Light-sensitive polymeric nanoparticles based on photo-cleavable chromophores

Der Fokus dieser Arbeit liegt in dem Design, der Synthese und der Charakterisierung neuartiger photosensitiver Mikrogele und Nanopartikel als potentielle Materialien für Beladungs- und Freisetzungsanwendungen. Zur Realisierung dieses Konzepts wurden verschiedene Ansätze untersucht.Es wurden neuartige niedermolekulare lichtspaltbare Vernetzermoleküle auf der Basis von o-Nitrobenzylderivaten synthetisiert, charakterisiert und zur Herstellung von photosensitiven PMMA und PHEMA Mikrogelen verwendet. Diese sind unter Bestrahlung in organischen Lösungsmitteln quellbar und zersetzbar. Durch die Einführung anionischer MAA Gruppen in solche PHEMA Mikrogele wurde dieses Konzept auf doppelt stimuliresponsive p(HEMA-co-MAA) Mikrogele erweitert. Hierbei wurde ein pH-abhängiges Quellbarkeitsprofil mit der lichtinduzierten Netzwerkspaltung in wässrigen Medien kombiniert. Diese duale Sensitivität zu zwei zueinander orthogonalen Reizen stellt ein vielversprechendes Konzept zur Kombination einer pH-abhängigen Beladung mit einer lichtinduzierten Freisetzung von funktionellen Substanzen dar. Desweiteren wurden PAAm Mikrogele entwickelt, welche sowohl eine Sensitivität gegenüber Enzymen als auch Licht aufweisen. Dieses Verhalten wurde durch die Verwendung von (meth-)acrylatfunktionalisierten Dextranen als polymere Vernetzungsmoleküle erreicht. Das entsprechende stimuliresponsive Profil basiert auf der enzymatischen Zersetzbarkeit der Polysaccharid-Hauptkette und der Anbindung der polymerisierbaren Vinyleinheiten an diese über photospaltbare Gruppen. Die gute Wasserlöslichkeit der Vernetzermoleküle stellt einen vielversprechenden Ansatz zur Beladung solcher Mikrogele mit funktionellen hydrophilen Substanzen bereits während der Partikelsynthese dar. Ein weiteres Konzept zur Beladung von Mikrogelen basiert auf der Verwendung von photolabilen Wirkstoff-Mikrogel Konjugaten. In einem ersten Schritt zur Realisierung solch eines Ansatzes wurde ein neuartiges Monomer entwickelt. Hierbei wurde Doxorubicin über eine lichtspaltbare Gruppe an eine polymerisierbare Methacrylatgruppe angebunden. Für die Freisetzung hydrophober Substanzen in wässrigen Medien wurden polymere Photolack-Nanopartikel entwickelt, welche sich unter Bestrahlung in Wasser zersetzen. Die lichtinduzierte Änderung der Hydrophobizität des Polymers ermöglichte die Freisetzung von Nilrot durch das Auflösen der partikulären Struktur. Ein interessanter Ansatz zur Verhinderung einer unkontrollierten Freisetzung funktioneller Substanzen aus Mikrogelen ist die Einführung einer stimuliresponsiven Schale. In diesem Kontext wurden Untersuchungen zur Bildung von nicht-stimulisensitiven Schalen um vorgefertigte Mikrogelkerne und zur Synthese von Hydrogelkernen in vorgefertigten polymeren Schalen (Nanokapseln) durchgeführt.

