Synthesis and characterization of temperature- and light-responsive polymers and block copolymers

In summary, thermoresponsive polyacrylamides with various amounts of different photoswitchable side groups, i. e. azobenzene, salicylideneaniline and fulgimide were successfully prepared. As such, in a first step three different chromophores with an amine functionality were synthesized. The synthesis of the stimuli-responsive materials was based on the RAFT polymerization of activated ester acrylates followed by a polymer analogous reaction with different amines. The procedure has been designed to allow the synthesis of well-defined materials with functional groups. All copolymers prepared in this way showed a LCST in aqueous solution. The LCST was in general decreased by increasing the amount of hydrophobic dye incorporated into the thermoresponsive polymer. However, in the case of the fulgimide, the LCST was hardly affected by the chromophore. For azobenzene containing PNIPAM polymers and analogues, higher LCST values were measured after irradiation of the polymer sample solutions with UV-light (Delta LCSTmax = 7.3°C). A reversible light-induced solubility change within a certain temperature range was possible. In contrast to this, irradiated samples of salicylideneaniline containing thermoresponsive copolymers showed an irreversible increase in the LCST (Delta LCSTmax = 13.0°C). Fulgimide chromophores did not influence the LCST of PNIPAM based copolymers after UV-light exposure.rnSimilar to the thermoresponsive polyacrylamides with azobenzene side groups, poly(oligo(ethylene glycol) methyl ether methacrylate) [P(OEGMA)] polymers with azobenzene end groups showed a LCST shift upon UV-irradiation. These polymers were synthesized by RAFT polymerization using a functional chain transfer agent (CTA). For this, PFP-CTA was used as a RAFT-agent for end group functionalization of (thermoresponsive) polymers. In contrast to the statistically arranged copolymers with azobenzene side groups, P(OEGMA) polymers with terminal azobenzene showed a linear increase of the LCST shifts with increasing amount of chromophore (Delta LCSTmax = 4.3°C). Noteworthy, the chemical nature of the end group exhibited a strong influence on the LCST in the case of short thermoresponsive P(OEGMA) polymers.rnThe investigation on temperature- and lightresponsive polymers was transferred onto block copolymers capable to self-assemble into polymeric micelles. Therefore, PEO-b-PNIPAM block copolymers with azobenzene moieties were synthesized successfully. These polymers showed a “smart” behavior in aqueous solution, as the reversible formation and disruption of the micelles could either be controlled by temperature or using light as a stimulus. The usefulness of these materials was demonstrated by encapsulation of a hydrophobic dye in the core of the micelle. Such materials might have a great potential as a model system for several technical or biological applications.rnFinally, double thermoresponsive block copolymers forming micellar structures in a certain temperature range with functional end groups could successfully be synthesized. These “smart materials” based on POEGMA-b-PNIPMAM have been demonstrated to be very promising for a temperature selective immobilization on a protein surface. This might be a suitable concept for further biological applications.rnConcluding, different thermoresponsive copolymers and block copolymers with lightresponsive moieties arranged along the backbone or located at the chain ends were successfully prepared and investigated. By controlling the nature of functional groups and their respective incorporation ratios, the LCST could be dialed in precisely. Further, the LCST of the polymers could be triggered by light. A light-controlled disruption of micellar structures could be shown for functional block copolymers. The importance of end groups of thermoresponsive polymers was demonstrated by a temperature-controlled protein-polymer binding of a terminal biotin-functionalized double thermoresponsive polymer. The synthetic approaches and the material properties presented here should be promising for further research and applications beyond this dissertation.rn

Alpha, Omega end group functionalization of RAFT polymers based on pentafluorophenyl esters and methane thiosulfonates

