and biochemical parameters of subjects with Of were evaluated. Methods: Patients with type I OI (n = 13) and type III OI (n = 13) and healthy controls (n = 8) were selected. Nutritional status and bone mineral density were assessed by a 3-d food diary and dual-energy X-ray absorptiometry at the lumbar spine, respectively. Body mass index, serum albumin, calcium, creatinine, cross-linked C-telopeptide, parathyroid hormone, and 25-hydroxivitamin D-3 were also evaluated. Results: Patients with OI had lower bone mineral density (P < 0.05 versus controls). Patients with type III OI had the highest body mass index (P < 0.05 versus patients with type I OI and controls) and the lowest lean body mass (P < 0.05 versus patients with type I OI and controls). In patients with OI, the number of fractures was positively correlated with body mass index (r = 0.581, P = 0.002) and the percentage of body fat (r = 0.451, P = 0.027) and negatively correlated to lean body mass (r = -0.523, P = 0.009). Even when taking dietary supplements, 58% and 12% of subjects with OI did not achieve the calcium and vitamin D recommendations, respectively. Conclusions: Body composition is a risk factor for bone fractures in subjects with OI. Individualized nutritional support is recommended not only to improve body composition but also to potentiate pharmacologic and physical therapies. (C) 2012 Elsevier Inc. All rights reserved.

Electrical characterization of poly(amide-imide) for application in organic field effect devices

The admittance spectra and current-voltage (I-V) characteristics are reported of metal-insulator-metal (MIM) and metal-insulator-semiconductor (MIS) capacitors employing cross-linked poly(amide-imide) (c-PAI) as the insulator and poly(3-hexylthiophene) (P3HT) as the active semiconductor. The capacitance of the MIM devices are constant in the frequency range from 10 Hz to 100 kHz, with tan delta values as low as 7 x 10(-3) over most of the range. Except at the lowest voltages, the I-V characteristics are well-described by the Schottky equation for thermal emission of electrons from the electrodes into the insulator. The admittance spectra of the MIS devices displayed a classic Maxwell-Wagner frequency response from which the transverse bulk hole mobility was estimated to be similar to 2 x 10(-5) cm(2) V(-1)s(-1) or similar to 5 x 10(-8) cm(2) V(-1)s(-1) depending on whether or not the surface of the insulator had been treated with hexamethyldisilazane (HMDS) prior to deposition of the P3HT. From the maximum loss observed in admittance-voltage plots, the interface trap density was estimated to be similar to 5 x 10(10) cm(-2) eV(-1) or similar to 9 x 10(10) cm(-2) eV(-1) again depending whether or not the insulator was treated with HMDS. We conclude, therefore, that HMDS plays a useful role in promoting order in the P3HT film as well as reducing the density of interface trap states. Although interposing the P3HT layer between the insulator and the gold electrode degrades the insulating properties of the c-PAI, nevertheless, they remain sufficiently good for use in organic electronic devices. (c) 2012 Elsevier B.V. All rights reserved.

ROMP como um método versátil para a obtenção de materiais poliméricos diferenciados

Ring Opening Metathesis Polymerization (ROMP) of cyclic olefins is a powerful transition metal-catalyzed reaction for syntheses of polymers and copolymers. The key feature of this reaction is the [2+2]-cycloaddition mechanism, with retention of the olefinic unsaturation in the polymer chain and occurrence of living polymerization. With the development of metal-carbene type catalysts for this process, many addressed polymeric materials have been successfully prepared to be employed in several fields of the science and technology. This review summarizes recent examples of syntheses of polymers with amphiphilic features such as block, graft, brush or star copolymers; as well syntheses of biomaterials, dendronized architectures, photoactive polymers, cross-linked or self-healing materials, and polymers from renewed supplies.

