11 resultados para NONCOVALENT SIDEWALL-FUNCTIONALIZATION
em Cochin University of Science
Resumo:
Vacuum-ultraviolet (VUV) irradiation (kexc: 172 ± 12 nm) of polystyrene films in the presence of oxygen produced not only oxidatively functionalized surfaces, but generated also morphological changes. Whereas OH- and C=O-functionalized surfaces might be used for e.g. secondary functionalization, enhanced aggregation or printing, processes leading to morphological changes open new possibilities of microstructurization. Series of experiments made under different experimental conditions brought evidence of two different reaction pathways: introduction of OH- and C=O-groups at the polystyrene pathways is mainly due to the reaction of reactive oxygen species (hydroxyl radicals, atomic oxygen, ozone) produced in the gas phase between the VUV-radiation source and the substrate. However, oxidative fragmentation leading to morphological changes, oxidation products of low molecular weight and eventually to mineralization of the organic substrate is initiated by electronic excitation of the polymer leading to C–C-bond homolysis and to a complex oxidation manifold after trapping of the C-centred radicals by molecular oxygen. The pathways of oxidative functionalization or fragmentation could be differentiated by FTIR-ATR analysis of irradiated polystyrene surfaces before and after washing with acetonitrile and microscopic fluorescence analysis of the surfaces secondarily functionalized with the N,N,N-tridodecyl-triaza-triangulenium (TATA) cation. Ozonization of the polystyrene leads to oxidative functionalization of the polymer surface but cannot initiate the fragmentation of the polymer backbone. Oxidative fragmentation is initiated by electronic excitation of the polymer (contact-mode AFM analysis), and evidence of the generation of intermediate C-centred radicals is given e.g. by experiments in the absence of oxygen leading to cross-linking (solubility effects, optical microscopy, friction-mode AFM) and disproportionation (fluorescence).
Resumo:
A systematic investigation of the reactivity and functionalization of two heterocyclic analogs of triphenylmethane , namely tris(2-thienyl)methane and tris(2-furyl)methane have been carried out and the results are presented in this thesis entitled "NOVEL REACTIONS OF TRIS(2-THIENYL)METHANE AND TRIS(2-FURYL)METHANE.". The history of organic free radicals dates back to Gomberg's monumental discovery of the triphenylmethyl radical in 1900. The heterocyclic analogs of triarylmethane are also interesting from the vantage point of their transformation to the corresponding radicals akin to Gomberg ' s triphenylmethyl radical and also they are prone to further transformation leading to three dimensionally elongated molecules such as dendrimers. Dendritic architectures are one of the most pervasive topologies observed in nature at the macro- and microdimensional length devices. Because of their ability to combine both organic and inorganic compounds and their propensity to either encapsulate or be engineered into unimolecular functional devices , dendrimers are versatile amongst existing nanoscale building blocks and materials.
Resumo:
The main objective of the present study is to have a detailed investigation on the gelation properties, morphology and optical properties of small π-conjugated oligomers. For this purpose we have chosen oligo(p-phenylenevinylene)s (OPVs), a class of molecules which have received considerable attention due to their unique optical and electronic properties. Though a large number of reports are available in the literature on the self-assembly properties of tailor made OPVs, none of them pertain to the design of nanostructures based on organogels. In view of this, we aimed at the creation of functional chromophoric assemblies of π-conjugated OPVs through the formation of organogels, with the objective of crafting nanoscopic assemblies of different size and shape thereby modulating their optical and electronic properties.In order to fulfill the above objectives, the design and synthesis of a variety of OPVs with appropriate structural variations were planned. The design principle involves the derivatization of OPVs with weak H-bonding hydroxymethyl end groups and with long aliphatic hydrocarbon side chains. The noncovalent interactions in these molecules were expected to lead the formation of supramolecular assembly and gels in hydrocarbon solvents. In such an event, detailed study of gelation and extensive analysis of the morphology of the gel structures were planned using advanced microscopic techniques. Since OPVs are strongly fluorescent molecules, gelation is expected to perturb the optical properties. Therefore, detailed study on the gelation induced optical properties as a way to probe the nature and stability of the selfassembly was planned. Apart from this, the potential use of the modulation of the optical properties for the purpose of light harvesting was aimed. The approach to this problem was to entrap an appropriate energy trap to the OPV gel matrix which may lead to the efficient energy transfer from the OPV gel based donor to the entrapped acceptor. The final question that we wanted to address in this investigation was the creation of helical nanostructures through proper modification of the OPV backbone With chiral handles.The present thesis is a detailed and systematic approach to the realization of the above objectives which are presented in different chapters of the thesis.
