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Improvement of a fluorescence immunoassay with a compact diode-pumped solid state laser at 315 nm
(2006)
We demonstrate the improvement of fluorescence immunoassay (FIA) diagnostics in deploying a newly developed compact diode-pumped solid state (DPSS) laser with emission at 315 nm. The laser is based on the quasi-three-level transition in Nd:YAG at 946 nm. The pulsed operation is either realized by an active Q-switch using an electro-optical device or by introduction of a Cr<SUP>4+</SUP>:YAG saturable absorber as passive Q-switch element. By extra-cavity second harmonic generation in different nonlinear crystal media we obtained blue light at 473 nm. Subsequent mixing of the fundamental and the second harmonic in a β-barium-borate crystal provided pulsed emission at 315 nm with up to 20 μJ maximum pulse energy and 17 ns pulse duration. Substitution of a nitrogen laser in a FIA diagnostics system by the DPSS laser succeeded in considerable improvement of the detection limit. Despite significantly lower pulse energies (7 μJ DPSS laser versus 150 μJ nitrogen laser), in preliminary investigations the limit of detection was reduced by a factor of three for a typical FIA.
Quantum dots (QDs) are common as luminescing markers for imaging in biological applications because their optical properties seem to be inert against their surrounding solvent. This, together with broad and strong absorption bands and intense, sharp tuneable luminescence bands, makes them interesting candidates for methods utilizing Förster Resonance Energy Transfer (FRET), e. g. for sensitive homogeneous fluoroimmunoassays (FIA). In this work we demonstrate energy transfer from Eu<SUP>3+</SUP>-trisbipyridin (Eu-TBP) donors to CdSe-ZnS-QD acceptors in solutions with and without serum. The QDs are commercially available CdSe-ZnS core-shell particles emitting at 655 nm (QD655). The FRET system was achieved by the binding of the streptavidin conjugated donors with the biotin conjugated acceptors. After excitation of Eu-TBP and as result of the energy transfer, the luminescence of the QD655 acceptors also showed lengthened decay times like the donors. The energy transfer efficiency, as calculated from the decay times of the bound and the unbound components, amounted to 37%. The Förster-radius, estimated from the absorption and emission bands, was ca. 77 Å. The effective binding ratio, which not only depends on the ratio of binding pairs but also on unspecific binding, was obtained from the donor emission dependent on the concentration. As serum promotes unspecific binding, the overall FRET efficiency of the assay was reduced. We conclude that QDs are good substitutes for acceptors in FRET if combined with slow decay donors like Europium. The investigation of the influence of the serum provides guidance towards improving binding properties of QD assays.
Nonaqueous synthesis of metal oxide nanoparticles and their assembly into mesoporous materials
(2006)
This thesis mainly consist of two parts, the synthesis of several kinds of technologically interesting crystalline metal oxide nanoparticles via nonaqueous sol-gel process and the formation of mesoporous metal oxides using some of these nanoparticles as building blocks via evaporation induced self-assembly (EISA) technique. In the first part, the experimental procedures and characterization results of successful syntheses of crystalline tin oxide and tin doped indium oxide (ITO) nanoparticles are reported. SnO2 nanoparticles exhibit monodisperse particle size (3.5 nm in average), high crystallinity and particularly high dispersibility in THF, which enable them to become the ideal particulate precursor for the formation of mesoporous SnO2. ITO nanoparticles possess uniform particle morphology, narrow particle size distribution (5-10 nm), high crystallinity as well as high electrical conductivity. The synthesis approaches and characterization of various mesoporous metal oxides, including TiO2, SnO2, mixture of CeO2 and TiO2, mixture of BaTiO3 and SnO2, are reported in the second part of this thesis. Mesoporous TiO2 and SnO2 are presented as highlights of this part. Mesoporous TiO2 was produced in the forms of both films and bulk material. In the case of mesoporous SnO2, the study was focused on the high order of the porous structure. All these mesoporous metal oxides show high crystallinity, high surface area and rather monodisperse pore sizes, which demonstrate the validity of EISA process and the usage of preformed crystalline nanoparticles as nanobuilding blocks (NBBs) to produce mesoporous metal oxides.
