Les moisissures sont des biocontaminants courants des environnements intérieurs causant la biodégradation des matériaux qu'ils colonisent et favorisant l'apparition de diverses pathologies, notamment respiratoires telles que des allergies, des infections ou des toxi-infections.En raison de ces impacts, la maîtrise de la contamination fongique constitue une préoccupation majeure pour des secteurs aussi divers que les industries agro-alimentaires, pharmaceutiques, les hôpitaux ou encore les établissements patrimoniaux. Actuellement, les techniques utilisées pour surveiller ces environnements sensibles reposent sur la mesure de particules biologiques en suspension dans l'air émises après sporulation des moisissures. Afin de prévenir les effets de la prolifération de moisissures, le Centre Scientifique et Technique du Bâtiment (CSTB) a développé un indice de contamination fongique basé sur la détection de Composés Organiques Volatils (COV) spécifiques émis dès le début de cette croissance microbienne avant même l'émission dans l'air de particules délétères (Moularat, Robine et al. 2008; Moularat, Robine et al. 2008). Cet outil, breveté en 2007 (Moularat 2007), a été employé lors de différentes campagnes de mesures dans l'habitat, les bureaux, les écoles, les crèches, les musées…(Moularat, Derbez et al. 2008; Joblin, Moularat et al. 2010; Moularat, Hulin et al. 2011; Hulin, Moularat et al. 2012). Depuis le CSTB a élaboré un prototype de balise de surveillance intégrant cet indice et constitué de capteurs gaz à base de Polymères Conducteurs Electroniques (PCE), en collaboration avec l'ESIEE Paris (l'Ecole d'Ingénieurs de la Chambre de Commerce et d'Industrie de Paris) (pour la balise) et le Laboratoire de Physico-chimie des Polymères et des Interfaces (LPPI) (pour les PCE). Ainsi des capteurs à base de polypyrrole (PPy) et de Poly-(3,4-éthylènedioxythiophène)-poly(styrènesulfonate) (PEDOT-PSS) ont permis de différencier un environnement contaminé d'un environnement sain. Si ces couches sensibles se sont montrées efficaces pour la détection par l'identification d'une empreinte globale de COV d'origine fongique, elles ne s'avèrent pas encore suffisamment sélectives pour réaliser l'identification de chaque COV, indispensable pour le calcul de l'indice.Dans le cadre de la surveillance de la qualité microbiologique de l'air des environnements intérieurs, cette thèse a pour ambition de prolonger ces travaux en étudiant les mécanismes d'interaction entre COV et PCE en vue de l'application au développement de micro-capteurs chimiques adaptés à la mesure in situ. Cette recherche implique à la fois l'optimisation de la sensibilité et de la sélectivité de ces polymères et le développement d'une matrice de capteurs.Le premier aspect de cette étude a consisté à synthétiser de nouveaux PCE, plus spécifiques sur la base de ceux identifiés comme pertinents lors de la thèse de Joblin en 2011. Ainsi, des polymères, à base de pyrrole fonctionnalisés en position 1 et 3, ont été synthétisés par voie électrochimique. Le PEDOT-PSS, polymère commercial (sous forme de suspension dans l'eau), a, quant-à-lui, été conditionné par différents traitements thermiques.Le second aspect a porté sur l'étude de l'influence de l'exposition des COV à ces PCE sur leurs propriétés physico-chimiques. Ainsi, des caractérisations morphologiques, électrochimiques, optiques ainsi que la variation des propriétés de surface ont permis de mettre en évidence des interactions faibles, en général de type van der Waals ou par liaison hydrogène, entre COV et PCE.Enfin, le dernier aspect a porté sur l'étude expérimentale de la réponse des capteurs en contact avec différents COV issus ou non du métabolisme fongique. Cette dernière étape a permis de vérifier les hypothèses de mécanismes d'interaction. Par ailleurs, la spécificité de la matrice de capteurs vis-à-vis des composés fongiques a été démontrée. Cette matrice de capteurs a également permis d'obtenir des signatures spéci / Conducting polymers can be used as active materials of sensing devices that find application in different areas, such as quality control of products in industries such as food and beverage, cosmetics and solvents, in the monitoring of air quality for environmental and safety purposes, and as an auxiliary tool in the diagnosis of diseases. In spite of this, as a general rule, the details of the prevailing interactions of the volatile compounds and the polymer are not well understood. For this reason, we have focused the work of this thesis on the characterization of the interactions between vapors of volatile organic compounds and thin films of conducting polymers. These films, that were the active components of the sensors, were prepared atop of different geometry of interdigitated electrodes via electropolymerization, where several preparation parameters (such as doping agents nature and concentrations, monomer nature, thermal annealing) were observed to assure an homogeneous growth of the polymeric film. Several characterizations such as electrochemical studies, AFM observations and UV-VIS-NIR spectra studies were used to obtain detailed information about the interaction mechanisms between VOC and conducting polymers. We have also measured the contact angle of water, formamide and diiodomethane deposited on the surface of the polymeric films to evaluate surface free energy (and its acid-base and dispersive components). The selectivity and sensitivity of the polymeric sensors when exposed to different volatile organic compounds (VOCs) have shown to be dependent not only of the properties of the analyzed VOC but also on the nature of the counter-ion used to dope the polypyrrole film. As a final conclusion, we can say that as a result of this work it becomes possible to optimize the design of an arrangement of sensors such that both a better sensitivity and a better selectivity sensitivity to a given chemical environment can be achieved.