Derivati polimerici organometallici ancorati su matrice inorganica per applicazioni in chimica fine

Organotin compounds have found in the last few decades a wide variety of applications. Indeed, they are used successfully as antifouling paints, PVC stabilizers and ion carriers, as well as homogeneous catalysts. In this context, it has been proved that the Lewis acidity of the metal centre allows these compounds to promote the reaction between alcohol and ester. However their use is now limited by their well-known toxicity, moreover they are hardly removable from the reaction mixture. This problem can be overcome by grafting the organotin derivative onto a polymeric cross-linked support. In this way the obtained heterogeneous catalyst can be easily filtered off from the reaction mixture, thus creating the so-called "clean organotin reagents", avoiding the presence of toxic organotin residues in solution and the tin release in the environment. In the last few years several insoluble polystyrene resins containing triorganotin carboxylate moieties have been synthesized with the aim of improving their catalytic activity: in particular we have investigated and opportunely modified their chemical structure in order to optimize the accessibility to the metal centre and its Lewis acidity. Recently, we replaced the polymeric matrix with an inorganic one, in order to dispose of a relatively cheaper and easily available support. For this purpose an ordered mesoporous silica, characterized by 2D-hexagonal pores, named MCM-41, and an amorphous silica have been selected. In the present work two kinds of MCM-41 silica containing the triorganotin carboxylate moiety have been synthesized starting from a commercial Cab-O-Sil M5 silica. These catalysts have two different spacers between the core and the tin-carboxylate moiety, namely a polyaliphatic chain (compound FT29) or a poliethereal one (compound FT6), with the aim to improve the interaction between catalyst and reacting ester. Three catalysts supported onto an amorphous silica have been also synthesized: the structure is the same as silica FT29, i.e. a compound having a polialiphatic chain, and they have different percentage of organotin derivative grafted on the silica surface (10, 30, 50% respectively for silica MB9, SU27 and SU28). The performances of the above silica as heterogeneous catalysts in transesterification reactions have been tested in a model reaction between ethyl acetate and 1-octanol, a primary alcohol sensitive to the reaction conditions. The alcohol conversion was assessed by gas-chromatography, determining the relative amount of transesterified product and starting alcohol after established time intervals.

Sistemi liquido cristallini complessi: simulazioni al calcolatore e studi ESR

The aim of this PhD thesis was to study at a microscopic level different liquid crystal (LC) systems, in order to determine their physical properties, resorting to two distinct methodologies, one involving computer simulations, and the other spectroscopic techniques, in particular electron spin resonance (ESR) spectroscopy. By means of the computer simulation approach we tried to demonstrate this tool effectiveness for calculating anisotropic static properties of a LC material, as well as for predicting its behaviour and features. This required the development and adoption of suitable molecular models based on a convenient intermolecular potentials reflecting the essential molecular features of the investigated system. In particular, concerning the simulation approach, we have set up models for discotic liquid crystal dimers and we have studied, by means of Monte Carlo simulations, their phase behaviour and self­-assembling properties, with respect to the simple monomer case. Each discotic dimer is described by two oblate Gay­Berne ellipsoids connected by a flexible spacer, modelled by a harmonic "spring" of three different lengths. In particular we investigated the effects of dimerization on the transition temperatures, as well as on the characteristics of molecular aggregation displayed and the relative orientational order. Moving to the experimental results, among the many experimental techniques that are typically employed to evaluate LC system distinctive features, ESR has proved to be a powerful tool in microscopic scale investigation of the properties, structure, order and dynamics of these materials. We have taken advantage of the high sensitivity of the ESR spin probe technique to investigate increasingly complex LC systems ranging from devices constituted by a polymer matrix in which LC molecules are confined in shape of nano- droplets, as well as biaxial liquid crystalline elastomers, and dimers whose monomeric units or lateral groups are constituted by rod-like mesogens (11BCB). Reflection-mode holographic-polymer dispersed liquid crystals (H-PDLCs) are devices in which LCs are confined into nanosized (50­-300 nm) droplets, arranged in layers which alternate with polymer layers, forming a diffraction grating. We have determined the configuration of the LC local director and we have derived a model of the nanodroplet organization inside the layers. Resorting also to additional information on the nanodroplet size and shape distribution provided by SEM images of the H-PDLC cross-section, the observed director configuration has been modeled as a bidimensional distribution of elongated nanodroplets whose long axis is, on the average, parallel to the layers and whose internal director configuration is a uniaxial quasi- monodomain aligned along the nanodroplet long axis. The results suggest that the molecular organization is dictated mainly by the confinement, explaining, at least in part, the need for switching voltages significantly higher and the observed faster turn-off times in H-PDLCs compared to standard PDLC devices. Liquid crystal elastomers consist in cross-linked polymers, in which mesogens represent the monomers constituting the main chain or the laterally attached side groups. They bring together three important aspects: orientational order in amorphous soft materials, responsive molecular shape and quenched topological constraints. In biaxial nematic liquid crystalline elastomers (BLCEs), two orthogonal directions, rather than the one of normal uniaxial nematic, can be controlled, greatly enhancing their potential value for applications as novel actuators. Two versions of a side-chain BLCEs were characterized: side­-on and end­-on. Many tests have been carried out on both types of LCE, the main features detected being the lack of a significant dynamical behaviour, together with a strong permanent alignment along the principal director, and the confirmation of the transition temperatures already determined by DSC measurements. The end­-on sample demonstrates a less hindered rotation of the side group mesogenic units and a greater freedom of alignment to the magnetic field, as already shown by previous NMR studies. Biaxial nematic ESR static spectra were also obtained on the basis of Molecular Dynamics generated biaxial configurations, to be compared to the experimentally determined ones, as a mean to establish a possible relation between biaxiality and the spectral features. This provides a concrete example of the advantages of combining the computer simulation and spectroscopic approaches. Finally, the dimer α,ω-bis(4'-cyanobiphenyl-4-yl)undecane (11BCB), synthesized in the "quest" for the biaxial nematic phase has been analysed. Its importance lies in the dimer significance as building blocks in the development of new materials to be employed in innovative technological applications, such as faster switching displays, resorting to the easier aligning ability of the secondary director in biaxial phases. A preliminary series of tests were performed revealing the population of mesogenic molecules as divided into two groups: one of elongated straightened conformers sharing a common director, and one of bent molecules, which display no order, being equally distributed in the three dimensions. Employing this model, the calculated values show a consistent trend, confirming at the same time the transition temperatures indicated by the DSC measurements, together with rotational diffusion tensor values that follow closely those of the constituting monomer 5CB.