In recent years, the aim of supramolecular syntheses is not only the creation of particular structures but also the introduction of specific functions in these supramolecules. The present work describes the use of the ionic self-assembly (ISA) route to generate nanostructured materials with integrated functionality. Since the ISA strategy has proved to be a facile method for the production of liquid-crystalline materials, we investigated the phase behaviour, physical properties and function of a variety of ISA materials comprising a perylene derivative as the employed oligoelectrolyte. Functionality was introduced into the materials through the use of functional surfactants. In order to meet the requirements to produce functional ISA materials through the use of functional surfactants, we designed and synthesized pyrrole-derived monomers as surfactant building blocks. Owing to the presence of the pyrrole moiety, these surfactants are not only polymerizable but are also potentially conductive when polymerized. We adopted single-tailed and double-tailed N-substituted pyrrole monomers as target molecules. Since routine characterization analysis of the double-tailed pyrrole-containing surfactant indicated very interesting, complex phase behaviour, a comprehensive investigation of its interfacial properties and mesophase behavior was conducted. The synthesized pyrrole-derived surfactants were then employed in the synthesis of ISA complexes. The self-assembled materials were characterized and subsequently polymerized by both chemical and electrochemical methods. The changes in the structure and properties of the materials caused by the in-situ polymerization were addressed. In the second part of this work, the motif investigated was a property rather than a function. Since chiral superstructures have obtained much attention during the last few years, we investigated the possibility of chiral ISA materials through the use of chiral surfactants. Thus, the work involved synthesis of novel chiral surfactants and their incorporation in ISA materials with the aim of obtaining ionically self-assembled chiral superstructures. The results and insights presented here suggest that the presented synthesis strategy can be easily extended to incorporate any kind of charged tectonic unit with desired optical, electrical, or magnetic properties into supramolecular assemblies for practical applications.
Adsorption layers of soluble surfactants enable and govern a variety of phenomena in surface and colloidal sciences, such as foams. The ability of a surfactant solution to form wet foam lamellae is governed by the surface dilatational rheology. Only systems having a non-vanishing imaginary part in their surface dilatational modulus, E, are able to form wet foams. The aim of this thesis is to illuminate the dissipative processes that give rise to the imaginary part of the modulus. There are two controversial models discussed in the literature. The reorientation model assumes that the surfactants adsorb in two distinct states, differing in their orientation. This model is able to describe the frequency dependence of the modulus E. However, it assumes reorientation dynamics in the millisecond time regime. In order to assess this model, we designed a SHG pump-probe experiment that addresses the orientation dynamics. Results obtained reveal that the orientation dynamics occur in the picosecond time regime, being in strong contradiction with the two states model. The second model regards the interface as an interphase. The adsorption layer consists of a topmost monolayer and an adjacent sublayer. The dissipative process is due to the molecular exchange between both layers. The assessment of this model required the design of an experiment that discriminates between the surface compositional term and the sublayer contribution. Such an experiment has been successfully designed and results on elastic and viscoelastic surfactant provided evidence for the correctness of the model. Because of its inherent surface specificity, surface SHG is a powerful analytical tool that can be used to gain information on molecular dynamics and reorganization of soluble surfactants. They are central elements of both experiments. However, they impose several structural elements of the model system. During the course of this thesis, a proper model system has been identified and characterized. The combination of several linear and nonlinear optical techniques, allowed for a detailed picture of the interfacial architecture of these surfactants.
To determine whether Förster resonance energy transfer (FRET) measurements can provide quantitative distance information in single-molecule fluorescence experiments on polypeptides, we measured FRET efficiency distributions for donor and acceptor dyes attached to the ends of freely diffusing polyproline molecules of various lengths. The observed mean FRET efficiencies agree with those determined from ensemble lifetime measurements but differ considerably from the values expected from Förster theory, with polyproline treated as a rigid rod. At donor–acceptor distances much less than the Förster radius R0, the observed efficiencies are lower than predicted, whereas at distances comparable to and greater than R0, they are much higher. Two possible contributions to the former are incomplete orientational averaging during the donor lifetime and, because of the large size of the dyes, breakdown of the point-dipole approximation assumed in Förster theory. End-to-end distance distributions and correlation times obtained from Langevin molecular dynamics simulations suggest that the differences for the longer polyproline peptides can be explained by chain bending, which considerably shortens the donor–acceptor distances.