Resumo:
Biodegradable polymers have opened an emerging area of great interest because they are the ultimate solution for the disposal problems of synthetic polymers used for short time applications in the environmental and biomedical field. The biodegradable polymers available until recently have a number of limitations in terms of strength and dimensional stability. Most of them have processing problems and are also very expensive. Recent developments in biodegradable polymers show that monomers and polymers obtained from renewable resources are important owing to their inherent biodegradability, biocompatibility and easy availability. The present study is, therefore, mostly concemed with the utilization of renewable resources by effecting chemical modification/copolymerization on existing synthetic polymers/natural polymers for introducing better biodegradability and material properties.The thesis describes multiple approaches in the design of new biodegradable polymers: (1) Chemical modification of an existing nonbiodegradable polymer, polyethylene, by anchoring monosaccharides after functionalization to introduce biodegradability. (2) Copolymerization of an existing biodegradable polymer, polylactide, with suitable monomers and/or polymers to tailor their properties to suit the emerging requirements such as (2a) graft copolymerization of lactide onto chitosan to get controlled solvation and biodegradability and (2b) copolymerization of polylactide with cycloaliphatic amide segments to improve upon the thermal properties and processability.
Resumo:
Most of the procedures reported for the synthesis of metal nanoparticles involve the use of strong reducing agents or elevated temperatures. This limits the possibility of developing metal nanoparticle based sensors for the in situ detection of analytes. One of the objectives of the present investigations is to (i) develop newer methodologies for the synthesis of metal nanoparticles in aqueous medium at ambient conditions and (ii) their use in the detection of metal cations by taking advantage of the unique coordination ability. Ideally, biocompatible molecules which possess both the reducing and stabilizing groups are desirable for such applications. Formation of stable supramolecular assembly, by bringing metal nanoparticles close to each other, results in plasmon coupling and this strategy can be effectively utilized for the development of metal nanoparticle based sensors.Another objective of the present study is to understand the supramolecular organization of molecules on surfaces. Various noncovalent interactions between the molecules and with surface play a decisive role in their organizations. An in-depth understanding of these interactions is essential for device fabrications. Recent photophysical studies have revealed that phenyleneethynylene based molecular systems are ideal for device application. The second objective of the thesis focuses on understanding the (i) organization of phenyleneethynylenes on highly oriented pyrolytic graphite (HOPG) surface with atomic level precision and (ii) weak intermolecular interactions which drive their organization.
Resumo:
Supra molecular architectures of coordination complexes of liydrazones through non covalent interactions have been explored. Molecular self—assernbly driven by weak interactions such as hydrogen— bonding, K '”T[, C-1-I‘ "TE, van der Waals interactions, and so forth are currently of tremendous research interest in the fields of molecule based materials. The directional properties of the hydrogembonding interaction associate discrete molecules into aggregate structures that are sufficiently stable to be considered as independent chemical species. Chemistry can borrow nature’s strategy to utilize hydrogen-bonding as Well as other noncovalent interactions as found in secondary and tertiary structures of proteins such as the double helix folding of DNA, hydrophobic selflorganization of phospholipids in cell membrane etc. In supramolecular chemistry hydrogen bonding plays an important role in forming a variety of architectures. Thus, the wise modulation and tuning of the complementary sites responsible for hydrogen—bond formation have led to its application in supramolecular electronics, host-guest chemistry, self-assembly of molecular capsules, nanotubes etc. The work presented in this thesis describes the synthesis and characterization of metal complexes derived from some substituted aroylhydrazones. The thesis is divided into seven chapters.
Resumo:
Fluorescence is a powerful tool in biological research, the relevance of which relies greatly on the availability of sensitive and selective fluorescent probes. Nanometer sized fluorescent semiconductor materials have attracted considerable attention in recent years due to the high luminescence intensity, low photobleaching, large Stokes’ shift and high photochemical stability. The optical and spectroscopic features of nanoparticles make them very convincing alternatives to traditional fluorophores in a range of applications. Efficient surface capping agents make these nanocrystals bio-compatible. They can provide a novel platform on which many biomolecules such as DNA, RNA and proteins can be covalently linked. In the second phase of the present work, bio-compatible, fluorescent, manganese doped ZnS (ZnS:Mn) nanocrystals suitable for bioimaging applications have been developed and their cytocompatibility has been assessed. Functionalization of ZnS:Mn nanocrystals by safe materials results in considerable reduction of toxicity and allows conjugation with specific biomolecules. The highly fluorescent, bio-compatible and water- dispersible ZnS:Mn nanocrystals are found to be ideal fluorescent probes for biological labeling
Resumo:
Gelation provides a unique medium, which often induces organization of molecules resulting in the modulation of their optical, morphological and electronic properties thereby opening a new world of fascinating materials with interesting physical properties at nano- meso- and macroscopic levels. Supramolecular gels based on linear π-systems have attracted much attention due to their inherent optical and electronic properties which find application in organic electronics, light harvesting and sensing. They exhibit reversible properties due to the dynamic nature of noncovalent forces. As a result, studies on such soft materials are currently a topic of great interest. Recently, researchers are actively involved in the development of sensors and stimuli-responsive materials based on self-assembled π-systems, which are also called smart materials. The present thesis is divided into four chapters
Resumo:
Design and study of molecular receptors capable of mimicking natural processes has found applications in basic research as well as in the development of potentially useful technologies. Of the various receptors reported, the cyclophanes are known to encapsulate guest molecules in their cavity utilizing various non–covalent interactions resulting in significant changes in their optical properties. This unique property of the cyclophanes has been widely exploited for the development of selective and sensitive probes for a variety of guest molecules including complex biomolecules. Further, the incorporation of metal centres into these systems added new possibilities for designing receptors such as the metallocyclophanes and transition metal complexes, which can target a large variety of Lewis basic functional groups that act as selective synthetic receptors. The ligands that form complexes with the metal ions, and are capable of further binding to Lewis-basic substrates through open coordination sites present in various biomolecules are particularly important as biomolecular receptors. In this context, we synthesized a few anthracene and acridine based metal complexes and novel metallocyclophanes and have investigated their photophysical and biomolecular recognition properties.