Functionalization of hyperbranched polycarbosilanes - block copolymers and electrochemistry

Polycarbosilanes are a class of polymers at the interface between organic and inorganic chemistry. They are characterized by a high thermal and chemical inertness and high flexibility, especially pronounced for branched structures. Linear polycarbosilanes are well known as precursors for the preparation of SiCx ceramics. Additionally, more sophisticated architectures like dendrimers, hyperbranched polymers or block copolymers have been the subject of research for more than a decade. The scope of this work was to expand the properties and fields of application for polycarbosilane-containing structures. Thus, the work is divided in two major parts. The first part covers the synthesis and characterization of hyperbranched polycarbosilanes containing organometallic moieties. Hyperbranched poly-carbosilanes were synthesized using hydrosilylation of diallylmethylsilane and methyldiundecenylsilane. The degree of branching for polydiallymethylsilane was determined using standard 1H-NMR spectroscopy. The functional building blocks ferrocenyldimethylsilane and diferrocenylmethylsilane were synthesized which contain an isolated ferrocene unit or two ferrocenes bridged by silicon, respectively. Hyperbranched polycarbosilanes functionalized with ferrocenyl moieties were synthesized by modification of preformed polymers or by copolymerization of AB2 carbosilane monomers with AX-type ferrocenylsilanes. Polymers with Mn = 2500-9000g/mol and ferrocene contents of up to 67wt% were obtained. Electrochemical characterization by cyclic voltammetry revealed that polymers functionalized with isolated ferrocene units showed a single reversible oxidation wave, while voltammograms for polymers functionalized with diferrocenyl silane exhibited two well-separated reversible oxidation-reduction waves. This shows that the polymer bound ferrocenes bridged by silicon are electronically communicating and thus oxidation of the first ferrocene shifts the oxidation potential for the adjacent one. The polymers were utilized successfully for the preparation of modified electrodes with persistent and reproducible electrochemical response in organic solvents as well as in aqueous solution. The presented work has proven that ferrocenyl-functionalized hyperbranched polymers exhibit similar electrochemical properties as the analogous dendrimers. In a further approach it was shown that hyperbranched polymers containing organometallic moieties can be synthesized by polymerization of a new ferrocene-containing AB2 monomer - diallylferrocenylsilane. The second part of this work is dedicated to the preparation of core-functional hyperbranched polycarbosilanes. Low molecular weight ambifunctional molecules were synthesized that contain double bonds for the attachment of a polycarbosilane polymer as well as a second functionality available for further reaction and modification. Reactive vinyl groups in the core molecule allow an efficient attachment of hyperbranched polycarbosilane which was proven by MALDI-ToF and GPC. In combination with slow monomer addition techniques molecular weight and polydispersity of the polymers were controlled successfully. Core-functional polymers were characterized by NMR-spectroscopy, MALDI-ToF and GPC. Polymers with polydispersities <2 and molecular weights up to 5300g/mol were obtained. Transformation of the double bonds of the carbosilane was demonstrated with various silanes using hydrosilylation reaction or hydrogenation. Additionally, the core-functionality was varied resulting in polymers with bromo-, phthalimide-, amine- or azide moieties. Thus, a versatile synthetic strategy was developed that allows the synthesis of tailor-made polymers.A promising approach is the application of the polymer building blocks in copolymer synthesis. Bisglycidolization of amine-functional polycarbosilanes produces macro-initiators that are suitable for the multibranching-ring opening polymerization of glycidol. This experiments lead to the first example of hyperbranched-hyperbranched amphiphilic block copolymers, hb-PG-b-hb-PCS. Furthermore, the implementation of copper-catalyzed cycloaddition between azide-functional polycarbosilane and alkyne-functional poly(ethoxyethyl glycidylether) resulted in linear-hyperbranched block copolymers. The facile removal of acetal protecting groups provided convenient access to lin-PG-b-hb-PCS.