Absorption and fluorescence properties of 4 hydraulic oils (3 biological and 1 petroleum-based) were investigated. In-situ LIF (laser-induced fluorescence) analysis of the oils on a brown sandy loam soil was performed. With calibration, quantitative detection was achieved. Estimated limits of detection were below ca. 500 mg/kg for the petroleum-based oil and ca. 2000 mg/kg for one biological oil. A semi-quantitative classification scheme is proposed for monitoring of the biological oils. This approach was applied to investigate the migration of a biological oil in soil-containing compartments, namely a soil column and a soil bed.
The interactions between peptides and lipids are of fundamental importance in the functioning of numerous membrane-mediated biochemical processes including antimicrobial peptide action, hormone-receptor interactions, drug bioavailability across the blood-brain barrier and viral fusion processes. Alteration of peptide structure could be a cause of many diseases. Biological membranes are complex systems, therefore simplified models may be introduced in order to understand processes occurring in nature. The lipid monolayers at the air/water interface are suitable model systems to mimic biological membranes since many parameters can be easily controlled. In the present work the lipid monolayers were used as a model membrane and their interactions with two different peptides B18 and Amyloid beta (1-40) peptide were investigated. B18 is a synthetic peptide that binds to lipid membranes that leads to the membrane fusion. It was demonstrated that it adopts different structures in the aqueous solutions and in the membrane interior. It is unstructured in solutions and forms alpha-helix at the air/water interface or in the membrane bound state. The peptide has affinity to the negatively charged lipids and even can fold into beta-sheet structure in the vicinity of charged membranes at high peptide to lipid ratio. It was elucidated that in the absence of electrostatic interactions B18 does not influence on the lipid structure, whereas it provides partial liquidization of the negatively charged lipids. The understanding of mechanism of the peptide action in model system may help to develop the new type of antimicrobial peptides as well as it can shed light on the general mechanisms of peptide/membrane binding. The other studied peptide - Amyloid beta (1-40) peptide, which is the major component of amyloid plaques found in the brain of patients with Alzheimer's disease. Normally the peptide is soluble and is not toxic. During aging or as a result of the disease it aggregates and shows a pronounced neurotoxicity. The peptide aggregation involves the conformational transition from a random coil or alpha-helix to beta-sheets. Recently it was demonstrated that the membrane can play a crucial role for the peptide aggregation and even more the peptide can cause the change in the cell membranes that leads to a neuron death. In the present studies the structure of the membrane bound Amyloid beta peptide was elucidated. It was found that the peptide adopts the beta-sheet structure at the air/water interface or being adsorbed on lipid monolayers, while it can form alpha-helical structure in the presence of the negatively charged vesicles. The difference between the monolayer system and the bulk system with vesicles is the peptide to lipid ratio. The peptide adopts the helical structure at low peptide to lipid ratio and folds into beta-sheet at high ratio. Apparently, Abeta peptide accumulation in the brain is concentration driven. Increasing concentration leads to a change in the lipid to peptide ratio that induces the beta-sheet formation. The negatively charged lipids can act as seeds in the plaque formation, the peptide accumulates on the membrane and when the peptide to lipid ratio increases it the peptide forms toxic beta-sheet containing aggregates.