Preparazione e caratterizzazione di espansi in PVC per la produzione di pannelli compositi utilizzati in campo eolico e navale

I materiali polimerici espansi sono utilizzati come core di pannelli compositi di tipo sandwich (tipicamente a base di polivinilcloruro, polistirene e poliuretani). Negli ultimi anni molte ricerche si sono concentrate sulla possibilità di aumentare le loro proprietà meccaniche, termiche, di resistenza agli agenti esterni, ignifughe, etc cercando contemporaneamente la diminuzione del peso e del costo (sia delle materia prime che di processo). In questo contesto, l’obiettivo di questa tesi di laurea è lo studio, la preparazione e la caratterizzazione di espansi in PVC di natura cross-linked per la produzione di pannelli compositi a sandwich potenzialmente utilizzabili in campo eolico e navale.

Amalgamersatz

Amalgamersatz:Neue Wege zur Herstellung von Dentalkompositen mit geringem Polymerisationsschrumpf auf (Meth-)Acrylat-Basis Aufgrund der ästhetischen und gesundheitlichen Bedenken wird seit Jahrzehnten nach einer Alternative für Amalgam als Zahnfüllmaterial gesucht. Der größte Nachteil von organischen Monomeren liegt in der Volumenkontraktion während der Aushärtung, welche sich negativ auf die Materialeigenschaften auswirkt. Aus diesem Grund war das Hauptziel dieser Arbeit, eine Minimierung des Schrumpfes bei der radikalischen Polymerisation zu erreichen. Dazu wurden verschiedene, zum Teil neue, (Meth-)Acrylate synthetisiert und auf ihre Einsetzbarkeit als Bestandteil von Dentalkompositen geprüft.Um die Volumenkontraktion während der Polymerisation zu minimieren, wurde die Beweglichkeit der polymerisierbaren Gruppe eingeschränkt. Im ersten Teil der Arbeit wurden dazu flüssigkristalline Substanzen eingesetzt. Durch Mischen von flüssigkristallinen Diacrylaten konnte eine Mesophase im gewünschten Temperaturintervall von 25 bis 35 °C erhalten werden. Der Einsatz dieser Flüssigkristalle zeigte einen positiven Einfluss auf den Polymerisationsschrumpf. Zudem wurden neue Monomere synthetisiert, deren Methacrylgruppe in direkter Nachbarschaft zum Mesogen angebunden wurde, um die Stabilität der erhaltenen Polymere zu erhöhen.Im zweiten Teil der Arbeit wurde die Beweglichkeit der polymerisierbaren Gruppe durch eine Fixierung an einem starren Kern reduziert. Als Grundkörper wurden Polyphenole, enzymatisch polymerisierte Phenole und ߖCyclodextrin verwendet. Bei den modifizierten Polyphenolen auf Basis von Gallussäure und 3,5-Dihydroxybenzoesäure konnte eine leichte Reduzierung des Polymerisationsschrumpfes erreicht werden. Mit HRP (Horseradish Peroxidase) katalysierten enzymatisch polymerisierten Phenole konnte dagegen nicht photochemisch vernetzt werden, da diese Oligomere in Lösung gefärbt vorlagen. Zudem zeigten die freien, phenolischen Hydroxygruppen eine sehr geringe Reaktivität. Die besten Ergebnisse wurden mit modifizierten ߖCyclodextrinen als Komponente einer Komposite erreicht. Dabei wurde in einem Fall sogar eine leichte Volumenexpansion während der Polymerisation erzielt.

Cellulose based Lithium ion polymer electrolytes for Lithium batteries