While polymers with different functional groups along the backbone have intensively been investigated, there is still a challenge in orthogonal functionalization of the end groups. Such well-defined systems are interesting for the preparation of multiblock (co) polymers or polymer networks, for bio-conjugation or as model systems for examining the end group separation of isolated polymer chains. rnHere, Reversible Addition Fragmentation Chain Transfer (RAFT) polymerization was employed as method to investigate improved techniques for an a, w end group functionalization. RAFT produces polymers terminated in an R group and a dithioester-Z group, where R and Z stem from a suitable chain transfer agent (CTA). rnFor alpha end group functionalization, a CTA with an activated pentafluorophenyl (PFP) ester R group was designed and used for the polymerization of various methacrylate monomers, N-isopropylacrylamide and styrene yielding polymers with a PFP ester as a end group. This allowed the introduction of inert propyl amides, of light responsive diazo compounds, of the dyes NBD, Texas Red, or Oregon Green, of the hormone thyroxin and allowed the formation of multiblocks or peptide conjugates. rnFor w end group functionalization, problems of other techniques were overcome through an aminolysis of the dithioester in the presence of a functional methane thiosulfonate (MTS), yielding functional disulfides. These disulfides were stable under ambient conditions and could be cleaved on demand. Using MTS chemistry, terminal methyl disulfides (enabling self-assembly on planar gold surfaces and ligand substitution on gold and semiconductor nanoparticles), butynyl disulfide end groups (allowing the “clicking” of the polymers onto azide functionalized surfaces and the selective removal through reduction), the bio-target biotin, and the fluorescent dye Texas Red were introduced into polymers. rnThe alpha PFP amidation could be performed under mild conditions, without substantial loss of DTE. This way, a step-wise synthesis produced polymers with two functional end groups in very high yields. rnAs examples, polymers with an anchor group for both gold nanoparticles (AuNP) and CdSe / ZnS semi-conductor nanoparticles (QD) and with a fluorescent dye end group were synthesized. They allowed a NP decoration and enabled an energy transfer from QD to dye or from dye to AuNP. Water-soluble polymers were prepared with two different bio-target end groups, each capable of selectively recognizing and binding a certain protein. The immobilization of protein-polymer-protein layers on planar gold surfaces was monitored by surface plasmon resonance.Introducing two different fluorescent dye end groups enabled an energy transfer between the end groups of isolated polymer chains and created the possibility to monitor the behavior of single polymer chains during a chain collapse. rnThe versatility of the synthetic technique is very promising for applications beyond this work.

Tracing AGN accretion and star formation in Herschel galaxies

In this Thesis, we study the physical properties and the cosmic evolution of AGN and their host galaxies since z∼3. Our analysis exploits samples of star forming galaxies detected with Herschel at far-IR wavelengths (from 70 up to 500 micron) in different extragalactic surveys, such as COSMOS and the deep GOODS (South and North) fields. The broad-band ancillary data available in COSMOS and the GOODS fields, allows us to implement Herschel and Spitzer photometry with multi-wavelength ancillary data. We perform a multicomponent SED-fitting decomposition to decouple the emission due to star formation from that due to AGN accretion, and to estimate both host-galaxy parameters (such as stellar mass, M* and star formation rate, SFR), and nuclear intrinsic bolometric luminosities. We use the individual estimates of AGN bolometric luminosity obtained through SED-fitting decomposition to reconstruct the redshit evolution of the AGN bolometric luminosity function since z∼3. The resulting trends are used to estimate the overall AGN accretion rate density at different cosmic epochs and to trace the first ever estimate of the AGN accretion history from an IR survey. Later on, we focus our study on the connection between AGN accretion and integrated galaxy properties. We analyse the relationships of AGN accretion with galaxy properties in the SFR-M* plane and at different cosmic epochs. Finally, we infer what is the parameter that best correlates with AGN accretion, comparing our results with previous studies and discussing their physical implications in the context of current scenarios of AGN/galaxy evolution.

Hyperbranched polyglycerols as building blocks for complex amphiphilic structures: synthesis, characterization and applications

