Nonlinear Optical Properties of Organic and Polymer Systems

Present thesis has discussed the design and synthesis of polymers suitable for nonlinear optics. Most of the molecules that were studied have shown good nonlinear optical activity. The second order nonlinear optical activity of the polymers was measured experimentally by Kurtz and Perry powder technique. The thesis comprises of eight chapters.The theory of NLO phenomenon and a review about the various nonlinear optical polymers has been discussed in chapter 1. The review has provided a survey of NLO active polymeric materials with a general introduction, which included the principles and the origin of nonlinear optics, and has given emphasis to polymeric materials for nonlinear optics, including guest-host systems, side chain polymers, main chain polymers, crosslinked polymers, chiral polymers etc.Chapter 2 has discussed the stability of the metal incorporated tetrapyrrole molecules, porphyrin, chlorin and bacteriochlorin.Chapter 3 has provided the NLO properties of certain organic molecules by computational tools. The chapter is divided into four parts. The first part has described the nonlinear optical properties of chromophore (D-n-A) and bichromophore (D-n-A-A-n-D) systems, which were separated by methylene spacer, by making use of DPT and semiempirical calculations.Chapter 4: A series of polyurethanes was prepared from cardanol, a renewable resource and a waste of the cashew industry by previously designed bifunctional and multifunctional polymers using quantum theoretical approach.Chapter 5: A series of chiral polyurethanes with main chain bis azo diol groups in the polymer backbone was designed and NLO activity was predicted by ZlNDO/ CV methods.In Chapter 7, polyurethanes were first designed by computational methods and the NLO properties were predicted by correction vector method. The designed bifunctional and multifunctional polyurethanes were synthesized by varying the chiral-achiral diol compositions

Design and study of self-assembled functional organic and hybrid systems for biological applications