This thesis begins with a brief analysis of the synthetic methodologies utilized in polymer science. A conclusion is drawn inferring that upper limits in molecular design are inevitable, arising as a direct consequence of the predominance of covalent strategies in the field. To address these concerns, the universal polymer backbone (UPB) concept has been hypothesized. A UPB has been defined as any copolymer, side-chain functionalized with multiple recognition elements that are individually capable of forming strong, directional, and reversible non-covalent bonds. Non-covalent functionalization of these scaffolds can lead to the formation of a multitude of new polymer structures, each stemming from a single parent or universal polymer backbone. To prepare such a UPB, isomerically pure exo-norbornene esters containing either a PdII SCS pincer complex or a diaminopyridine residue were synthesized, polymerized, and copolymerized via ROMP. All polymerizations were living under mild reaction conditions. Kinetic studies showed that the kp values are highly dependent upon the isomeric purity but completely independent of the terminal recognition units. Non-covalent functionalization of these copolymers was accomplished via 1) directed self-assembly, 2) multi-step self- assembly, and 3) one-step orthogonal self-assembly. This system shows complete specificity of each recognition motif for its complementary unit with no observable changes in the association constant upon functionalization. To explore potential applications of this UPB concept, random terpolymers possessing high concentrations of pendant alkyl chains and small amounts of recognition units were synthesized. Non-covalent crosslinking using a directed functionalization strategy resulted in dramatic increases in solution viscosities for metal crosslinked polymers with only minor changes in viscosity for hydrogen bonding motifs. The crosslinked materials were further functionalized via self-assembly by employing the second recognition motif, which gave rise to functionalized materials with tailored crosslinks. This non-covalent crosslinking/functionalization strategy could allow for rapid and tunable materials synthesis by overcoming many difficulties inherent to the preparation of covalently crosslinked polymers. Finally, the current status of the UPB concept is reviewed and methodological extensions of the concept are suggested. Evaluation of how UPBs may be used to optimize materials and their potential use in fabricating unique electro-optical materials, sensors, and drug delivery vesicles are explored.