The separator membrane in batteries and fuel cells is of crucial importance for the function of these devices. In lithium ion batteries the separator membrane as well as the polymer matrix of the electrodes consists of polymer electrolytes which are lithium ion conductors. To overcome the disadvantage of currently used polymer electrolytes which are highly swollen with liquids and thus mechanically and electrochemically unstable, the goal of this work is a new generation of solid polymer electrolytes with a rigid backbone and a soft side chain structure. Moreover the novel material should be based on cheap substrates and its synthesis should not be complicated aiming at low overall costs. The new materials are based on hydroxypropylcellulose and oligoethyleneoxide derivatives as starting materials. The grafting of the oligoethyleneoxide side chains onto the cellulose was carried out following two synthetic methods. One is based on a bromide derivative and another based on p-toluolsulfonyl as a leaving group. The side chain reagents were prepared form tri(ethylene glycol) monoethyl ether. In order to improve the mechanical properties the materials were crosslinked. Two different conceptions have been engaged based on either urethane chemistry or photosensitive dimethyl-maleinimide derivatives. PEO - graft - cellulose derivatives with a high degree of substitution between 2,9 and 3,0 were blended with lithium trifluoromethane-sulfonate, lithium bis(trifluorosulfone)imide and lithium tetrafluoroborate. The molar ratios were in the range from 0,02 to 0,2 [Li]/[O]. The products have been characterized with nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and laserlight scattering (LS) with respect to their degree of substitution and molecular weight. The effect of salt concentration on ionic conductivity, thermal behaviour and morphology has been investiga-ted with impedance spectroscopy, differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The crosslinking reactions were controlled with dynamic mechanical analysis (DMS). The degree of substitution of our products is varying between 2,8 and 3,0 as determined by NMR. PEO - graft - cellulose derivatives are highly viscous liquids at room temperature with glass transition temperatures around 215 K. The glass transition temperature for the Lithium salt complexes of PEO - graft - cellulose deri-vatives increase with increasing salt content. The maximum conductivity at room temperature is about 10-4 and at 100°C around 10-3 Scm-1. The presence of lithium salt decreases the thermal stability of the complexes in comparison to pure PEO - graft - cellulose derivatives. Complexes heated over 140 – 150°C completely lose their ionic conductivity. The temperature dependence of the conductivity presented as Arrhenius-type plots for all samples is similar in shape and follows a VTF behaviour. This proofs that the ionic transport is closely related to the segmental motions of the polymer chains. Novel cellulose derivatives with grafted oligoethylen-oxide side chains with well-defined chemical structure and high side chain grafting density have been synthesized. Cellulose was chosen as stiff, rod like macromolecule for the backbone while oligoethylen-oxides are chosen as flexible side chains. A maximum grafting density of 3.0 have been obtained. The best conductivity reaches 10-3 Scm-1 at 100°C for a Li-triflate salt complex with a [Li]/[O] ratio of 0.8. The cross-linked complexes containing the lithium salts form elastomeric films with convenient mechanical stability. Our method of cellulose modification is based on relatively cheap and commercially available substrates and as such appears to be a promising alternative for industrial applications.