The focus of self-assembly as a strategy for the synthesis has been confined largely to molecules, because of the importance of manipulating the structure of matter at the molecular scale. We have investigated the influence of temperature and pH, in addition to the concentration of the capping agent used for the formation of the nano-bio conjugates. For example, the formation of the narrower size distribution of the nanoparticles was observed with the increase in the concentration of the protein, which supports the fact that γ-globulin acts both as a controller of nucleation as well as stabiliser. As analyzed through various photophysical, biophysical and microscopic techniques such as TEM, AFM, C-AFM, SEM, DLS, OPM, CD and FTIR, we observed that the initial photoactivation of γ-globulin at pH 12 for 3 h resulted in small protein fibres of ca. Further irradiation for 24 h, led to the formation of selfassembled long fibres of the protein of ca. 5-6 nm and observation of surface plasmon resonance band at around 520 nm with the concomitant quenching of luminescence intensity at 680 nm. The observation of light triggered self-assembly of the protein and its effect on controlling the fate of the anchored nanoparticles can be compared with the naturally occurring process such as photomorphogenesis.Furthermore,our approach offers a way to understand the role played by the self-assembly of the protein in ordering and knock out of the metal nanoparticles and also in the design of nano-biohybrid materials for medicinal and optoelectronic applications. Investigation of the potential applications of NIR absorbing and water soluble squaraine dyes 1-3 for protein labeling and anti-amyloid agents forms the subject matter of the third chapter of the thesis. The study of their interactions with various proteins revealed that 1-3 showed unique interactions towards serum albumins as well as lysozyme. 69%, 71% and 49% in the absorption spectra as well as significant quenching in the fluorescence intensity of the dyes 1-3, respectively. Half-reciprocal analysis of the absorption data and isothermal titration calorimetric (ITC) analysis of the titration experiments gave a 1:1 stoichiometry for the complexes formed between the lysozyme and squaraine dyes with association constants (Kass) in the range 104-105 M-1. We have determined the changes in the free energy (ΔG) for the complex formation and the values are found to be -30.78, -32.31 and -28.58 kJmol-1, respectively for the dyes 1, 2 and 3. Furthermore, we have observed a strong induced CD (ICD) signal corresponding to the squaraine chromophore in the case of the halogenated squaraine dyes 2 and 3 at 636 and 637 nm confirming the complex formation in these cases. To understand the nature of interaction of the squaraine dyes 1-3 with lysozyme, we have investigated the interaction of dyes 1-3 with different amino acids. These results indicated that the dyes 1-3 showed significant interactions with cysteine and glutamic acid which are present in the side chains of lysozyme. In addition the temperature dependent studies have revealed that the interaction of the dye and the lysozyme are irreversible. Furthermore, we have investigated the interactions of these NIR dyes 1-3 with β- amyloid fibres derived from lysozyme to evaluate their potential as inhibitors of this biologically important protein aggregation. These β-amyloid fibrils were insoluble protein aggregates that have been associated with a range of neurodegenerative diseases, including Huntington, Alzheimer’s, Parkinson’s, and Creutzfeldt-Jakob diseases. We have synthesized amyloid fibres from lysozyme through its incubation in acidic solution below pH 4 and by allowing to form amyloid fibres at elevated temperature. To quantify the binding affinities of the squaraine dyes 1-3 with β-amyloids, we have carried out the isothermal titration calorimetric (ITC) measurements. The association constants were determined and are found to be 1.2 × 105, 3.6× 105 and 3.2 × 105 M-1 for the dyes, 1-3, respectively. To gain more insights into the amyloid inhibiting nature of the squaraine dyes under investigations, we have carried out thioflavin assay, CD, isothermal titration calorimetry and microscopic analysis. The addition of the dyes 1-3 (5μM) led to the complete quenching in the apparent thioflavin fluorescence, thereby indicating the destabilization of β-amyloid fibres in the presence of the squaraine dyes. Further, the inhibition of the amyloid fibres by the squaraine dyes 1-3, has been evidenced though the DLS, TEM AFM and SAED, wherein we observed the complete destabilization of the amyloid fibre and transformation of the fibre into spherical particles of ca. These results demonstrate the fact that the squaraine dyes 1-3 can act as protein labeling agents as well as the inhibitors of the protein amyloidogenesis. The last chapter of the thesis describes the synthesis and investigation of selfassembly as well as bio-imaging aspects of a few novel tetraphenylethene conjugates 4-6.Expectedly, these conjugates showed significant solvatochromism and exhibited a hypsochromic shift (negative solvatochromism) as the solvent polarity increased, and these observations were justified though theoretical studies employing the B3LYP/6-31g method. We have investigated the self-assembly properties of these D-A conjugates though variation in the percentage of water in acetonitrile solution due to the formation of nanoaggregates. Further the contour map of the observed fluorescence intensity as a function of the fluorescence excitation and emission wavelength confirmed the formation of J-type aggregates in these cases. To have a better understanding of the type of self-assemblies formed from the TPE conjugates 4-6, we have carried out the morphological analysis through various microscopic techniques such as DLS, SEM and TEM. 70%, we observed rod shape architectures having ~ 780 nm in diameter and ~ 12 μM in length as evidenced through TEM and SEM analysis. We have made similar observations with the dodecyl conjugate 5 at ca. 70% and 50% water/acetonitrile mixtures, the aggregates formed from 4 and 5 were found to be highly crystalline and such structures were transformed to amorphous nature as the water fraction was increased to 99%. To evaluate the potential of the conjugate as bio-imaging agents, we have carried out their in vitro cytotoxicity and cellular uptake studies though MTT assay, flow cytometric and confocal laser scanning microscopic techniques. Thus nanoparticle of these conjugates which exhibited efficient emission, large stoke shift, good stability, biocompatibility and excellent cellular imaging properties can have potential applications for tracking cells as well as in cell-based therapies. In summary we have synthesized novel functional organic chromophores and have studied systematic investigation of self-assembly of these synthetic and biological building blocks under a variety of conditions. The investigation of interaction of water soluble NIR squaraine dyes with lysozyme indicates that these dyes can act as the protein labeling agents and the efficiency of inhibition of β-amyloid indicate, thereby their potential as anti-amyloid agents.