Conjugated polymers and oligomers have been widely studied based on their wide range of useful properties and applications. Given the importance of self-assembly and charge transfer in the development of conjugated materials for use in electronic applications, it is crucial to: (i) prepare functional materials by molecular design, (ii) evaluate the structure-property relationships of new materials, and (iii) develop fundamental understanding of electronic structure and charge transport behavior. The use of conjugated polymeric materials in electronic applications relies on control of the assembly and orientation of the polymer chains in the solid state. Conjugated polymers with liquid crystalline behavior could be used to implement an additional level of control over orientation and resultant properties. Substitution of the conjugated polythiophene backbone with semifluoroalkyl side chains (i.e., the diblock -(CH2)m(CF2)nF) has afforded materials with unusual properties. The mutual immiscibility of the aromatic backbone, the alkyl side-chain segments, and the fluoroalkyl side-chain termini provides control over supramolecular packing. A series of eight polymers has been synthesized, in which the lengths of the alkyl (m) and fluoroalkyl (n) segments are varied. One regiorandom analogue and two poly(3-alkylthiophene)s were also synthesized for comparative purposes. The structure, molecular weight, and regioregularity of the polymers were evaluated using a variety of techniques. The semifluoroalkyl-substituted polymers have been systematically studied to determine the effect of side chain length and m:n block ratios on their solution state, liquid crystalline, and solid state properties. The effect of side chains on conjugation was determined, where solubility allowed, by solution-state UV-visible and fluorescence spectroscopy. The thermal and liquid crystalline properties of the homopolymers were evaluated by DSC, variable-temperature X-ray diffraction, and polarized optical microscopy. Several semifluoroalkyl-substituted polythiophene homologues show liquid crystalline behavior. Molecular packing and charge transport are key factors governing the use of conjugated materials in electronic applications. A wide variety of oligomers have been studied as models for charge migration in conjugated polymers. One-dimensional models do not adequately represent two-dimensional charge transport; thus, a variety of two-dimensional, covalently-linked models have been developed. Previous work by our group, and others, led to the proposal of bis(oligothienyl) compounds as models to study the interaction of the ð-conjugated chains. Previous reports by other researchers described the synthesis and characterization of hydrogen-terminated analogues of 1,8-bis(oligothienyl)naphthalenes. However, these materials proved to be unsuitable for use as charge transport models, as they were subject to irreversible polymerization upon oxidation. Installation of methyl groups at the terminal a-positions of 1,8-bis(oligothienyl)naphthalenes allowed us to create a series of models in which conjugated chains are held in close proximity. This provides access to multiple redox states, and future systems based on these molecules may be used as models for charge transport or as functional materials for incorporation into devices.

Block copolymer self-assembly has demonstrated sub-optical lithographic resolution . High values of chi, the block copolymer interaction parameter, are required to achieve next-generation lithographic resolution . Unfortunately, high values of chi can lead to thin film orientation control difficulties , which are believed to be caused by large differences in the surface energy of each block relative to the substrate and the free surface. The substrate-block interface can be modified to achieve a surface energy intermediate to that of each individual block ; the air-polymer interface, however, presents additional complications. This thesis describes the synthesis of polymers for top coat surface treatments, which are designed to modify the surface energy of the air-block copolymer interface and enable block copolymer orientation control upon thermal annealing. Polymers with β-keto acid functionality were synthesized to allow polarity switching upon decarboxylation. Syntheses of anhydride containing polymers were established that provide another class of polarity switching materials. / text

To enable future environmentally friendly access to space by means of solid rocket propulsion a viable replacement to the hazardous ammonium perchlorate oxidizer is needed. Ammonium dinitramide (ADN) is one of few such compounds currently known. Unfortunately compatibility issues with many polymer binder systems and unexplained solid-state behavior have thus far hampered the development of ADN-based propellants. Chapters one, two and three offer a general introduction to the thesis, and into relevant aspects of quantum chemistry and polymer chemistry. Chapter four of this thesis presents extensive quantum chemical and spectroscopic studies that explain much of ADN’s anomalous reactivity, solid-state behavior and thermal stability. Polarization of surface dinitramide anions has been identified as the main reason for the decreased stability of solid ADN, and theoretical models have been developed to explain and predict the solid-state stability of general dinitramide salts. Experimental decomposition characteristics for ADN, such as activation energy and decomposition products, have been explained for different physical conditions. The reactivity of ADN towards many chemical groups is explained by ammonium-mediated conjugate addition reactions. It is predicted that ADN can be stabilized by changing the surface chemistry with additives, for example by using hydrogen bond donors, and by trapping radical intermediates using suitable amine-functionalities. Chapter five presents several conceptual green energetic materials (GEMs), including different pentazolate derivatives, which have been subjected to thorough theoretical studies. One of these, trinitramide (TNA), has been synthesized and characterized by vibrational and nuclear magnetic resonance spectroscopy. Finally, chapter six covers the synthesis of several polymeric materials based on polyoxetanes, which have been tested for compatibility with ADN. Successful formation of polymer matrices based on the ADN-compatible polyglycidyl azide polymer (GAP) has been demonstrated using a novel type of macromolecular curing agent. In light of these results further work towards ADN-propellants is strongly encouraged. / QC 20101103