Reversible addition-fragmentation transfer (RAFT) was used as a controlling technique for studying the aqueous heterophase polymerization. The polymerization rates obtained by calorimetric investigation of ab initio emulsion polymerization of styrene revealed the strong influence of the type and combination of the RAFT agent and initiator on the polymerization rate and its profile. The studies in all-glass reactors on the evolution of the characteristic data such as average molecular weight, molecular weight distribution, and average particle size during the polymerization revealed the importance of the peculiarities of the heterophase system such as compartmentalization, swelling, and phase transfer. These results illustrated the important role of the water solubility of the initiator in determining the main loci of polymerization and the crucial role of the hydrophobicity of the RAFT agent for efficient transportation to the polymer particles. For an optimum control during ab-initio batch heterophase polymerization of styrene with RAFT, the RAFT agent must have certain hydrophilicity and the initiator must be water soluble in order to minimize reactions in the monomer phase. An analytical method was developed for the quantitative measurements of the sorption of the RAFT agents to the polymer particles based on the absorption of the visible light by the RAFT agent. Polymer nanoparticles, temperature, and stirring were employed to simulate the conditions of a typical aqueous heterophase polymerization system. The results confirmed the role of the hydrophilicity of the RAFT agent on the effectiveness of the control due to its fast transportation to the polymer particles during the initial period of polymerization after particle nucleation. As the presence of the polymer particles were essential for the transportation of the RAFT agents into the polymer dispersion, it was concluded that in an ab initio emulsion polymerization the transport of the hydrophobic RAFT agent only takes place after the nucleation and formation of the polymer particles. While the polymerization proceeds and the particles grow the rate of the transportation of the RAFT agent increases with conversion until the free monomer phase disappears. The degradation of the RAFT agent by addition of KPS initiator revealed unambigueous evidence on the mechanism of entry in heterophase polymerization. These results showed that even extremely hydrophilic primary radicals, such as sulfate ion radical stemming from the KPS initiator, can enter the polymer particles without necessarily having propagated and reached a certain chain length. Moreover, these results recommend the employment of azo-initiators instead of persulfates for the application in seeded heterophase polymerization with RAFT agents. The significant slower rate of transportation of the RAFT agent to the polymer particles when its solvent (styrene) was replaced with a more hydrophilic monomer (methyl methacrylate) lead to the conclusion that a complicated cooperative and competitive interplay of solubility parameters and interaction parameter with the particles exist, determining an effective transportation of the organic molecules to the polymer particles through the aqueous phase. The choice of proper solutions of even the most hydrophobic organic molecules can provide the opportunity of their sorption into the polymer particles. Examples to support this idea were given by loading the extremely stiff fluorescent molecule, pentacene, and very hydrophobic dye, Sudan IV, into the polymer particles. Finally, the first application of RAFT at room temperature heterophase polymerization is reported. The results show that the RAFT process is effective at ambient temperature; however, the rate of fragmentation is significantly slower. The elevation of the reaction temperature in the presence of the RAFT agent resulted in faster polymerization and higher molar mass, suggesting that the fragmentation rate coefficient and its dependence on the temperature is responsible for the observed retardation.
The Reversible Addition Fragmentation Chain Transfer (RAFT) process using the new RAFT agent benzyldithiophenyl acetate is shown to be a powerful polymerization tool to synthesize novel well-defined amphiphilic diblock copolymers composed of the constant hydrophobic block poly(butyl acrylate) and of 6 different hydrophilic blocks with various polarities, namely a series of non-ionic, non-ionic comb-like, anionic and cationic hydrophilic blocks. The controlled character of the polymerizations was supported by the linear increase of the molar masses with conversion, monomodal molar mass distributions with low polydispersities and high degrees of end-group functionalization. The new macro-surfactants form micelles in water, whose size and geometry strongly depend on their composition, according to dynamic and static light scattering measurements. The micellization is shown to be thermodynamically favored, due to the high incompatibility of the blocks as indicated by thermal analysis of the block copolymers in bulk. The thermodynamic state in solution is found to be in the strong or super strong segregation limit. Nevertheless, due to the low glass transition temperature of the core-forming block, unimer exchange occurs between the micelles. Despite the dynamic character of the polymeric micellar systems, the aggregation behavior is strongly dependent on the history of the sample, i.e., on the preparation conditions. The aqueous micelles exhibit high stability upon temperature cycles, except for an irreversibly precipitating block copolymer containing a hydrophilic block exhibiting a lower critical solution temperature (LCST). Their exceptional stability upon dilution indicates very low critical micelle concentrations (CMC) (below 4∙10<sup>-4 g∙L<sup>-1). All non-ionic copolymers with sufficiently long solvophobic blocks aggregated into direct micelles in DMSO, too. Additionally, a new low-toxic highly hydrophilic sulfoxide block enables the formation of inverse micelles in organic solvents. The high potential of the new polymeric surfactants for many applications is demonstrated, in comparison to reference surfactants. The diblock copolymers are weakly surface-active, as indicated by the graduate decrease of the surface tension of their aqueous solutions with increasing concentration. No CMC could be detected. Their surface properties at the air/water interface confer anti-foaming properties. The macro-surfactants synthesized are surface-active at the interface between two liquid phases, too, since they are able to stabilize emulsions. The polymeric micelles are shown to exhibit a high ability to solubilize hydrophobic substances in water.