Statistical thermodynamics of polydisperse polymer systems in the framework of lattice fluid model: Effect of molecular weight and its distribution on the spinodal in polymer solution

With the aid of thermodynamics of Gibbs, the expression of the spinodal was derived for the polydisperse polymer-solvent system in the framework of Sanchez-Lacombe Lattice Fluid Theory (SLLFT). For convenience, we considered that a model polydisperse polymer contains three sub-components. According to our calculation, the spinodal depends on both weight-average ((M) over bar (w)) and number-average ((M) over bar (n)) molecular weights of the polydisperse polymer, but the z-average molecular weight ((M) over bar (z)) dependence on the spinodal is invisible. The dependence of free volume on composition, temperature, molecular weight, and its distribution results in the effect of (M) over bar (n) on the spinodal. Moreover, it has been found that the effect of changing (M) over bar (w) on the spinodal is much bigger than that of changing (M) over bar (n) and the extrema of the spinodal increases with the rise of the weight-average molecular weight of the polymer in the solutions with upper critical solution temperature (UCST). However, the effect of polydispersity on the spinodal can be neglected for the polymer with a considerably high weight-average molecular weight. A more simple expression of the spinodal for the polydisperse polymer solution in the framework of SLLFT was also derived under the assumption of upsilon(*)=upsilon(1)(*)=upsilon(2)(*) and (1/r(1)(0))-(1/r(2i)(0))-->(1/r(1)(0)).

Ring-chain interconversion in high-performance polymer systems. 3. Cyclodepolymerization of poly(m-phenylene isophthalamide) (Nomex) and entropically driven ring-opening polymerization of the macrocyclic oligomers so produced

A homologous series of macrocyclic oligoamides has been prepared in high yield by reaction of isophthaloyl chloride with m-phenylenediamine under pseudo-high-dilution conditions. The products were characterized by infrared and H-1 NMR spectroscopies, matrix assisted laser desorption-ionization time-of-flight mass spectrometry, and gel permeation chromatography (GPC). A series of linear oligomers was prepared for comparison. The macrocycles ranged in size from the cyclic trimer up to at least the cyclic nonamer (90 ring atoms). The same homologous series of macrocyclic oligomers was prepared in high yield by the cyclodepolymerization of poly(m-phenylene isophthalamide) (Nomex). Cyclodepolymerization was best achieved by treating a 1% w/v solution of the polymer in dimethyl sulfoxide containing calcium chloride or lithium chloride with 3-4 mol % of sodium hydride or the sodium salt of benzanilide at 150 degreesC for 70 h. Treatment of a concentrated solution of the macrocyclic oligomers (25% w/v) with 4 mol % of sodium hydride or the sodium salt of benzanilide in a solution of lithium chloride in dimethyl sulfoxide at 170 degreesC for 6 h resulted in efficient entropically driven ring-opening polymerizations to give poly(m-phenylene isophthalamide), characterized by infrared and H-1 NMR spectroscopies and by GPC. The molecular weights obtained were comparable with those of the commercial polymer.

Orientational behaviour of thermotropic and lyotropic liquid crystal polymer systems under shear flow

A comparison is made of the development of global orientation during shearing of lyotropic solutions of hydroxypropylcellulose with that observed for the thermotropic phase of hydroxypropylcellulose. At shear rates the behaviour of the two systems is similar, both during steady-state shear, and in terms of relaxation following cessation of shear flow. At low shear rates, the levels of orientation observed for the thermotropic system are substantially greater than observed for the lyotropic solutions. The relationship of these differences to variations in molecular parameters, viscous stress and to director tumbling is discussed.

Fat and fatty acid composition of cooked meat from UK retail chickens labelled as from organic and non-organic production systems

This study compared fat and fatty acids in cooked retail chicken meat from conventional and organic systems. Fat contents were 1.7, 5.2, 7.1 and 12.9 g/100 g cooked weight in skinless breast, breast with skin, skinless leg and leg with skin respectively, with organic meat containing less fat overall (P < 0.01). Meat was rich in cis-monounsaturated fatty acids, although organic meat contained less than did conventional meat (1850 vs. 2538 mg/100 g; P < 0.001). Organic meat was also lower (P < 0.001) in 18:3 n−3 (115 vs. 180 mg/100 g) and, whilst it contained more (P < 0.001) docosahexaenoic acid (30.9 vs. 13.7 mg/100 g), this was due to the large effect of one supermarket. This system by supermarket interaction suggests that poultry meat labelled as organic is not a guarantee of higher long chain n−3 fatty acids. Overall there were few major differences in fatty acid contents/profiles between organic and conventional meat that were consistent across all supermarkets.