Polymer properties measured by micromechanical cantilever technique

Surface stress changes induced by specific adsorption of molecules were investigated using a micromechanical cantilever sensor (MCS) device. 16 MCS are grouped within four separate wells. Each well can be addressed independently by different liquid enabling functionalization of MCS separately by flowing different solutions through each well and performing sensing and reference experiments simultaneously. In addition, each well contains a fixed reference mirror, which allows measuring the absolute bending of MCS. The effect of the flow rate on the MCS bending change was found to be dependent on the absolute bending value of MCS. In addition, the signal from the reference mirror can be used to follow refractive index changes upon mixing different solutions. Finite element simulation of solution exchange in wells was compared with experiment results. Both revealed that one solution can be exchanged by another one after a total volume of 200 µl has flown through. Using MCS, the adsorption of thiolated deoxyribonucleic acid (DNA) molecules and 6-mercapto-1-hexanol (MCH) on gold surfaces, and the DNA hybridization were performed. The nanomechanical response is in agreement with data reported by Fritz et al.1 Thus, the multiwell device is readily applicable for sensing of multiple chemical and biological recognition events in a single step. In this context controlled release and uptake of drugs are currently widely discussed. As a model system, we have used polystyrene (PS) spheres with diameters in the order of µm. The swelling behavior of individual PS spheres in toluene vapor was studied via mass loading by means of micromechanical cantilever sensors. For 4–8% cross-linked PS a mass increase of 180% in saturated toluene vapor was measured. In addition, the diameter change in saturated toluene vapor was measured and the corresponding volume increase of 200% was calculated. The mass of the swollen PS sphere decreases with increasing exposure time to ultraviolet (UV) light. The swelling response is significantly different between the first and the second exposure to toluene vapor. This is attributed to the formation of a cross-linked shell at the surface of the PS spheres. Shape persistent parts were observed for locally UV irradiated PS spheres. These PS spheres were found to be fluorescent and cracks occur after exposure in toluene liquid. The diffusion time of dye molecules in PS spheres increases with increasing chemical cross-linking density. This concept of locally dissolving non cross-linked PS from the sphere was applied to fabricate donut structures on surfaces. Arrays of PS spheres were fabricated using spin coating. The donut structure was produced simply after liquid solvent rinsing. The complete cross-linking of PS spheres was found after long exposure time to UV. We found that stabilizers play a major role in the formation of the donut nanostructures.

Anhydrous proton conducting polymer electrolytes based on polymeric ionic liquids

Imidazolium types of ionic liquids were immobilized by tethering it to acrylate backbone. These imidazolium salt containing acrylate monomers were polymerize at 70oC by free radical polymerization to give polymers poly(AcIm-n) with n being the side chain lenght. The chemical structure of the polymer electrolytes obtained by the described synthetic routes was investigated by NMR-spectroscopy. The polymers were doped with various amounts of H3PO4 and LiN(SO2CF3)2, to obtain poly(AcIm-n) x H3PO4 and poly(AcIm-2-Li) x LiN(SO2CF3)2. The TG curves show that the polymer electrolytes are thermally stable up to about 200◦C. DSC results indicates the softening effect of the length of the spacers (n) as well as phosphoric acid. The proton conductivity of the samples increase with x and reaches to 10-2 Scm-1 at 120oC for both poly(AcIm-2)2H3PO4 and poly(AcIm-6)2H3PO4. It was observed that the lithium ion conductivity of the poly(AcIm-2-Li) x LiN(SO2CF3)2 increases with blends (x) up to certain composition and then leveled off independently from blend content. The conductivity reaches to about 10-5 S cm-1 at 30oC and 10-3 at 100oC for poly(AcIm-2-Li) x LiN(SO2CF3)2 where x is 10. The phosphate and phosphoric acid functionality in the resulting polymers, poly(AcIm-n) x H3PO4, undergoes condensation leading to the formation of cross-linked materials at elevated temperature which may improve the mechanical properties to be used as membrane materials in fuel cells. High resolution nuclear magnetic resonance (NMR) spectroscopy was used to obtain information about hydrogen bonding in solids. The low Tg enhances molecular mobility and this leads to better resolved resonances in both the backbone region and side chain region. The mobile and immobile protons can be distinguished by comparing 1H MAS and 1H-DQF NMR spectra. The interaction of the protons which may contribute to the conductivity is observed from the 2D double quantum correlation (DQC) spectra.