Among hyperbranched polymers, polyglycerol is one of the most promising and commonly used macromolecules due to its biocompatibility and versatility. However, the synthesis of high molecular weight polyglycerols still involves many intricacies and has only been understood to a limited extent. Furthermore, only few complex structures like star or block copolymers incorporating polyglycerol have been realized so far. Particularly biocompatible block copolymers are considered promising candidates for biomedical applications.rnThe scope of this thesis was the enhancement of the synthetic process leading to polyglycerol derivatives which implies improved molecular weight control for a broad molecular weight range as well as the assembly of more complex structures like amphiphilic block copolymers. Further insight into the relation between reaction solvent, degree of deprotonation during the ring-opening multibranching polymerization of glycidol and the characteristics of the obtained polymers were achieved within the scope of this work. Based on these results, a novel concept for the preparation of hyperbranched polyglycerols with molecular weights up to 20,000 g/mol was developed, applying a two step synthesis pathway. Starting from a partially deprotonated TMP core, low molecular weight hb-PGs were prepared using the known synthetic protocol that has been established since the late 1990ies. In a subsequent reaction sequence, these well defined polymers were used as hyperbranched macroinitiator cores in order to obtain high molecular weight hb-PGs with remarkably low polydispersity (Mw/Mn < 1.8). Molecular weight control was shown to be excellent and undesired low molecular weight side products were absent. Furthermore, the technique of continuous spin fractionation has been discovered as an efficient method for polyglycerol work-up to remove quantitatively residual monomer- and oligomer traces from hb-PG compositions to result in samples with significantly reduced polydispersities. Based on these results the synthesis of amphiphilic block copolymers containing hydrophilic hyperbranched polyglycerol blocks and linear, apolar poly(propylene oxide) blocks has been significantly improved and augmented to hb-PG-b-l-PPO-b-hb-PG ABA block copolymers. The influence of different polyglycerol-based amphiphiles on the fibril formation was studied by Thioflavin T Fluorescence showing remarkable increasing lag times which is promising in order to enhance the stability of this protein. In addition the first synthesis of poly(glyceryl glycerols) (PGG), introducing a new solketyl glycidyl ether monomer (IGG) was shown. It was furthermore demonstrated that core-functional carbosilane wedges allow application in block copolymer synthesis. Bisglycidolized amine functional polymers were successfully employed as macroinitiators for glycidol polymerization. This resulted in the first example of amphiphilic hyperbranched-hyperbranched polymer structures. Finally, it has been shown that the previously reported synthetic pathway to carboxylated hyperbranched polyglycerol polyelectrolytes can also be applied for the amphiphilic linear-hyperbranched block copolymers. These novel biocompatible and highly amphiphilic polyelectrolytes offer great potential for further investigations. rnrn

Laser heating of polymers

Zur Untersuchung von Effekten beim Laserheizen von Polymeren wurde ein Temperaturmessaufbau entwickelt. Das Messprinzip basiert auf der Auswertung der thermischen Emission. Der Messaufbau besteht aus einer hochauflösenden Kamera, ausgestattet mit Bildverstärker, sowie Interferenzfiltern um eine spektrale Auflösung zu gewährleisten und einem gepulster NIR-Heizlaser. Die Pulsdauer des Lasers liegt in der Größenordnung von 10 µs, der Strahldurchmesser durch entsprechende Fokussierung in der Größenordnung von 10 µm. Mittels Fit des Planck‘schen Strahlungsgesetzes an die aufgenommene thermische Emission konnten 2D Temperaturgraphen erhalten werden. Eine Ortsauflösung von 1 µm und eine Zeitauflösung von 1 µs konnten realisiert werden. In Kombination mit Finite-Elemente-Simulationen wurde mit diesem Aufbau die Laserablation verschiedener Polymere untersucht. Dabei hat sich gezeigt, dass bei Polymeren mit einem Glasübergang im Temperaturbereich zwischen Raum- und Zerfallstemperatur, photomechanische Ablation stattfand. Die Ablationsschwelle lag für diese Polymere mehrere 10 K über dem Glasübergang, weit unter der Zerfallstemperatur aus thermogravimetrischen Experimenten mit typischen Heizraten von 10 K/min. Bei hohen Laserenergien und damit verbundenen hohen Temperaturen konnte dagegen thermischer Zerfall beobachtet werden. Ein Übergang des Mechanismus von photomechanischer Ablation zu Ablation durch thermischen Zerfall ergab sich bei Temperaturen deutlich über der Zerfallstemperatur des Polymers aus der Thermogravimetrie. Dies wurde bedingt durch die kurzen Reaktionszeiten des Laserexperiments in der Größenordnung der Pulsdauer und steht im Einklang mit dem Gesetz von Arrhenius. Polymere ohne Glasübergang im Heizbereich zeigten dagegen keine photomechanische Ablation, sondern ausschließlich thermischen Zerfall. Die Ablationsschwelle lag auch hier bei höheren Temperaturen, entsprechend dem Gesetz von Arrhenius. Hohe Temperaturen, mehrere 100 K über der Zerfallstemperatur, ergaben sich darüber hinaus bei hohen Laserenergien. Ein drastisches Überhitzen des Polymers, wie in der Literatur beschrieben, konnte nicht beobachtet werden. Experimentelle Befunde deuten vielmehr darauf hin, dass es sich bei dem heißen Material um thermische Zerfallsprodukte, Polymerfragmente, Monomer und Zerfallsprodukte des Monomers handelte bzw. das Temperaturprofil der Zerfallsreaktion selbst visualisiert wurde.