Einflüsse von Folienqualität und Blister-Design auf die Funktionalität von Blisterverpackungen

Ziel dieser Arbeit ist die Untersuchung der Einflüsse von Blister-Design und Folienqualität auf die Funktionalität von Blisterverpackungen. Hierzu werden analytische Methoden mittels Interferometrie, IR-Spektroskopie, Betarückstreuverfahren, Wirbelstromverfahren und Impedanzspektroskopie entwickelt, die zur quantitativen Bestimmung von Heißsiegellacken und Laminatbeschichtungen von Aluminium-Blisterfolien geeignet sind. Ein Vergleich der Methoden zeigt, dass sich das Betarückstreuverfahren, die Interferometrie und IR-Messungen für die Heißsiegellackbestimmung, die Interferometrie und das Wirbelstromverfahren für die Bestimmung von Kunststofflaminaten eignen.rnIm zweiten Abschnitt der Arbeit werden Einflüsse des Heißsiegellack-Flächengewichtes von Deckfolien auf die Qualität von Blisterverpackungen untersucht. Mit Zunahme des Flächengewichtes zeigt sich eine Erhöhung der Siegelnahtfestigkeit aber auch der Wasserdampfdurchlässigkeit von Blistern. Die untersuchten Heißsiegellacke zeigen Permeationskoeffizienten vergleichbar mit Polyvinylchlorid. In Untersuchungen zur Siegelprozessvalidität zeigt das Heißsiegellack-Flächengewicht nur geringfügige Auswirkungen auf diese. rnIm dritten Abschnitt der Arbeit werden Einflüsse des Blister-Designs auf die Benutzerfreundlichkeit von Blisterverpackungen durch eine Handlingstudie untersucht. Variationen der Öffnungskräfte von Durchdrück-Blistern wirken sich deutlich auf die Bewertungen der Blister durch die Probanden aus. Während die meisten Probanden alle getesteten Durchdrück-Blister innerhalb der Testdauer von 4 Minuten öffnen können (>84%), treten beim Peel-Blister und Peel-off-push-through-Blister deutlich mehr Handlingprobleme auf. Die Handlingprobleme korrelieren mit dem Alter, der Lebenssituation, der gesundheitlichen Verfassung und der Sehfähigkeit der Probanden. rn

Functional silicones and silicone-containing block copolymers

Polysiloxanes can be synthesized and subsequently modified (i) by the attachment of small molecules that change the properties of the silicone in such a way that it becomes more hydrophilic, but under the premise that this does not go together with a loss of the silicone-specific features. This can be done by adding hydrophilic sidechains to a polysiloxane. Polyethers like poly(ethylene glycol) or hyperbranched polyether-polyols are suitable in this regard. In order to assure that the silicone properties retain, these side groups can be attached to only one part of the polysiloxane backbone, which results in a block copolymer that consists of a common polysiloxane and a second block of the modified structure. (ii) Polysiloxanes can be equipped with functional groups that are capable of initializing polymerization of a different monomer (macroinitiator approach). For example, hydroxyl groups are used to initiate the ring opening polymerization of cyclic esters, or ATRP macroinitiators can be synthesized to add a second block via controlled radical polymerization. Stimuli responsive polymers like poly(oligoethylene glycol methacrylate) (POEGMA) can be added via this route to create “smart” siloxane-containing block copolymers that respond to certain stimuli. rnAn important premise for all synthetic routes is to achieve the targeted structure in a process as simple as possible, because facile availability of the material is crucial with regard to industrial applicability of the invented products. rnConcerning characterization of the synthesized macromolecules, emphasize is put on their (temperature dependent) aggregation behavior, which can be investigated by several microscopic and scattering methods, their behavior at the interface between silicone oils and water and their thermal properties.rnrn

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

The fabrication and application of semi-crystalline and thermoset-thermoplastic composite colloidal particles with well-defined microstructures