Neolignans, dehydrodimers of phenylpropenes, are natural products that exhibit different biological activities. 8,5’-Neolignans containing a trans- dihydrobenzofuran skeleton are the most abundant neolignans in nature. The published syntheses of trans-dihydrobenzofurans are multistep procedures that are time consuming and provide the product in low yield. Furthermore, all dimerisation reactions either in the presence of enzymes or mediated by metal salts are yielding dimers consisting of two units of the same phenylpropene compound, narrowing substantially the substitution pattern. Two different general synthetic approaches were examined. The first strategy was the enantioselective deprotonation at the α-carbon of the ο-alkyl phenols in the presence of a chiral diamine and sBuLi. Synthesis of several new phosphorous-based directed ortho-metalation groups was studied. The examined compounds having these new groups decomposed even under very mild reaction conditions and are not suitable for the application in the synthesis. The second strategy was to examine one [3+2] cycloaddition reaction, transition metal catalysed Heck oxyarylation reaction, in the synthetic approach to compounds having trans-dihydrobenzofuran skeleton. Palladium catalysed Heck oxyarylation reaction with halogenophenols or ortho-diazonium phenols as the starting material allowed the trans-dihydrobenzofuran compounds as the major products in acceptable yield and in one step. The products were formed under ligand free condition, as well as in the presence of some strong coordinating ligands (Ph3P). The experiments with several chiral ligands, showed that the obtained trans-dihydrobenzofurans were racemic mixtures. This result suggests formation of an achiral intermediate along the reaction pathway, which causes the lack of stereoselectivity in the products. Initially formed trans-dihydrobenzofuran compounds are the key precursors of many naturally occurring neolignans, and can be easily converted to 8,5’-neolignan derivatives.
The fluorescence properties and the fluorescence quenching by Tb3+ of substituted benzoic acid were investigated in solution at different pH. The substituted benzoic acids were used as simple model compounds for chromophores present in humic substances (HS). It is shown that the fluorescence properties of the model compounds resemble fluorescence of HS quite well. A major factor determining the fluorescence of model compounds are proton transfer reactions in the electronically excited state. It is intriguing that the fluorescence of the model compounds was almost not quenched by Tb3+ while the HS fluorescence was decreased very effectively. From our results we concluded that proton transfer reactions as well as conformational reorientation processes play an important role in the fluorescence of HS. The luminescence of bound Tb3+ was sensitized by an energy transfer step upon excitation of the model compounds and of HS, respectively. For HS the observed sensitization was dependent on its origin indicating differences 1) in the connection between chromophores and binding sites and 2) in the energy levels of the chromophore triplet states. Hence, the observed sensitization of the Tb3+ luminescence could be useful to characterize structural differences of HS in solution. Interlanthanide energy transfer between Tb3+ and Nd3+ was used to determine the average distance R between both ions using the well-known formalism of luminescence resonance energy transfer. R was dependent on the origin of the HS reflecting the difference in structure. The value of Rmin seemed to be a unique feature of the HS. It was further found that upon variation of the pH R also changed. This demonstrates that the measurement of interlanthanide energy transfer can be used as a direct method to monitor conformational changes in HS.
A technique has been developed to measure absolute intracellular oxygen concentrations in green plants. Oxygen-sensitive phosphorescent microbeads were injected into the cells and an optical multifrequency phase-modulation technique was used to discriminate the sensor signal from the strong autofluorescence of the plant tissue. The method was established using photosynthesis-competent cells of the giant algae Chara corallina L., and was validated by application to various cell types of other plant species.