Multiphase systems provide an opportunity to develop both novel processing methods and create advanced materials through combining the properties of dissimilar phases in a synergistic manner. In this work, we detail the halogenation of poly(ether ether ketone) (PEEK) through both solution-state and gel-state functionalization methods. The multiphase gel-state chemistry restricts functionalization to the amorphous regions of the semi-crystalline parent homopolymer and generates a copolymer with a blocky microstructure. Solution-state functionalization yields random copolymers which provide matched sets to the blocky analogs for fundamental investigations into the effects of polymer microstructure on material properties. Halogenating PEEK using N-halosuccinimides allows for direct installation of pendant halogens along the polymer backbone with facile control of halogen identity. For both bromination and iodination, blocky halogenation of PEEK provides faster crystallization kinetics, higher glass transition (Tg) and melting temperatures as well as superior crystallizability than random halogenation. When comparing halogen identity, increasing halogen size results in increased Tgs, decreased backbone planarity, and for copolymers with blocky microstructures, an earlier onset of phase separation. Increasing halogen size also results in decreased crystallizability and crystallization kinetics, however, these deleterious effects are mitigated in blocky microstructures due to colocalization of the pristine repeat units. Iodination also results in greater flame resistance than bromination for PEEK-based copolymers, and preserved crystallizability allows for the generation of flame retardant aerogels. Direct halogenation of PEEK in the gel-state also provided a reactive microstructural template for subsequent functionalization. Through the use of copper mediated cross-coupling chemistries, the aryl halide functionalities were leveraged to decorate the polymer backbone with pendant perfluoroalkyl chains. The blocky perfluoro alkyl PEEK demonstrated preserved crystallizability and serves as a candidate for compatibilization of poly(tetrafluoroethylene)-PEEK polymer blends. Superacid-modified PEEK was synthesized through a similar methodology and demonstrated over 50,000% increased hygroscopicity relative to the parent homopolymer, and exhibited preserved crystallizability. Multiphase systems were also designed to additively manufacture reinforced elastomers through vat photopolymerization using a degradable scaffold approach that challenged the current paradigm that the scaffold only serves as a geometrical template in vat photopolymerization. The scaffold crosslinks were cleaved through a reactive extraction process that liberated the glassy photopolymer backbone and resulted in over 200% increased ultimate strain and 50% increased ultimate stress relative to a control that was subjected to a neutral extraction. Lastly, thermoresponsive micellar ligands were synthesized as a multiphase approach to environmental remediation of metal-contaminated aqueous systems. / Doctor of Philosophy / Multiphase systems, such as a mixture of oil and water, are of great interest due to their ability to exhibit a multitude of properties from one material. Minimizing the size of the phases, through a technique called compatibilization, often improves the properties of the material. A common example is salad dressing, where the oil phase is compartmentalized into microscopic particles using surface-active molecules known as surfactants. Surfactants, also known as amphiphiles, partition to the interface between different phases due to the surfactants being comprised of dissimilar molecular constituents. One way to generate polymeric amphiphiles, where a polymer is a large molecule comprised of a molecular chain of repeating units, is through synthesizing block copolymers. Block copolymers have blocks of different constituents that are colocalized through covalent bonds in the polymer backbone and often exhibit phase separated structures, allowing for enhanced transport properties such as is seen in membranes. Using semi-crystalline polymers in membranes allows for enhanced mechanical integrity, as the crystallites act as physical crosslinks, or tie points, similar to the knots in a 3D rope ladder. These molecular knots limit the distance that the linear segments of the rope ladder can stretch, which in membranes leads to reduced swelling and increased mechanical performance. In this work we use semi-crystalline polymers to generate blocky copolymers through the use of halogenation. Halogenation installs halogen moieties as pendant groups on the polymer backbone, which can then by used as a chemical handle for subsequent reactions to further incorporate functionality into the copolymer and achieve desired properties such as proton (hydrogen nuclei) transport in fuel cell membranes. Halogenation also allows for the generation of blocky semi-crystalline copolymers for compatibilizing polymer blends of materials like poly(tetrafluoroethylene) and poly(ether ether ketone). Also in this work, we discuss the additive manufacturing of mechanically reinforced elastomers. An elastomer is another type of crosslinked network, and a mechanically reinforced elastomer can be through of as a 3D rope ladder where some of the linear segments of rope are replaced with steel bars, thus increasing the amount of work required to deform the network. The last multiphase systems discussed are similar to salad dressing, where there is a continuous water phase and a microscopic particle phase. The microscopic particles in this work are amphiphilic block copolymers that change their solubility in water with temperature and also have functionalities that should allow for the binding of metals from water-based systems.