Die Zielsetzung der Arbeit besteht darin, neue Ansätze zur Herstellung strukturierter Kompositpartikel in wässrigem Medium zu entwickeln, welche als die Bildung genau definierter heterogener Strukturen in Kolloidsystemen angesehen werden können. Im Allgemeinen wurden zwei verschiedene Herangehensweisen entwickelt, die sich aufgrund des Ursprungs der gebildeten heterogenen Strukturen unterscheiden: Heterogenität oder Homogenität. Der Erste Ansatz basiert auf der Aggregation heterogener Phasen zur Bildung strukturierter Kolloidpartikel mit Heterogenität in der zugrunde liegenden Chemie, während der Zweite Ansatz auf der Bildung heterogener Phasen in Kolloidpartikeln aus homogenen Mischungen heraus durch kontrollierte Phasenseparation beruht.rnIm Detail beschäftigt sich der erste Teil der Dissertation mit einer neuen Herstellungsmethode für teilkristalline Komposit-Kolloidpartikel mit hoher Stabilität basierend auf der Aggregation flüssiger Monomertropfen an teilkristalline Polyacrylnitrilpartikel. Nach der Aggregation wurden hochstabile Dispersionen bestehend aus strukturierten, teilkristallinen Kompositpartikeln durch freie radikalische Polymerisation erhalten, während ein direktes Mischen der PAN Dispersionen mit Methacrylat-Polymerdispersionen zur unmittelbaren Koagulation führte. In Abhängigkeit von der Glastemperatur des Methacrylatpolymers führt die anschließende freie radikalische Polymerisation zur Bildung von Rasberry oder Kern-Schale Partikeln. Die auf diese Weise hergestellten Partikel sind dazu in der Lage, kontinuierliche Filme mit eingebetteten teilkristallinen Phasen zu bilden, welche als Sauerstoffbarriere Anwendung finden können.rnDer zweite Teil der Dissertation beschreibt eine neue Methode zur Herstellung strukturierter Duroplast-Thermoplast Komposit-Kolloidpartikel. Die Bildung eines Duroplastnetzwerks mit einer thermoplastischen Hülle wurde in zwei Schritten durch verschiedene, separate Polymerisationsmechanismen erreicht: Polyaddition und freie radikalische Polymerisation. Es wurden stabile Miniemulsionen erhalten, welche aus Bisphenol-F basiertem Epoxidharz, Phenalkamin-basiertem Härter und Vinlymonomere bestehen. Sie wurden durch Ultraschall mit nachfolgender Härtung bei verschiedenen Temperaturen als sogenannte Seed-Emulsionen hergestellt. Weitere Vinylmonomere wurden hinzugegeben und nachfolgend polymerisiert, was zur Bildung von Kern-Schale, beziehungsweise Duroplast-Thermoplast Kolloidpartikeln führte. Dabei findet in beiden Fällen zwischen der duroplastischen und der thermoplastischen Phase eine chemisch induzierte Phasenseparation statt, welche essenziell für die Bildung heterogener Strukturen ist. Die auf diese Weise hergestellten Kompositpartikel sind dazu in der Lage, transparente Filme zu bilden, welche unter geeigneten Bedingungen deutlich verbesserte mechanische Eigenschaften im Vergleich zu reinen Duroplastfilmen bereitstellen.rn

Novel metallo-porphyrin based colourimetric amine sensors and their processing via plasma enhanced chemical vapour deposition at atmospheric pressure : synthesis, characterisation and mechanistic studies

Volatile amines are prominent indicators of food freshness, as they are produced during many microbiological food degradation processes. Monitoring and indicating the volatile amine concentration within the food package by intelligent packaging solutions might therefore be a simple yet powerful way to control food safety throughout the distribution chain.rnrnIn this context, this work aims to the formation of colourimetric amine sensing surfaces on different substrates, especially transparent PET packaging foil. The colour change of the deposited layers should ideally be discernible by the human eye to facilitate the determination by the end-user. rnrnDifferent tailored zinc(II) and chromium(III) metalloporphyrins have been used as chromophores for the colourimetric detection of volatile amines. A new concept to increase the porphyrins absorbance change upon exposure to amines is introduced. Moreover, the novel porphyrins’ processability during the deposition process is increased by their enhanced solubility in non-polar solvents.rnrnThe porphyrin chromophores have successfully been incorporated into polysiloxane matrices on different substrates via a dielectric barrier discharge enhanced chemical vapour deposition. This process allows the use of nitrogen as a cheap and abundant plasma gas, produces minor amounts of waste and by-products and can be easily introduced into (existing) roll-to-roll production lines. The formed hybrid sensing layers tightly incorporate the porphyrins and moreover form a porous structure to facilitate the amines diffusion to and interaction with the chromophores.rnrnThe work is completed with the thorough analysis of the porphyrins’ amine sensing performance in solution as well as in the hybrid coatings . To reveal the underlying interaction mechanisms, the experimental results are supported by DFT calculations. The deposited layers could be used for the detection of NEt3 concentrations below 10 ppm in the gas phase. Moreover, the coated foils have been tested in preliminary food storage experiments. rnrnThe mechanistic investigations on the interaction of amines with chromium(III) porphyrins revealed a novel pathway to the formation of chromium(IV) oxido porphyrins. This has been used for electrochemical epoxidation reactions with dioxygen as the formal terminal oxidant.rn