In this work, the nonaqueous synthesis of binary and ternary metal oxide nanoparticles is investigated for a number of technologically important materials. A strong focus was put on studying the reaction mechanisms leading to particle formation upon solvothermal treatment of the precursors, as an understanding of the formation processes is expected to be crucial for a better control of the systems, offering the potential to tailor particle size and morphology. The synthesis of BaTiO3 was achieved by solvothermal reaction of metallic barium and titanium isopropoxide in organic solvents. Phase-pure, highly crystalline particles about 6 nm in size resulted in benzyl alcohol, whereas larger particles could be obtained in ketones such as acetone or acetophenone. In benzyl alcohol, a novel mechanism was found to lead to BaTiO3, involving a C–C coupling step between the isopropoxide ligand and the benzylic carbon of the solvent. The resulting coupling product, 4-phenyl-2-butanol, is found in almost stoichiometric yield. The particle formation in ketones proceeds via a Ti-mediated aldol condensation of the solvent, involving formal elimination of water which induces formation of the oxide. These processes also occurred when reacting solely the titanium alkoxide with ketones or aldehydes, leading to highly crystalline anatase nanoparticles for all tested solvents. In ketones, also the synthesis of nanopowders of lead zirconate titanate (PZT) was achieved, which were initially amorphous but could be crystallized by calcination at moderate temperatures. Additionally, PZT films were prepared by simply casting a suspension of the powder onto Si substrates followed by calcination.Solvothermal synthesis however is not restricted to alkoxides as precursors but is also achieved from metal acetylacetonates. The use of benzylamine as solvent proved particularly versatile, making possible the synthesis of nanocrystalline In2O3, Ga2O3, ZnO and iron oxide from the respective acetylacetonates. During the synthesis, the acetylacetonate ligand undergoes a solvolysis under C–C cleavage, resulting in metal-bound enolate ligands which, in analogy to the synthesis in ketones, induce ketimine and aldol condensation reactions. In the last section of this work, surface functionalization of anatase nanoparticles is explored. The particles were first capped with various organic ligands via a facile in situ route, which resulted in altered properties such as enhanced dispersibility in various solvents. In a second step, short functional oligopeptide segments were attached to the particles by means of a catechol linker to achieve advanced self-assembly properties.
In this work, the basic principles of self-organization of diblock copolymers having the in¬herent property of selective or specific non-covalent binding were examined. By the introduction of electrostatic, dipole–dipole, or hydrogen bonding interactions, it was hoped to add complexity to the self-assembled mesostructures and to extend the level of ordering from the nanometer to a larger length scale. This work may be seen in the framework of biomimetics, as it combines features of synthetic polymer and colloid chemistry with basic concepts of structure formation applying in supramolecular and biological systems. The copolymer systems under study were (i) block ionomers, (ii) block copolymers with acetoacetoxy chelating units, and (iii) polypeptide block copolymers.
Understanding the principles of self-organisation exhibited by block copolymers requires the combination of synthetic and physicochemical knowledge. The ability to synthesise block copolymers with desired architecture facilitates the ability to manipulate their aggregation behaviour, thus providing the key to nanotechnology. Apart from relative block volumes, the size and morphology of the produced nanostructures is controlled by the effective incompatibility between the different blocks. Since polymerisation techniques allowing for the synthesis of well-defined block copolymers are restricted to a limited number of monomers, the ability to tune the incompatibility is very limited. Nevertheless, Polymer Analogue Reactions can offer another possibility for the production of functional block copolymers by chemical modifications of well-defined polymer precursors. Therefore, by applying appropriate modification methods both volume fractions and incompatibility, can be adjusted. Moreover, copolymers with introduced functional units allow utilization of the concept of molecular recognition in the world of synthetic polymers. The present work describes a modular synthetic approach towards functional block copolymers. Radical addition of functional mercaptanes was employed for the introduction of diverse functional groups to polybutadiene-containing block copolymers. Various modifications of 1,2-polybutadiene-poly(ethylene oxide) block copolymer precursors are described in detail. Furthermore, extension of the concept to 1,2-polybutadiene-polystyrene block copolymers is demonstrated. Further investigations involved the self-organisation of the modified block copolymers. Formed aggregates in aqueous solutions of block copolymers with introduced carboxylic acid, amine and hydroxyl groups as well as fluorinated chains were characterised. Study of the aggregation behaviour allowed general conclusions to be drawn regarding the influence of the introduced groups on the self-organisation of the modified copolymers. Finally, possibilities for the formation of complexes, based on electrostatic or hydrogen-bonding interactions in mixtures of block copolymers bearing mutually interacting functional groups, were investigated.