Template-assisted patterning of functional polymers

In this thesis, anodic aluminum oxide (AAO) membranes, which provide well-aligned uniform mesoscopic pores with adjustable pore parameters, were fabricated and successfully utilized as templates for the fabrication of functional organic nanowires, nanorods and the respective well-ordered arrays. The template-assisted patterning technique was successfully applied for the realization of different objectives:rnHigh-density and well-ordered arrays of hole-conducting nanorods composed of cross-linked triphenylamine (TPA) and tetraphenylbenzidine (TPD) derivatives on conductive substrates like ITO/glass have been successfully fabricated. By applying a freeze-drying technique to remove the aqueous medium after the wet-chemical etching of the template, aggregation and collapsing of the rods was prevented and macroscopic areas of perfectly freestanding nanorods were feasible. Based on the hole-conducting nanorod arrays and their subsequent embedding into an electron-conducting polymer matrix via spin-coating, a novel routine concept for the fabrication of well-ordered all-organic bulk heterojunction for organic photovoltaic applications was successfully demonstrated. The increased donor/acceptor interface of the fabricated devices resulted in a remarkable increase of the photoluminescence quenching compared to a planar bilayer morphology. Further, the fundamental working principle of the templating approach for the solution-based all-organic photovoltaic device was demonstrated for the first time.rnFurthermore, in order to broaden the applicability of patterned surfaces, which are feasible via the template-based patterning of functional materials, AAO with hierarchically branched pores were fabricated and utilized as templates. By pursuing the common templating process hierarchically polymeric replicas, which show remarkable similarities with interesting biostructures, like the surface of the lotus leaf and the feet of a gecko, were successfully prepared.rnIn contrast to the direct infiltration of organic functional materials, a novel route for the fabrication of functional nanowires via post-modification of reactive nanowires was established. Therefore, reactive nanowires based on cross-linked pentafluorophenylesters were fabricated by utilizing AAO templates. The post-modification with fluorescent dyes was demonstrated. Furthermore, reactive wires were converted into well-dispersed poly(N-isopropylacrylamide) (PNIPAM) hydrogels, which exhibit a thermal-responsive reversible phase transition. The reversible thermal-responsible swelling of the PNIPAM nanowires exhibited a more than 50 % extended length than in the collapsed PNIPAM state. rnLast but not least, the shape-anisotropic pores of AAO were utilized to uniformly align the mesogens of a nematic liquid crystalline elastomer. Liquid crystalline nanowires with a narrow size distribution and uniform orientation of the liquid crystalline material were fabricated. It was shown that during the transition from the nematic to the isotropic phase the rod’s length shortened by roughly 40 percent. As such these liquid crystalline elastomeric nanowires may find application, as wire-shaped nanoactuators in various fields of research, like lab-on-chip systems, micro fluidics and biomimetics.rn