Sulfonated poly(arylene ether sulfone)s as ion conductive copolymers have numerous potential applications. Membranes cast from these copolymers are desirable due to their good chemical and thermal stability, excellent mechanical strength, satisfactory conductivity, and excellent transport properties of water and ions. These copolymers can be used in a variety of topologies. Structure-property-performance relationships of these membranes as candidates for electrolysis of water for hydrogen production and for purification of water from dissolved ions have been studied. Linear and multiblock sulfonated poly(arylene ether sulfone)s are potential alternative candidates to Nafion membranes for hydrogen gas production via electrolysis of water. In this investigation, these copolymers were prepared from the direct polymerization of di-sulfonated and non-sulfonated comonomers with bisphenol monomers. In systematic investigations, a series of copolymers with modified properties were synthesized and characterized by changing the ratio of the sulfonated/non-sulfonated comonomers in each reaction. These copolymers were investigated in terms of mechanical stability, proton conductivity and H2 gas permeability at a range of temperatures and under fully hydrated conditions. A multiblock copolymer was synthesized and evaluated for its potential as membranes for electrolysis of water and for fuel cell applications. The multiblock copolymer contained some fluorinated repeat units in the hydrophobic blocks, and these were coupled with a fully disulfonated hydrophilic block prepared from 3,3'-disulfonate-4,4'-dichlorodiphenyl sulfone and biphenol. After annealing, the multiblock copolymer showed enhanced proton conductivity and a more ordered morphology in comparison to the random copolymer counterparts. At 90 oC and under fully hydrated conditions, improved proton conductivity and controlled H2 gas permeability was observed. Finally, the performance of the multiblock copolymer, which was measured as the ratio of proton conductivity to H2 gas permeability, was improved when compared to the state-of-the-art membrane, Nafion 212, by a factor of 3. In another systematic study, two series of random copolymers were synthesized and characterized, and then cast into membranes to evaluate for electrolysis of water. One series contained solely hydroquinone as the phenolic monomer, while the second series contained a mixture of resorcinol and hydroquinone as phenolic comonomers. The polymers that contained only the hydroquinone monomer showed exceptionally good mechanical properties due to the para-substituted comonomer in the composition of the polymer. In the resorcinol-hydroquinone series, gas permeability was constrained due to the presence of 25% of the meta-substituted comonomer incorporated into its structure. Low gas permeability and high proton conductivity at elevated temperatures were obtained for both the linear random and multiblock copolymers. Performance of these copolymers was superior to Nafion at elevated temperatures (80-95°C). In order to enhance the durability of these materials in their hydrated states at elevated temperatures, the surfaces of these copolymer films were treated with fluorine gas. In comparison with pristine non-fluorinated membranes, the modified membranes showed decreased water uptake and longer durability in Fenton's reagent. A series of linear and crosslinked copolymers were investigated with respect to their potential for use as membranes for desalination of water by electrodialysis and reverse osmosis. The crosslinked membranes were prepared by reacting controlled molecular weight, disulfonated oligomers that were terminated with meta-aminophenol with an epoxy reagent. The oligomers had systematically varied degrees of disulfonation and either 5000 or 10,000 Da controlled molecular weights. Membrane casting conditions were established to fabricate highly crosslinked systems with greater than 90% gel fractions. At such a high gel fraction, the water uptake of the crosslinked membranes was lower than that of the linear biphenol-based, disulfonated random copolymer with a similar IEC. Among these series of copolymers, it was shown that the crosslinked membranes cast from the oligomers with 50% degree of disulfonation and a molecular weight of 10,000 Da had the lowest salt permeability of 10-8 cm2/sec. For desalination applications, a comonomer was synthesized with one sulfonate substituent on 4,4'-dichlorodiphenyl sulfone. This new monosulfonated comonomer allows for even distribution of the ions on the linear copolymer backbone, and this may be important for controlling ion transport. Mechanical tests were conducted on the membranes while they were submerged in a water bath. The ultimate strength of a fully hydrated copolymer with an IEC of 1.36 meq/g was approximately 60 MPa with an elongation at break of 160%. Moreover, in a monovalent/divalent mixed salt solution, the monosulfonated linear copolymer exhibited a constant Na+ passage of less than 1.0%. / Ph. D. / Purification systems have become an increasingly important scientific and technological need for millions around who face water shortages and/or impure sources of potable water. In response, water purification and hydrogen gas production have been widely used to produce pure products from a variety of water sources. In general, current state-of-the-art methods in separation technologies feature two major drawbacks: they are energy intensive and costly processes. In response to the growing need for purified water or pure hydrogen gas for energy generation, polymeric materials are increasingly used in the form of membranes to produce a purer product and overcome the hindrances associated with current energy intensive and inefficient methods. These membranes serve as a barrier for unwanted species, while at the same time allowing the desired species to pass through. Under proper conditions, these purification or chemical processes would generate pure materials that can be used on demand. The chemistry of candidate polymeric materials is extremely important to design a membrane with desired properties. Therefore, the principal goals of this investigation were to synthesize polymers for use as membranes in three areas: 1) Electrolysis of water for ultra-pure hydrogen gas generation 2) Fuel cells applications for electricity generation, and 3) Desalination of water to provide drinking water. For each technology, a series of sulfonated poly(arylene ether sulfone) copolymers were synthesized and characterized. By applying different monomers or chemistries, a range of appropriate copolymers were synthesized whose characteristics varied in topology and architecture, depending on the desired application. Once these copolymers were synthesized, they were cast into membranes under proper established conditions. In addition, the structure-property-performance relationship of these sulfonated polysulfone membranes were further investigated to provide a direction for future studies.