Diffusion in polymer systems studied by fluorescence correlation spectroscopy

Fluorescence correlation spectroscopy (FCS) is a powerful technique to determine the diffusion of fluorescence molecules in various environments. The technique is based on detecting and analyzing the fluctuation of fluorescence light emitted by fluorescence species diffusing through a small and fixed observation volume, formed by a laser focused into the sample. Because of its great potential and high versatility in addressing the diffusion and transport properties in complex systems, FCS has been successfully applied to a great variety of systems. In my thesis, I focused on the application of FCS to study the diffusion of fluorescence molecules in organic environments, especially in polymer melts. In order to examine our FCS setup and a developed measurement protocol, I first utilized FCS to measure tracer diffusion in polystyrene (PS) solutions, for which abundance data exist in the literature. I studied molecular and polymeric tracer diffusion in polystyrene solutions over a broad range of concentrations and different tracer and matrix molecular weights (Mw). Then FCS was further established to study tracer dynamics in polymer melts. In this part I investigated the diffusion of molecular tracers in linear flexible polymer melts [polydimethylsiloxane (PDMS), polyisoprene (PI)], a miscible polymer blend [PI and poly vinyl ethylene (PVE)], and star-shaped polymer [3-arm star polyisoprene (SPI)]. The effects of tracer sizes, polymer Mw, polymer types, and temperature on the diffusion coefficients of small tracers were discussed. The distinct topology of the host polymer, i.e. star polymer melt, revealed the notably different motion of the small tracer, as compared to its linear counterpart. Finally, I emphasized the advantage of the small observation volume which allowed FCS to investigate the tracer diffusions in heterogeneous systems; a swollen cross-linked PS bead and silica inverse opals, where high spatial resolution technique was required.

Inorganic-organic hybrid polymers: Solution-processible coating materials for defined surface functionalization