Phenothiazine based polymers for energy and data storage application

Die vorliegende Arbeit befasst sich mit der Synthese und Charakterisierung von Polymeren mit redox-funktionalen Phenothiazin-Seitenketten. Phenothiazin und seine Derivate sind kleine Redoxeinheiten, deren reversibles Redoxverhalten mit electrochromen Eigenschaften verbunden ist. Das besondere an Phenothiazine ist die Bildung von stabilen Radikalkationen im oxidierten Zustand. Daher können Phenothiazine als bistabile Moleküle agieren und zwischen zwei stabilen Redoxzuständen wechseln. Dieser Schaltprozess geht gleichzeitig mit einer Farbveränderung an her.rnrnIm Rahmen dieser Arbeit wird die Synthese neuartiger Phenothiazin-Polymere mittels radikalischer Polymerisation beschrieben. Phenothiazin-Derivate wurden kovalent an aliphatischen und aromatischen Polymerketten gebunden. Dies erfolgte über zwei unterschiedlichen synthetischen Routen. Die erste Route beinhaltet den Einsatz von Vinyl-Monomeren mit Phenothiazin Funktionalität zur direkten Polymerisation. Die zweite Route verwendet Amin modifizierte Phenothiazin-Derivate zur Funktionalisierung von Polymeren mit Aktivester-Seitenketten in einer polymeranalogen Reaktion. rnrnPolymere mit redox-funktionalen Phenothiazin-Seitenketten sind aufgrund ihrer Elektron-Donor-Eigenschaften geeignete Kandidaten für die Verwendung als Kathodenmaterialien. Zur Überprüfung ihrer Eignung wurden Phenothiazin-Polymere als Elektrodenmaterialien in Lithium-Batteriezellen eingesetzt. Die verwendeten Polymere wiesen gute Kapazitätswerte von circa 50-90 Ah/kg sowie schnelle Aufladezeiten in der Batteriezelle auf. Besonders die Aufladezeiten sind 5-10 mal höher als konventionelle Lithium-Batterien. Im Hinblick auf Anzahl der Lade- und Entladezyklen, erzielten die Polymere gute Werte in den Langzeit-Stabilitätstests. Insgesamt überstehen die Polymere 500 Ladezyklen mit geringen Veränderungen der Anfangswerte bezüglich Ladezeiten und -kapazitäten. Die Langzeit-Stabilität hängt unmittelbar mit der Radikalstabilität zusammen. Eine Stabilisierung der Radikalkationen gelang durch die Verlängerung der Seitenkette am Stickstoffatom des Phenothiazins und der Polymerhauptkette. Eine derartige Alkyl-Substitution erhöht die Radikalstabilität durch verstärkte Wechselwirkung mit dem aromatischen Ring und verbessert somit die Batterieleistung hinsichtlich der Stabilität gegenüber Lade- und Entladezyklen. rnrnDes Weiteren wurde die praktische Anwendung von bistabilen Phenothiazin-Polymeren als Speichermedium für hohe Datendichten untersucht. Dazu wurden dünne Filme des Polymers auf leitfähigen Substraten elektrochemisch oxidiert. Die elektrochemische Oxidation erfolgte mittels Rasterkraftmikroskopie in Kombination mit leitfähigen Mikroskopspitzen. Mittels dieser Technik gelang es, die Oberfläche des Polymers im nanoskaligen Bereich zu oxidieren und somit die lokale Leitfähigkeit zu verändern. Damit konnten unterschiedlich große Muster lithographisch beschrieben und aufgrund der Veränderung ihrer Leitfähigkeit detektiert werden. Der Schreibprozess führte nur zu einer Veränderung der lokalen Leitfähigkeit ohne die topographische Beschaffenheit des Polymerfilms zu beeinflussen. Außerdem erwiesen sich die Muster als besonders stabil sowohl mechanisch als auch über die Zeit.rnrnZum Schluss wurden neue Synthesestrategien entwickelt um mechanisch stabile als auch redox-funktionale Oberflächen zu produzieren. Mit Hilfe der oberflächen-initiierten Atomtransfer-Radikalpolymerisation wurden gepfropfte Polymerbürsten mit redox-funktionalen Phenothiazin-Seitenketten hergestellt und mittels Röntgenmethoden und Rasterkraftmikroskopie analysiert. Eine der Synthesestrategien geht von gepfropften Aktivesterbürsten aus, die anschließend in einem nachfolgenden Schritt mit redox-funktionalen Gruppen modifiziert werden können. Diese Vorgehensweise ist besonders vielversprechend und erlaubt es unterschiedliche funktionelle Gruppen an den Aktivesterbürsten zu verankern. Damit können durch Verwendung von vernetzenden Gruppen neben den Redoxeigenschaften, die mechanische Stabilität solcher Polymerfilme optimiert werden. rn rn

Solubility, diffusivity and permeability of gases in glassy polymers

Gas separation membranes of high CO2 permeability and selectivity have great potential in both natural gas sweetening and carbon dioxide capture. Many modified PIM membranes results permselectivity above Robinson upper bound. The big problem that should be solved for these polymers to be commercialized is their aging through time. In high glassy polymeric membrane such as PIM-1 and its modifications, solubility selectivity has more contribution towards permselectivity than diffusivity selectivity. So in this thesis work pure and mixed gas sorption behavior of carbon dioxide and methane in three PIM-based membranes (PIM-1, TZPIM-1 and AO-PIM-1) and Polynonene membrane is rigorously studied. Sorption experiment is performed at different temperatures and molar fraction. Sorption isotherms found from the experiment shows that there is a decrease of solubility as the temperature of the experiment increases for both gases in all polymers. There is also a decrease of solubility due to the presence of the other gas in the system in the mixed gas experiments due to competitive sorption effect. Variation of solubility is more visible in methane sorption than carbon dioxide, which will make the mixed gas solubility selectivity higher than that of pure gas solubility selectivity. Modeling of the system using NELF and Dual mode sorption model estimates the experimental results correctly Sorption of gases in heat treated and untreated membranes show that the sorption isotherms don’t vary due to the application of heat treatment for both carbon dioxide and methane. But there is decrease in the diffusivity coefficient and permeability of pure gases due to heat treatment. Both diffusivity coefficient and permeability decreases with increasing of heat treatment temperature. Diffusivity coefficient calculated from transient sorption experiment and steady state permeability experiment is also compared in this thesis work. The results reveal that transient diffusivity coefficient is higher than steady state diffusivity selectivity.