Mesoporous organosilica materials with amine functions : surface characteristics and chirality
(2005)
In this work mesoporous organisilica materials are synthesized through the silica sol-gel process. For this a new class of precursors which are also surfactant are synthesized and self-assembled. This leads to a high surface area functionality which is analysized with copper (II) and water adsorption.
Polymer optical fibers (POFs) are a rather new tool for high-speed data transfer by modulated light. They allow the transport of high amounts of data over distances up to about 100 m without be influenced by external electromagnetic fields. Due to organic chemical nature of POFs, they are sensitive to the climate of their environment and therefore the optical fiber properties are as well. Hence, the optical stability is a key issue for long-term applications of POFs. The causes for a loss of optical transmission due to climatic exposures (aging/degradation) are researched by means of chemical analytical tools such as chemiluminescence (CL) and Fourier transform infrared (FTIR) spectroscopy for five different (with respect to manufacturers) step-index multimode PMMA based POFs and for seven different climatic conditions. Three of the five POF samples are studied more in detail to realize the effects of individual parameters and for forecasting longterm optical stability by short-term exposure tests. At first, the unexposed POF components (core, cladding, and bare POF as combination of core and cladding) are characterized with respect to important physical and chemical properties. The glass transition temperature Tg, and the melting temperature Tm are in the region of 120 °C to 140 °C, the molecular weight (Mw) of cores is in the order of 105 g mol-1. POFs are found to have different chemical compositions of their claddings as could be detected by FTIR, but identical compositions of their cores. Two of the POFs are exposed as cables (core, cladding and jacket) for about 3300 hours to the climate 92 °C / 95 % relative humidity (RH) resulting in a different transmission decrease. Investigating the related unexposed and exposed bare POFs for degradation using CL, FTIR, thermogravimetry (TG), UV/visible transmittance and gel permeation chromatography (GPC) suggest that claddings of POFs are more affected than cores. Probably the observed loss of transmission is mainly due to increased light absorption and imperfections at the core-cladding boundary caused by a large degradation of claddings. Hence, it is highly possible that the optical transmission stability of POFs is governed mainly by the thermo-oxidative stability of the cladding and minor of the core. Three bare POFs (core and cladding only) are exposed for different duration of exposure time (30 hours to 4500 hours) to 92 °C / 95 %RH, 92 °C / 50 %RH, 50 °C / 95 %RH, 90 °C / low humidity, 100 °C / low humidity, 110 °C / low humidity and 120 °C / low humidity. In these climates their transmission variations are found to be different from each other, too. The outcomes strongly inform that under high temperature and high humid climates physical changes such as volume expansion, are the main sources for the loss of optical transmission. Also, the optical transmission stability of POFs is found to be dependent on chemical compositions of claddings. Under high temperature and low humid conditions, a loss of transmission at the early stages of the exposure is mainly caused by physical changes, presumable by corecladding interface imperfections. For the later stages of exposures it is proposed to an additional increase of light absorption by core and cladding owes to degradation. Optical simulation results obtained parallel by Mr. L. Jankowski (a PhD student of BAM) are found to confirm these results. For bare POFs, too, the optical stability of POFs seems to depend on their thermo-oxidative stability. Some short-term exposure tests are conducted to realize influences of individual climatic parameters on the transmission property of POFs. It is found that at stationary high temperature and variable humidity conditions POFs display to a certain amount a reversible transmission loss due to physically absorbed water. But in the case of varying temperature and constant high humidity such reversibility is hardly noticeable. However, at room temperature and varying humidity, POFs display fully reversible transmission loss. The whole research described above has to be regarded as a starting point for further investigations. The restricted distribution of fundamental POF data by the manufacturers and the time consuming aging by climatic exposures restrict the results more or less to the samples, investigated here. Significant general statements require for example additional information concerning the variation of POF properties due to production. Nevertheless the tests, described here, have the capability for approximating and forecasting the long-term optical transmission stability of POFs. -------------- Auch im Druck erschienen: Appajaiah, Anilkumar: Climatic stability of polymer optical fibers (POF) / Anilkumar Appajaiah. - Bremerhaven : Wirtschaftsverl. NW, Verl. für neue Wiss., 2005. - Getr. Zählung [ca. 175 S.]. : Ill., graph. Darst. - (BAM-Dissertationsreihe ; 9) ISBN 3-86509-302-7