From anionic polymerization in continuous flow to macromolecular architectures and stimuli-responsive surfaces

The thesis can be divided in four parts and summarized as follows:(i) The investigation and development of a continuous flow synthesis procedure affording end-functional polymers by anionic polymerization and subsequent termination in one reaction step and on a multigram scale was carried out. Furthermore, the implementation of not only a single hydroxyl but multiple orthogonal functionalities at the chain terminus was achieved by utilizing individually designed, functional epoxide-based end-capping reagents.(ii) In an additional step, the respective polymers were used as macroinitiators to prepare in-chain functionalized block copolymers and star polymers bearing intriguing novel structural and material properties. Thus, the second part of this thesis presents the utilization of end-functional polymers as precursors for the synthesis of amphiphilic complex and in some cases unprecedented macromolecular architectures, such as miktoarm star polymers based on poly(vinyl pyridine), poly(vinyl ferrocene) and PEO.(iii) Based on these structures, the third part of this thesis represents a detailed investigation of the preparation of stimuli-responsive ultrathin polymer films, using amphiphilic junction point-reactive block copolymers. The single functionality at the block interface can be employed as anchor group for the covalent attachment on surfaces. Furthermore, the change of surface properties was studied by applying different external stimuli.(iv) An additional topic related to the oxyanionic polymerizations carried out in the context of this thesis was the investigation of viscoelastic properties of different hyperbranched polyethers, inspired by the recent and intense research activities in the field of biomedical applications of multi-functional hyperbranched materials.

Studio sulla distribuzione dell'inquinamento da idrocarburi clorurati nelle falde della Provincia di Ferrara.

La Provincia di Ferrara ha avuto (ed ha tuttora) sul suo territorio, insediamenti produttivi di varia natura, che nel tempo hanno fatto uso di idrocarburi alifatici clorurati, per scopi diversi: solventi, sgrassanti, refrigeranti, supporti chimici e farmaceutici, ecc. Soprattutto nei decenni passati, a causa di normative poco restringenti sull’uso e sullo smaltimento di questi composti, si sono verificate le condizioni per provocare l’inquinamento delle falde del territorio provinciale. Nel corso degli anni, si sono svolti studi di diverso carattere, finalizzati ad individuare e caratterizzare siti (o raggruppamenti di siti) contaminati da idrocarburi clorurati. In questo lavoro si è allargata l’attenzione a tutti i siti presenti nel territorio definito dai limiti amministrativi della Provincia di Ferrara, che, nell‘arco temporale 2000 – 2015, hanno evidenziato contaminazioni da CAHs nell’acquifero superficiale A0 e/o nell’acquifero confinato A1. Si sono create, quindi, carte di distribuzione dei siti inquinati su scala provinciale, analizzandone principalmente caratteristiche idrogeologiche e variazioni di distribuzione chimica nello spazio e nel tempo, in relazione agli studi di caratterizzazione ed a eventuali messe in sicurezza e/o bonifiche. I dati necessari sono stati reperiti dagli atti amministrativi e dai relativi documenti tecnici, messi a disposizione dalla Provincia di Ferrara. L’attenzione è ricaduta in particolare sul cloruro di vinile (Vinyl Chloride, VC) ritrovato in alte concentrazioni e in un alto numero di siti. Il suo non utilizzo diretto nei processi produttivi in esame, ne esclude la presenza in qualità di contaminante primario, classificandolo come prodotto della degradazione di altri idrocarburi clorurati più complessi, in larga parte etileni clorurati. Si è inoltre appurato, come la presenza di VC non sia solo attribuibile a siti operanti nel settore metallurgico o chimico, ma riguardi in alcuni casi inquinamenti provocati da commercio o stoccaggio di carburanti, a cui, in passato, furono aggiunti solventi clorurati per migliorarne le caratteristiche chimico-fisiche. Si è concluso infine, come nel territorio della Provincia di Ferrara siano frequenti condizioni particolari, che favoriscono la degradazione di composti organo-clorurati complessi, ed agevolano l’accumulo di cloruro di vinile. Tali caratteristiche, sono state principalmente individuate nella diffusa presenza di livelli fini, anche torbosi, e nella altrettanto diffusa presenza di ambienti riducenti, non solo nel caso dell’acquifero confinato A1 ma anche nel caso dell’acquifero superficiale A0.