Introduction Oral delivery of proteins faces numerous challenges due to their enzymatic susceptibility and instability in the gastrointestinal tract. In recent years, the polyelectrolyte complexes have been explored for their ability to complex protein and protect them against chemical and enzymatic degradation. However, most of the conventional binary polyelectrolyte complexes (PECs) are formed by polycations which are associated with toxicity and non-specific bio-interactions. The aim of this thesis was to prepare a series of ternary polyelectrolyte complexes (APECs) by introduction of a polyanion in the binary complexes to alleviate the aforementioned limitations. Method Eight non-insulin loaded ternary complexes (NIL APECs) were spontaneously formed upon mixing a polycation [polyallylamine (PAH), palmitoyl grafted-PAH (Pa2.5), dimethylamino-1-naphthalenesulfonyl grafted-PAH (Da10) or quaternised palmitoyl-PAH (QPa2.5)] with a polyanion [dextran sulphate (DS) or polyacrylic acid (PAA)] at 2:1 ratio, in the presence of ZnSO4 (4μM). A model protein i.e., insulin was added to a polycation, prior to addition of a polyanion and ZnSO4 to form eight insulin loaded (IL) APECs. PECs were used as a control to compare APECs. The complexes were characterised by dynamic light scattering (DLS) and transmission electron microscope (TEM). In vitro stability of the complexes was investigated at pH (1.2-7.4), temperature (25˚C, 37˚C and 45˚C) and ionic strength (NaCl-68mM, 103mM and 145mM). Insulin complexation efficiency was assessed by using bovine insulin ELISA assay kit. The in vitro cytotoxicity was investigated on CaCo2 and J774 cells by MTT (3-4,5 dimethyl thialzol2,5 diphenyl tetrazolium bromide) assay. All complexes were evaluated for their haemocompatibility by using haemolysis assay, oxidative stress by reactive oxygen species (ROS) assay and immunotoxicity by in vitro and in vivo cytokine generation assay. The potential of the uptake of complexes across CaCo2 cells was determined by flow cytometry and fluorescent microscopy. The underlying mechanism of transport of complexes was determined by TEER measurement, assessment of FITC-Dextran and insulin transport across CaCo2 cells. 15 Results NIL QPa2.5 APECs (except IL QPa2.5-DS) exhibited larger hydrodynamic sizes (228-468nm) than all other APECs, due to the presence of bulky quaternary ammonium moieties. QPa2.5 APECs exhibited lower insulin association efficiency (≤40%) than other APECs (≥55%) due to a competition between the polyanion and insulin for QPa2.5 leading to reduced association of insulin in the complexes. DS based APECs generally offered higher insulin association efficiency (≥75%) than PAA based APECs (≤55%) due to higher molecular weight (6-10kDa) of DS. In comparison to other complexes, Pa2.5 PECs and APECs were more stable at varying temperature, ionic strength and pH due to the presence of long palmitoyl alkyl chain (C16) which reduced the chain flexibility and provided stronger hydrophobic association. The cytotoxicity of polycations on CaCo2 and J774 cells is rated as PAH>Da10=Pa2.5>QPa2.5. The introduction of PAA in Pa2.5 and Da10 brought most significant improvement in IC50 i.e., 14 fold and 16 fold respectively on CaCo2 cells; 9.3 fold and 3.73 fold respectively on J774 cells. In comparison to other complexes, Da10 (8mgml-1) induced higher haemolytic activity (~37%) due to a higher hydrophobic load of 10 percent mole grafting of dansyl pendants. The entire range of APECs displayed ≤12% ROS generation by the CaCo2 cells. The degree of in vitro TNFα production (QPa2.5≥Da10≥Pa2.5=PAH) and in vitro IL-6 generation (QPa2.5≥Pa2.5=PAH≥Da10) by J774 cells established an inverse relationship of cytotoxicity with the cytokine generation. Similar to MTT data, the introduction of PAA in APECs brought more significant reduction in in vitro cytokine secretion than DS based APECs. Pa2.5-PAA brought the most significant reduction in both in vitro and in vivo cytokine generation. All the formulations were able to significantly reduce original TEER, however did not demonstrate appreciable paracellular permeation of a hydrophilic macromolecular tracer of paracellular transport i.e., FITC Dextran. The uptake study revealed internalisation of APECs predominantly by a transcellular route. Transcellular uptake of IL QPa2.5 (≤73%), IL QPa2.5-DS (67%) was higher than their NIL counterparts, whereas the uptake of NIL Pa2.5 (≤89%), NIL Pa2.5-PAA (42%) was higher than their IL counterparts. Conclusion In essence, amphiphilic APECs have shown polyanion dependent ability to reduce polycation associated toxicity and they are able to facilitate transcellular uptake of insulin across CaCo2 cells.