Comparative analysis of performance and stability among composite cross populations, variety mixtures and pure lines of winter wheat in organic and conventional cropping systems

This study investigated the effects of increased genetic diversity in winter wheat (Triticum aestivum L.), either from hybridization across genotypes or from physical mixing of lines, on grain yield, grain quality, and yield stability in different cropping environments. Sets of pure lines (no diversity), chosen for high yielding ability or high quality, were compared with line mixtures (intermediate level of diversity), and lines crossed with each other in composite cross populations (CCPn, high diversity). Additional populations containing male sterility genes (CCPms) to increase outcrossing rates were also tested. Grain yield, grain protein content, and protein yield were measured at four sites (two organically-managed and two conventionally-managed) over three years, using seed harvested locally in each preceding year. CCPn and mixtures out-yielded the mean of the parents by 2.4% and 3.6%, respectively. These yield differences were consistent across genetic backgrounds but partly inconsistent across cropping environments and years. Yield stability measured by environmental variance was higher in CCPn and CCPms than the mean of the parents. An index of yield reliability tended to be higher in CCPn, CCPms and mixtures than the mean of the parents. Lin and Binns’ superiority values of yield and protein yield were consistently and significantly lower (i.e. better) in the CCPs than in the mean of the parents, but not different between CCPs and mixtures. However, CCPs showed greater early ground cover and plant height than mixtures. When compared with the (locally non-predictable) best-yielding pure line, CCPs and mixtures exhibited lower mean yield and somewhat lower yield reliability but comparable superiority values. Thus, establishing CCPs from smaller sets of high-performing parent lines might optimize their yielding ability. On the whole, the results demonstrate that using increased within-crop genetic diversity can produce wheat crops with improved yield stability and good yield reliability across variable and unpredictable cropping environments.

A comparative study of production performance and animal health practices in organic and conventional dairy systems

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Core-shell macromolecules with dendritic polyphenylene core and polymer shells

Core-shell macromolecules with dendritic polyphenylene core and polymer shell Zusammenfassung / Abstract Core-shell macromolecular structures have become of great interest in materials science because they gave an opportunity to combine a large variety of chemical and physical properties in the single molecule, by combination of different (in terms of chemistry and physics) cores and shells. The interest in such complex structures was provoked by their potential applications in the coating and painting industry (latexes), as supports for catalysts in polymer industry, or as nano-containers and transporters for genes or drug delivery. The aim of this study was the synthesis, characterization and further application of core-shell macromolecules possessing a hydrophobic stiff core (polyphenylene dendrimers) surrounded with a hydrophilic, soft, covalently bonded polymer shell (poly(ethylene oxide) and its copolymers). The requirements for such complex substances were that they should be well-defined in terms of molecular weight (narrow molecular weight distribution) and in molecular structure. The preparation of core-shell molecules containing dendrimer as a core was possible via two synthetic routs: “grafting-onto” and “grafting-from”. The resulting core-shell macromolecules possessed narrow polydispersity as guaranteed by the excellent structural and functional definition of the dendrimer and the narrow polydispersity of the PEO, PS-b-PEO and PI-b-PEO attached to the dendrimer surface. Additional investigation of the size of the particles indicated a relation between both the length and the number of the polymer chains and the hydrodynamic radius determined by Dynamic Light Scattering and Fluorescent Correlation Spectroscopy. Core-shell nano-particles were applied as metallocene supports in heterogeneous olefin polymerizations. Our results indicate that such catalyst systems, that have a size of at least one order of magnitude smaller than the used by now organic supports, could be very useful as model compounds for investigations on catalyst fragmentation and its influence on the product parameters.