Stereoselective synthesis of a monocyclic peloruside a analogue

The stereoselective synthesis of the monocyclic peloruside A analogue 4 has been achieved, following a new efficient approach for the introduction of the side chain, involving a late-stage addition of vinyl lithium species 7a to aldehyde 8. Further key steps are a highly diastereoselective allyltitanation reaction and a RCM-based macrocyclization.

Core-crosslinked compartmentalized cylinders

We present a detailed study on the preparation of compartmentalized cylindrical nanoparticles via a templated approach: the polybutadiene part of a linear polybutadiene-block-poly(2-vinyl pyridine)-block-poly(tert-butyl methacrylate) block terpolymer, B420V280T790, having a bulk microstructure with PB cylinders covered by a P2VP double helix and embedded in a PtBMA matrix was selectively crosslinked. Subsequent sonication-assisted dissolution and chemical modifications such as quaternization (P2VP to P2VPq) and ester hydrolysis (PtBMA to poly(sodium methacrylate), PMANa) resulted in core-crosslinked cylinders soluble in organic and aqueous media. Different amounts of crosslinker and the influence of the sonication treatment on size and shape of the cylindrical aggregates were investigated. The cylinders always exhibit a compartmentalized corona. Under certain conditions, in particular quaternization of P2VP in mixtures of THF and MeOH, the helical arrangement of the P2VPq shell could be preserved even in solution, whereas in most other cases randomly distributed P2VP/P2VPq patches were observed. In aqueous solution at high pH, intramicellar interpolyelectrolyte complex (im-IPEC) formation occurred between the positively charged P2VPq shell and the negatively charged PMANa corona. We further show that different noble metal nanoparticles can be generated either selectively within the im-IPEC compartments (Pd) or randomly distributed among shell and corona of the cylinders (Au and Pt).

Acid, Silver, and Solvent-Free Gold-Catalyzed Hydrophenoxylation of Internal Alkynes

A range of arylgold compounds have been synthesized and investigated as single-component catalysts for the hydrophenoxylation of unactivated internal alkynes. Both carbene and phosphine-ligated compounds were screened as part of this work, and the most efficient catalysts contained either JohnPhos or IPr/SIPr. Phenols bearing either electron-withdrawing or electron-donating groups were efficiently added using these catalysts. No silver salts, acids, or solvents were needed for the catalysis, and either microwave or conventional heating afforded moderate to excellent yields of the vinyl ethers.