The present thesis provides a systematic investigation of coordination polymers of 3d, rare-earth (4f) and main group element (Bi) using both rigid aromatic, flexible aliphatic linkers. Luminescent sensing behavior towards nitro aromatics, metal ions and ferroelectric behavior have been investigated using some of the prepared compounds. The possible usefulness of lone pair on the structure has been investigated using bismuth based coordination polymers. The thermal and optical behavior of lanthanide coordination polymers (Ce, Pr and Nd) have also been studied. Chapter 1 An Overview of Coordination Polymer (CP) Compounds This chapter presents a brief introduction to coordination polymer (CP) compounds. Starting from the brief historical background on coordination compounds, this chapter shed light on some earlier developments in this family of compounds by Yaghi, Robson and others. The usefulness of carboxylate and imidazolates in construction of some important coordination polymer compounds like MOF-5, HKUST-1, ZIFs, MIL-53, UiO-66, CD-MOF-1 etc has been described in detail along with its properties. The coordination polymers exhibit many important properties and some of the properties like sorption, separation, ionic conductivity, catalysis and ferroelectricity have been discussed briefly and summerized. Chapter 1 also provides the general synthetic and characterization approaches that have been employed during the present studies. Chapter 2 Part A: Adenine Based Coordination Polymers with Cyclohexane dicarboxylic acids This chapter presents the synthesis, structure and properties of four new coordination polymers [Zn4(C8H10O4)2.5(C5H4N5)3.2H2O].7H2O.2DMA (I), [Cd3(C8H10O4)2(C5H4N5)2.H2O] (II), [Cd(C8H11O4)2(C5H5N5)2.2H2O] (III), [Cd(C8H10O4)(C7H8N5O).H2O]. 4H2O (IV), (CHDA = cyclohexane dicarboxylic acid, ad = adenine, DMA = dimethylacetamide, 9-HEA = 9-hydroxyethyl adenine). The compound I and II forms three-dimensional structure having distinct arrangements of 1,4-CHDA and adenine units with Zn and Cd metals respectively. The molecular complex unit is observed in compound III with 1,2-CHDA and adenine. Compound IV forms two-dimensional structure with 9-HEA and 1,2-CHDA. The observation of base-pairing interactions in the above compounds is noteworthy. In compounds I, II and IV amino groups are appears to be free and utilized for the detection of nitro aromatic explosives through fluorescence quenching. The results revealed that the emission behavior of the present compounds is greatly influenced by the hydroxyl nitroaromatic analyses like indophenol, dinitrophenyl and trinitrophenols with very low detection limits. The compound I also exhibits considerable sensitivity towards metal ion detection, especially Fe2+/Fe3+, Cr3+, Ag+ and Hg2+ ions in solution. The presence of free nitrogen sites in compound II has been explored for the base catalyzed Knoevenagel condensation reaction, the quantitative yields are observed with various aldehyde substrates. Part B: Adenine Based Coordination Polymer with Oxydiacetic acid: [Cd2(C4H4O5)2(C5H5N5)].H2O.DMA The synthesis, structure and properties of a Cd based coordination polymer with oxydiacetic acid and adenine, [Cd2(C4H4O5)2(C5H5N5)].H2O. DMA is described. The compound has a two-dimensional structure formed by the connectivity involving Cd and oxydiacetic acid. The adenine ligand binds with the Cd metal center through the pyrimidine nitrogen and hangs in the inter layer spaces. The layers are stacked in a ABAB.... fashion and the inter layer spaces occupied by the dimethyl amine and water molecules. The