Novel materials for direct X-ray detectors based on semiconducting organic polymers

Conventional inorganic materials for x-ray radiation sensors suffer from several drawbacks, including their inability to cover large curved areas, me- chanical sti ffness, lack of tissue-equivalence and toxicity. Semiconducting organic polymers represent an alternative and have been employed as di- rect photoconversion material in organic diodes. In contrast to inorganic detector materials, polymers allow low-cost and large area fabrication by sol- vent based methods. In addition their processing is compliant with fexible low-temperature substrates. Flexible and large-area detectors are needed for dosimetry in medical radiotherapy and security applications. The objective of my thesis is to achieve optimized organic polymer diodes for fexible, di- rect x-ray detectors. To this end polymer diodes based on two different semi- conducting polymers, polyvinylcarbazole (PVK) and poly(9,9-dioctyluorene) (PFO) have been fabricated. The diodes show state-of-the-art rectifying be- haviour and hole transport mobilities comparable to reference materials. In order to improve the X-ray stopping power, high-Z nanoparticle Bi2O3 or WO3 where added to realize a polymer-nanoparticle composite with opti- mized properities. X-ray detector characterization resulted in sensitivties of up to 14 uC/Gy/cm2 for PVK when diodes were operated in reverse. Addition of nanoparticles could further improve the performance and a maximum sensitivy of 19 uC/Gy/cm2 was obtained for the PFO diodes. Compared to the pure PFO diode this corresponds to a five-fold increase and thus highlights the potentiality of nanoparticles for polymer detector design. In- terestingly the pure polymer diodes showed an order of magnitude increase in sensitivity when operated in forward regime. The increase was attributed to a different detection mechanism based on the modulation of the diodes conductivity.

Biomimetic coating of organic polymers with a protein-functionalized layer of calcium phosphate: the surface properties of the carrier influence neither the coating characteristics nor the incorporation mechanism or release kinetics of the protein

Polymers that are used in clinical practice as bone-defect-filling materials possess many essential qualities, such as moldability, mechanical strength and biodegradability, but they are neither osteoconductive nor osteoinductive. Osteoconductivity can be conferred by coating the material with a layer of calcium phosphate, which can be rendered osteoinductive by functionalizing it with an osteogenic agent. We wished to ascertain whether the morphological and physicochemical characteristics of unfunctionalized and bovine-serum-albumin (BSA)-functionalized calcium-phosphate coatings were influenced by the surface properties of polymeric carriers. The release kinetics of the protein were also investigated. Two sponge-like materials (Helistat® and Polyactive®) and two fibrous ones (Ethisorb and poly[lactic-co-glycolic acid]) were tested. The coating characteristics were evaluated using state-of-the-art methodologies. The release kinetics of BSA were monitored spectrophotometrically. The characteristics of the amorphous and the crystalline phases of the coatings were not influenced by either the surface chemistry or the surface geometry of the underlying polymer. The mechanism whereby BSA was incorporated into the crystalline layer and the rate of release of the truly incorporated depot were likewise unaffected by the nature of the polymeric carrier. Our biomimetic coating technique could be applied to either spongy or fibrous bone-defect-filling organic polymers, with a view to rendering them osteoconductive and osteoinductive.

T2 star relaxation times for assessment of articular cartilage at 3 T: a feasibility study

T2 mapping techniques use the relaxation constant as an indirect marker of cartilage structure, and the relaxation constant has also been shown to be a sensitive parameter for cartilage evaluation. As a possible additional robust biomarker, T2* relaxation time is a potential, clinically feasible parameter for the biochemical evaluation of articular cartilage.

Chemical Research with Undergraduate Collaborators: Building Cyclic Polymers

Undergraduate research in chemistry provides not only a meaningful experience for the students, but is essential in getting research done. This talk will focus on an ongoing project in my lab: designing large molecules of specific shapes by studying the fundamental reactions. While results will be discussed, the talk will be tailored towards a general audience. I will attempt to highlight the outstanding contributions made by Bucknell students that have worked in my lab.