A new class of inorganic-organic hybrid polymers could successfully been prepared by the combination of different polymerization techniques. The access to a broad range of organic polymers incorporated into the hybrid polymer was realized using two independent approaches.rnIn the first approach a functional poly(silsesquioxane) (PSSQ) network was pre-formed, which was capable to initiate a controlled radical polymerization to graft organic vinyl-type monomers from the PSSQ precursor. As controlled radical polymerization techniques atom transfer radical polymerization (ATRP), as well as reversible addition fragmentation chain transfer (RAFT) polymerization could be used after defined tuning of the PSSQ precursor either toward a PSSQ macro-initiator or to a PSSQ macro-chain-transfer-agent. The polymerization pathway, consisting of polycondensation of trialkoxy-silanes followed by grafting-from polymerization of different monomers, allowed synthesis of various functional hybrid polymers. A controlled synthesis of the PSSQ precursors could successfully be performed using a microreactor setup; the molecular weight could be adjusted easily while the polydispersity index could be decreased well below 2.rnThe second approach aimed to incorporate differently derived organic polymers. As examples, polycarbonate and poly(ethylene glycol) were end-group-modified using trialkoxysilanes. After end-group-functionalization these organic polymers could be incorporated into a PSSQ network.rnThese different hybrid polymers showed extraordinary coating abilities. All polymers could be processed from solution by spin-coating or dip-coating. The high amount of reactive silanol moieties in the PSSQ part could be cross-linked after application by annealing at 130° for 1h. Not only cross-linking of the whole film was achieved, which resulted in mechanical interlocking with the substrate, also chemical bonds to metal or metal oxide surfaces were formed. All coating materials showed high stability and adhesion onto various underlying materials, reaching from metals (like steel or gold) and metal oxides (like glass) to plastics (like polycarbonate or polytetrafluoroethylene).rnAs the material and the synthetic pathway were very tolerant toward different functionalities, various functional monomers could be incorporated in the final coating material. The incorporation of N-isopropylacrylamide yielded in temperature-responsive surface coatings, whereas the incorporation of redox-active monomers allowed the preparation of semi-conductive coatings, capable to produce smooth hole-injection layers on transparent conductive electrodes used in optoelectronic devices.rnThe range of possible applications could be increased tremendously by incorporation of reactive monomers, capable to undergo fast and quantitative conversions by polymer-analogous reactions. For example, grafting active esters from a PSSQ precursor yielded a reactive surface coating after application onto numerous substrates. Just by dipping the coated substrate into a solution of a functionalized amine, the desired function could be immobilized at the interface as well as throughout the whole film. The obtained reactive surface coatings could be used as basis for different functional coatings for various applications. The conversion with specifically tuned amines yielded in surfaces with adjustable wetting behaviors, switchable wetting behaviors or as recognition element for surface-oriented bio-analytical devices. The combination of hybrid materials with orthogonal reactivities allowed for the first time the preparation of multi-reactive surfaces which could be functionalized sequentially with defined fractions of different groups at the interface. rnThe introduced concept to synthesis functional hybrid polymers unifies the main requirements on an ideal coating material. Strong adhesion on a wide range of underlying materials was achieved by secondary condensation of the PSSQ part, whereas the organic part allowed incorporation of various functionalities. Thus, a flexible platform to create functional and reactive surface coatings was achieved, which could be applied to different substrates. rn

Nicht-wässrige Emulsionen zur Erzeugung neuer Nanopartikel

In der eingereichten Arbeit wurde die Nutzung von nicht-wässrigen Emulsionen, bestehend aus zwei organischen, aprotischen Lösungsmitteln, zur Erzeugung verschiedener polymerer Nanopartikel beschrieben. Diese Zweiphasenmischungen und die Verwendung maßgeschneiderter Emulgatoren bestehend aus Poly(isopren-block-methylmethacrylat) ermöglichten den Zugang zu einer Vielzahl an Reaktionen und Prozessen, welche in wässrigen Emulsionen bisher nicht oder nur schwer möglich waren. Die Generierung von Partikeln auf Basis katalytischer Polymerisationen erfolgte unter Verwendung der Ringöffnenden Metathese-Polymerisation (ROMP), der Acyclischen Dien-Metathese-Polymerisation (ADMET), der Cyclopolymerisation von α,ω-Diinen und der Ni-katalysierten Polymerisation von Isocyaniden. Mittels ROMP konnten stabile Dispersionen erzeugt werden, welche Partikel mit verschiedensten Molekulargewichten, Größen und Morphologien enthielten. Diese Eigenschaften konnten durch die Wahl des Monomers, die Katalysatorkonzentration oder den Emulgatortyp beeinflusst werden. Des Weiteren wurden Partikel mit komplexen Morphologien wie Kern-Schale-Strukturen synthetisiert. Dazu erfolgte die Generierung von Partikeln aus Poly(urethan) oder Poly(norbornenderivaten), welche in situ und ohne intermediäre Aufarbeitung mit einer Schale aus Poly(methacrylat) versehen wurden. Der Nachweis dieser Strukturen gelang mittels verschiedener Schwermetall-Markierungsverfahren in der Transmissionselektronenmikroskopie. Schlussendlich erfolgte die Herstellung von hochvernetzten und molekular geprägten Poly(acrylsäure)-Partikeln. Hierbei wurden unterschiedliche pharmakologische Wirkstoffe und Farbstoffe in die Partikel eingebracht, um deren Migrationsverhalten und Wiederanbindung an die Partikel zu untersuchen. Weiterhin wurden die Partikel erfolgreich in Zellaufnahmeexperimenten eingesetzt.