Testing the TICT State Hypothesis: an Investigation into the Solvatochromic Behavior of 2-Naphthalenylmethylene Malononitrile

Towards the goal of investigating the possible Twisted Intramolecular Charge Transfer (TICT) state mechanism of fluorescence emission, two aromatic dicyanovinyl compounds, 2-(naphthalene-2-ylmethylene) malononitrile (DCN) and a rigidified analogue, 3,4-dihydrophenanthren-1(2H)-ylidene)malononitrile (RDCN) were synthesized and their absorption and steady-state fluorescence emission spectra characterized. The spectral characterization was divided into two studies: first, DCN and RDCN were characterized in liquid solvents of increasing polarity; second, DCN and RDCN were characterized in viscous solvents and rigid glass media. The absorption spectra for both DCN and RDCN in all solvents demonstrated little to no solvatochromism. Emission results for DCN and RDCN in liquid solvents of increasing polarity showed DCN possessing strong solvatochromism while RDCN showed much less solvatochromism. Using the Lippert-Mataga equation, the difference between the ground and excited state dipole moment for DCN was estimated to be 8.4 + 0.4 Debye and between ~3.0 to 5.0 Debye for RDCN. Quantum yield measurements for DCN and RDCN in hexane, diethyl ether and acetonitrile were less than 0.01 and independent of polarity for both both solvents, with DCN generally possessing a quantum yield 3-4 times greater than RDCN. Experiments in glass media for DCN and RDCN showed a lessening of their solvatochromic character in both polar and non-polar glasses. These data provide strong evidence for a link between molecular flexibility and solvatochromism. However, while these data are consistent with a TICT state hypothesis for the emission mechanism, an alternative mechanism proposed by Maroncelli et al.10 involving rotation about the dicyanovinyl double bond in the excited state remains a possibility as well.

Determination of caries risk at resin composite margins

PURPOSE: To design an artificial mouth in order to evaluate if a new diagnostic tool (Clinpro Cario Diagnosis) can be used for early detection of secondary caries at resin composite margins in vitro. METHODS: 32 intact human third molars received standardized Class-V resin composite restorations (Tetric Ceram bonded with Syntac SC). After storage for 4 weeks at 37 degrees C, teeth were subjected to 5,000 or 10,000 thermocycles (+/- 5 degrees C and +/- 55 degrees C) and polysiloxane impressions were taken. Streptococcus mutans 10449 (SM) was used in a nutrition medium to initiate a secondary caries process. Daily, the teeth were incubated for 2 x 2.5 hours in SM containing nutrition medium followed by 2 x 9.5 hours incubation in artificial saliva. Teeth were investigated after total incubation periods of 4, 6, and 8 weeks. After the different incubation protocols, the restoration margins were evaluated for infection and secondary caries processes in using Clinpro Cario Diagnosis which measures site-specifically the lactic acid production of SM in response to a sucrose challenge. The color signal was read 5 minutes after removal of the diagnostic impression. After thermocycling and biological load cycling, precision polysiloxane impressions were taken and replicas were investigated under a light microscope for gap widths at enamel and dentin margins. Demineralization was evaluated by fluorescence microscopy in using a special FITC filter. The demineralization depths at the cavity margin were calculated with Xpert for Windows using a pixel distance of 5 microm. RESULTS: After the different thermocycling protocols, no differences in gap widths and demineralization depths were found (P > 0.05). After SM incubation, gap widths and demineralization depths were significantly dependent on SM incubation time and previous number of thermocycles (P < 0.05). Lactic acid formations of SM were detectable by Clinpro Cario Diagnosis at dentin cavosurface margins formed after 6 weeks of incubation with SM (P < 0.05).