Resumo:
Mesoporous silica nanoparticles provide a non-invasive and biocompatible delivery platform for a broad range of applications in therapeutics, pharmaceuticals and diagnosis. Additionally, mesoporous silica materials can be synthesized together with other nanomaterials to create new nanocomposites, opening up a wide variety of potential applications. The ready functionalization of silica materials makes them ideal candidates for bioapplications and catalysis. These properties of mesoporous silica like high surface areas, large pore volumes and ordered pore networks allow them for higher loading of drugs or biomolecules. Comparative studies have been made to evaluate the different procedures; much of the research to date has involved quick exploration of new methods and supports. Requirements for different enzymes may vary, and specific conditions may be needed for a particular application of an immobilized enzyme such as a highly rigid support. In this endeavor, mesoporous silica materials having different pore size were synthesized and easily modified with active functional groups and were evaluated for the immobilization of enzymes. In this work, Aspergillus niger glucoamylase, Bovine liver catalase, Candida rugosa lipase were immobilized onto support by adsorption and covalent binding. The structural properties of pure and immobilized supports are analyzed by various characterization techniques and are used for different reactions of industrial applications.
Resumo:
In this venture three distinct class of catalysts such as, pillared clays and transition metal loaded pillared clays , porous clay heterostructures and their transition metal loaded analogues and DTP supported on porous clay heterostructures etc. were prepared and characterized by various physico chemical methods. The catalytic activities of prepared catalysts were comparatively evaluated for the industrially important alkylation, acetalization and oxidation reactions.The general conclusions drawn from the present investigation are Zirconium, iron - aluminium pillared clays were synthesized by ion exchange method and zirconium-silicon porous heterostructures were Summary and conclusions 259 prepared by intergallery template method. Transition metals were loaded in PILCs and PCHs by wet impregnation method. Textural and acidic properties of the clays were modified by pillaring and post pillaring modifications. The shift in 2θ value to lower range and increase in d (001) spacing indicate the success of pillaring process. Surface area, pore volume, average pore size etc. increased dramatically as a result of pillaring process. Porous clay heterostructures have higher surface area, pore volume, average pore diameter and narrow pore size distribution than that of pillared clays. The IR spectrum of PILCs and PCHs are in accordance with literature without much variation compared to parent montmorillonite which indicate that basic clay structure is retained even after modification. The silicon NMR of PCHs materials have intense peaks corresponding to Q4 environment which indicate that mesoporous silica is incorporated between clay layers. Thermo gravimetric analysis showed that thermal stability is improved after the pillaring process. PCH materials have higher thermal stability than PILCs. In metal loaded pillared clays, up to 5% metal species were uniformly dispersed (with the exception of Ni) as evident from XRD and TPR analysis. Chapter 9 260 Impregnation of transition metals in PILCs and PCHs enhanced acidity of catalysts as evident from TPD of ammonia and cumene cracking reactions. For porous clay heterostructures the acidic sites have major contribution from weak and medium acid sites which can be related to the Bronsted sites as evident from TPD of ammonia. Pillared clays got more Lewis acidity than PCHs as inferred from α- methyl styrene selectivity in cumene cracking reaction. SEM images show that layer structure is preserved even after modification. Worm hole like morphology is observed in TEM image of PCHs materials In ZrSiPCHS, Zr exists as Zr 4+ and is incorporated to silica pillars in the intergallary of clay layers as evident from XPS analysis. In copper loaded zirconium pillared clays, copper exists as isolated species with +2 oxidation state at lower loading. At higher loading, Cu exists as clusters as evident from reduction peak at higher temperatures in TPR. In vanadium incorporated PILCs and PCHs, vanadium exist as isolated V5+ in tetrahedral coordination which is confirmed from TPR and UVVis DRS analysis. In cobalt loaded PCHs, cobalt exists as CoO with 2+ oxidation state as confirmed from XPS. Cerium incorporated iron aluminium pillared clay was found to be the best catalyst for the hydroxylation of phenol in aqueous media due to the additional surface area provided by ceria mesopores and its redox properties. Summary and conclusions 261 Cobalt loaded zirconium porous clay heterostructures were found to be promising catalyst for the tertiary butylation of phenol due to higher surface area and acidic properties. Copper loaded pillared clays were found to be good catalyst for the direct hydroxylation of benzene to phenol. Vanadium loaded PCHs catalysts were found to be efficient catalysts for oxidation of benzyl alcohol. DTP was firmly fixed on the mesoporous channels of PCHs by Direct method and functionalization method. DTP supported PCHs catalyst were found to be good catalyst for acetalization of cyclohexanone with more than 90% conversion.