water molecules are very labile and its removal can be accomplished by heating the sample at 100°C, which is also confirmed by the single crystal XRD, PXRD and IR studies. The availability of free amino groups of adenine molecule has been utilized for the detection of nitroaromatics, especially nitrophenols with good sensitivity. The amino group was also found to be useful in catalyzing Knoevenagel condensation reactions. Chapter 3: Rare-Earth Metal Carboxylates: Ln2(µ3-OH)(C4H4O5)2(C4H2O4)].2H2O [Ln=Ce, Pr and Nd] This chapter describes synthesis, structure and properties of series of rare-earth based compounds, [Ln2(µ3-OH)(C4H4O5)2(C4H2O4)].2H2O (Ln = Ce, Pr and Nd). The malic acid and fumaric acid form part of the structure. The lanthanide centers are connected by the malate units to form a two dimensional layers, which are pillared by fumarate units forming the three-dimensional structure. Overall, structure can be described as I2O1 type inorganic in two-dimension (Ln-O-Ln layers) and organic in one dimension. The extra framework water molecules form a dimer and occupy the channels. The robustness of the framework was reflected in terms of facile removal and reinsertion of the water molecules, which is also confirmed by single crystal XRD, variable temperature IR and cyclic TGA study. The presence of water dimers and weakly interacting water chain suggested the possibility of proton migration in these compounds. Proton conductivity studies reveal the conductivity values of ~2.85 x 10-6 Ω-1cm-1 at 98% relative humidity. The optical studies revealed an up-conversion behavior involving more than one photon for the neodymium compound. Chapter 4: Bismuth Carboxylates with Brucite and Fluorite Related Structures The synthesis, structure and properties of three new bismuth based coordination polymers have been described in this chapter. The compounds [C4N2H10][Bi(C7H4NO4)(C7H3NO4)].H2O (I), [Bi(C5H3N2O4) (C5H2N2O4)] (II) and [Bi(µ2-OH)(C7H3NO4)] (III) were isolated employing hydrothermal condition with three different heterocyclicdicarboxylic acids, 3,6-pyridinedicarboxylic acid, 4,5-imidazoledicarboxylic acid and 3,4-pyridinedicarboxylic acid respectively. The structures of all the compounds have linkages between Bi2O2 and the corresponding dicarboxylate forming a simple molecular unit in I, a bilayer arrangement in II and a three-dimensional extended structure in III. The topological arrangement of the nodal building units in the structures resembles brucite related layers in II and fluorite related arrangement in compound III. By utilizing the secondary interactions, the structure of III can be correlated to a Kagome related net. The observation of such classical inorganic related structures in the bismuth carboxylates is noteworthy. Heterogeneous catalytic studies indicate Lewis acidic nature in the bismuth center in all three compounds. Chapter 5: Solvent dependent Delamination, Restacking and Ferroelectric studies in a Two-Dimensional Compound [NH4][Ag3(C9H5NO4S)2(C13H14N2)2].8H2O This chapter describes synthesis, structure, water dependent delamination/restacking and ferroelectric behavior in a layered coordination polymer compound, [NH4][Ag3(C9H5NO4S)2(C13H14N2)2].8H2O. The compound has a two-dimensional structure with the water molecules occupying the inter-lamellar spaces. The lattice water molecules can be fully removed and reinserted, which accompany the crystalline-amorphous-crystalline transformation. This transformation resembles the collapse/delamination and re-stacking of the layers. This transformation has also been investigated by in-situ IR and PXRD studies. The presence of a natural dipole (anionic framework and cationic ammonium ions) along with the non-centrosymmetric space group gives rise to a room-temperature ferroelectric behavior to the compound with saturation polarization (Ps) of 1.95 μC/cm2 and remnant polarization of 0.63 μC/cm2. The temperature dependent dielectric measurements indicate that the ferroelectric-paraelectric transformation occurs at 320 K. The ferroelectric-paraelectric transformation also follows the crystalline-amorphous-crystalline transitions.