Taking inspiration from nature, where composite materials made of a polymer matrix and inorganic fillers are often found, e.g. bone, shell of crustaceans, shell of eggs, etc., the feasibility on making composite materials containing chitosan and nanosized hydroxyapatite were investigated. A new preparation approach based on a co-precipitation method has been developed. In its earlier stage of formation, the composite occurs as hydrogel as suspended in aqueous alkaline solution. In order to get solid composites various drying procedures including freeze-drying technique, air-drying at room temperature and at moderate temperatures, between 50oC and 100oC were used. Physicochemical studies showed that the composites exhibit different properties with respect to their structure and composition. IR and Raman spectroscopy probed the presence of both chitosan and hydroxyapatite in the composites. Hydroxyapatite as dispersed in the chitosan matrix was found to be in the nanosize range (15-50 nm) and occurs in a bimodal distribution with respect to its crystallite length. Two types of distribution domains of hydroxyapatite crystallites in the composite matrix such as cluster-like (200-400 nm) and scattered-like domains were identified by the transmission electron microscopy (TEM), X-ray diffraction (XRD) and by confocal scanning laser microscopy (CSLM) measurements. Relaxation NMR experiments on composite hydrogels showed the presence of two types of water sites in their gel networks, such as free and bound water. Mechanical tests showed that the mechanical properties of composites are one order of magnitude less than those of compact bone but comparable to those of porous bone. The enzymatic degradation rates of composites showed slow degradation processes. The yields of degradation were estimated to be less than 10% by loss of mass, after incubation with lysozyme, for a period of 50 days. Since the composite materials were found biocompatible by the in vivo tests, the simple mode of their fabrication and their properties recommend them as potential candidates for the non-load bearing bone substitute materials.
New chain transfer agents based on dithiobenzoate and trithiocarbonate for free radical polymerization via Reversible Addition-Fragmentation chain Transfer (RAFT) were synthesized. The new compounds bear permanently hydrophilic sulfonate moieties which provide solubility in water independent of the pH. One of them bears a fluorophore, enabling unsymmetrical double end group labelling as well as the preparation of fluorescent labeled polymers. Their stability against hydrolysis in water was studied, and compared with the most frequently employed water-soluble RAFT agent 4-cyano-4-thiobenzoylsulfanylpentanoic acid dithiobenzoate, using UV-Vis and 1H-NMR spectroscopy. An improved resistance to hydrolysis was found for the new RAFT agents, providing good stabilities in the pH range between 1 and 8, and up to temperatures of 70°C. Subsequently, a series of non-ionic, anionic and cationic water-soluble monomers were polymerized via RAFT in water. In these experiments, polymerizations were conducted either at 48°C or 55°C, that are lower than the conventionally employed temperatures (>60°C) for RAFT in organic solvents, in order to minimize hydrolysis of the active chain ends (e.g. dithioester and trithiocarbonate), and thus to obtain good control over the polymerization. Under these conditions, controlled polymerization in aqueous solution was possible with styrenic, acrylic and methacrylic monomers: molar masses increase with conversion, polydispersities are low, and the degree of end group functionalization is high. But polymerizations of methacrylamides were slow at temperatures below 60°C, and showed only moderate control. The RAFT process in water was also proved to be a powerful method to synthesize di- and triblock copolymers including the preparation of functional polymers with complex structure, such as amphiphilic and stimuli-sensitive block copolymers. These include polymers containing one or even two stimuli-sensitive hydrophilic blocks. The hydrophilic character of a single or of several blocks was switched by changing the pH, the temperature or the salt content, to demonstrate the variability of the molecular designs suited for stimuli-sensitive polymeric amphiphiles, and to exemplify the concept of multiple-sensitive systems. Furthermore, stable colloidal block ionomer complexes were prepared by mixing anionic surfactants in aqueous media with a double hydrophilic block copolymer synthesized via RAFT in water. The block copolymer is composed of a noncharged hydrophilic block based on polyethyleneglycol and a cationic block. The complexes prepared with perfluoro decanoate were found so stable that they even withstand dialysis; notably they do not denaturate proteins. So, they are potentially useful for biomedical applications in vivo.