Photodegradation and photostabilization of weathered wood flour filled polyethylene composites

Wood plastic composites (WPCs) have gained popularity as building materials because of their usefulness in replacing solid wood in a variety of applications. These composites are promoted as being low-maintenance, high-durability products. However, it has been shown that WPCs exposed to weathering may experience a color change and/or loss in mechanical properties. An important requirement for building materials used in outdoor applications is the retention of their aesthetic qualities and mechanical properties during service life. Therefore, it is critical to understand the photodegradation mechanisms of WPCs exposed to UV radiation and to develop approaches to stabilize these composites (both unstabilized and stabilized) as well as the effect of weathering on the color fade and the retention of mechanical properties were characterized. Since different methods of manufacturing WPCs lead to different surface characteristics, which can influence weathering, the effect of manufacturing method on the photodegradation of WPCs was investigated first. Wood flour (WF) filled high-density polyethylene (HDPE) composite samples were either injection molded, extruded, or extruded and then planed. Fourier transform infrared (FTIR) spectroscopy was used to monitor the surface chemistry of the manufactured composites. The spectra showed that the surface of planed samples had more wood component than extruded and injection molded samples, respectively. After weathering, the samples were analyzed for color fade, and loss of flexural properties. The final lightness of the composites was not dependent upon the manufacturing method. However the mechanical property loss was dependent upon manufacturing method. The samples with more wood component at the surface (planed samples) experienced a larger percentage of total loss in flexural properties after weathering due to a greater effect of moisture on the samples. The change in surface chemistry of HDPE and WF/HDPE composites after weathering was studied using spectroscopic techniques. X-ray photoelectron spectroscopy (XPS) was used to characterize the occurrence of surface oxidation whereas FTIR spectroscopy was used to monitor the development of degradation products, such as carbonyl groups and vinyl groups, and to determine changes in HDPE crystallinity. Surface oxidation occurred immediately after exposure for both the neat HDPE and WF/HDPE composites. After weathering, the surface of the WF/HDPE composites was oxidized to a greater extent than the neat HDPE after weathering. This suggests that photodegradation is exacerbated by the addition of the carbonyl functional groups of the wood fibers within the HDPE atrix during composite manufacturing. While neat HDPE may undergo cross-linking in the initial stages of accelerated weathering, the WF may physically hinder the ability of the HDPE to cross-link resulting in the potential for HDPE chain scission to dominate in the initial weathering stages of the WF/HDPE composites. To determine which photostabilizers are most effective for WF/HDPE composites, factorial experimental designes were used to determine the effects of adding two hindered amine light stabilizers, an ultraviolet absorber, and a pigment on the color made and mechanical properties of both unweathered and UV weathered samples. Both the pigment and ultraviolet absorber were more effective photostabilizers for WF/HDPE composites than hinder amine light stabilizers. The ineffectiveness of hindered amine light stabilizers in protecting WPCs against UV radiation was attribuated to the acid/base reactions occurring between the WF and hindered amine light stabilizer. The efficiency of an ultraviolet absorber and/or pigment was also examined by incorporating different concentration of an ultraviolet absorber and/or pigment into WF/HDPE composites. Color change and flexural properties were determined after accelerated UV weathering. The lightness of the composite after weathering was influenced by the concentration of both the ultraviolet absorber by masking the bleaching wood component as well as blocking UV light. Flexural MOE loss was influenced by an increase in ultraviolet absorber concentration, but increasing pigment concentration from 1 to 2% had little influence on MOE loss. However, increasing both ultraviolet absorber and pigment concentration resulted in improved strength properties over the unstabilized composites after 3000 h of weather. Finally, the change in surface chemistry due to weathering of WF/HDPE composites that were either unstabilized or stabilized with an ultraviolet absorber and/or pigment was analyzed using FTIR spectroscopy. The samples were tested for loss in modulus of elasticity, carbonyl and vinyl group formation at the surface, and change in HDPE crystallinity. It was concluded that structural changes in the samples; carbonyl group formation, terminal vinyl group formation, and crystallinity changes cannot reliably be used to predict changes in modulus of elasticity using a simple linear relationship. The effect of cross-linking, chain scission, and crystallinity changes due to ultraviolet exposure as well as the interfacial degradation due to moisture exposure are inter-related factors when weathering HDPE and WF/HDPE composites.