CENTRIFUGE AND NUMERICAL MODELLING OF SOFT CLAY-PILE-RAFT FOUNDATIONS SUBJECTED TO SEISMIC SHAKING

Ph.DDOCTOR OF PHILOSOPH

Helimeric porphyrinoids: Stereostructure and chiral resolution of meso -tetraarylmorpholinochlorins

The synthesis and chiral resolution of free-base and Ni(II) complexes of a number of derivatives of meso-tetraphenylmorpholinochlorins, with and without direct β-carbon-to-o-phenyl linkages to the flanking phenyl groups, is described. The morpholinochlorins, a class of stable chlorin analogues, were synthesized in two to three steps from meso-tetraphenylporphyrin. The conformations and the relative stereostructures of a variety of free-base and Ni(II) complexes of these morpholinochlorins were elucidated by X-ray diffractometry. Steric and stereoelectronic arguments explain the relative stereoarray of the morpholino-substituents, which differ in the free-base and Ni(II) complexes, and in the monoalkoxy, β-carbon-to-o-phenyl linked morpholinochlorins, and the dialkoxy derivatives. The Ni(II) complexes were all found to be severely ruffled whereas the free-base chromophores are more planar. As a result of the helimeric distortion of their porphyrinoid chromophores, the ruffled macrocycles possess a stable inherent element of chirality. Most significantly, resolution of the racemic mixtures was achieved, both by classical methods via diastereomers and by HPLC on a chiral phase. Full CD spectra were recorded and modeled using quantum-chemical computational methods, permitting, for the first time, an assignment of the absolute configurations of the chromophores. The report expands the range of known pyrrole-modified porphyrins. Beyond this, it introduces large chiral porphyrinoid π-systems that exist in the form of two enantiomeric, stereochemically stable helimers that can be resolved. This forms the basis for possible future applications, for example, in molecular-recognition systems or in materials with chiroptic properties. © 2011 American Chemical Society

Porphyrin N-Oxidations and beta,beta\u27-Bond Modifications

This thesis begins with an introduction to porphyrins and chlorins, their natural and synthetic analogues, the biological roles of porphyrins, followed by the synthesis of porphyrins and their derivatization towards chlorins. The introduction also deals with the structural analysis of porphyrins and a classification of their optical spectra, followed by a brief outline of the applications of porphyrins and chlorins. Subsequently, there is a discussion on the various types of porphyrins present with substitution in the porphyrin core as well as in the periphery. The structure, synthesis and spectroscopic properties of core substituted and peripherally modified porphyrins are also discussed.^ A detailed description of porphyrin and chlorin N-oxides is carried out in the Results and Discussion Chapter 1, describing their synthesis, reactivity, crystal structure and a comparison of their optical spectra. A possible biological application is outlined.^ An exploration of the reactivity of the porphyrin α-position and synthesis of a pyrrole-ring contracted chlorin is discussed in Chapter 2. ^ In Results and Discussion Chapter 3, the synthesis, spectroscopy and stereochemical assignment of helimeric porphyrinoids with a morpholino subunit are discussed.^ In Results and Discussion Chapter 4, the synthesis of trans-diolchlorins and their manipulation leading up to the synthesis of pyrrole ring homologated porphyrins is discussed.

Spectroscopic and viscometric determination of DNA-binding modes of some bioactive dibenzodioxins and phenazines

Push-pull dibenzodioxins and phenazines having ‘anthracene-like’ planar structures and good charge transfer character had been previously synthesised in our laboratory. The dibenzodioxins had earlier proven their anti-proliferative nature against HeLa tumor cell lines. Since phenazines are structural analogues of the former, these molecules were evaluated in course of the current study for their cytotoxic action against HeLa cell lines and they exhibited strong anti-tumor activity. This behavior could be related to their good DNA binding property. The DNA binding modes of molecules 1–4 (Fig. 1) were evaluated using various experimental techniques and they interacted with DNA in a non-covalently by both intercalative as well as groove binding mechanisms. Molecule 1 follows predominantly intercalative binding mode whereas molecules 2 and 3 have nearly equal and opposite preferences for both groove binding and intercalative modes. For molecule 4, groove binding is preferred mode of binding to DNA. A rationale for such differential binding behaviour is provided based on the subtle structural differences in our synthesised dibenzodioxins and phenazines. Elucidation of the mode of a molecule-DNA-binding event is relevant for understanding the mechanism of action of these molecules and will help promote further research into designing better DNA targeting small molecules. Keywords: Intercalation, Minor groove binding, Dibenzodioxins, Phenazines, Push-pul

Carbon dioxide capture by metal organic frameworks

1223-1230The design and synthesis of functionalized metal organic framework  materials (MOFs) for reversible physisorption of CO2 is discussed. This strategy of CO2 adsorption in MOFs requires less energy for regeneration than materials relying on chemisorption. As a result the MOFs have received considerable attention as sorbent materials for strategic gases such as CO2 and H2. <span style="font-size:9.0pt;mso-bidi-font-size:10.0pt; mso-ansi-language:EN-US" lang="EN-US">In this review, we have discussed different MOFs and hybrid materials containing MOFs which can adsorb CO2 at room temperature.<span style="font-size:9.0pt;mso-bidi-font-size: 10.0pt" lang="EN-GB"> In order to achieve high adsorption capacity, fast CO2 adsorption-desorption and low energy requirement for regeneration are necessary. Several avenues for increasing the CO2 adsorption capacity of such materials, for instance, introduction of open metal sites and the use of ligand molecules with specific functionalities (like -OH or -NH2) have been described. <span style="font-size: 9.0pt;mso-bidi-font-size:10.0pt;mso-ansi-language:EN-US" lang="EN-US">It has been observed that CO2 loading capacity of MOFs increases with functionalization. Herein, we have discussed how N-containing and fluorinated MOFs are designed to achieve higher CO2 loading than their non-functionalized counterparts. Nanocarbons (e.g. carbon nanotubes, carbon nanofibres, etc.) are porous materials and a blend of these porous materials with porous MOFs or porous carbon derived from MOFs may act as a better adsorbate than even the pure materials. Enhancement of CO2 loading by nanocarbon-MOF hybrid material is also discussed. </span

Solitary intracavitory cardiac metastasis

Metastatic cardiac tumors are more common than the primary ones and they most commonly involve the pericardium or myocardium. Very rarely they may show partial or total intracavitory growth. Ours is one such case of solitary intracavitory cardiac metastasis in a patient with adenocarcinoma of the right lung who presented with hemoptysis and palpitation. Echocardiography and histopathological study clinched the diagnosis

Suitable Waves for Bender Element Tests: Interpretations, Errors and Modelling Aspects

Extensive research on bender element tests has been carried out by many researchers, but precise guidelines for carrying out such tests have not yet been established. It is often recommended that, when using a particular bender element test for the first time on a particular soil to determine its small strain dynamic properties, several methods should be tried and the results compared in order to improve confidence in the results obtained. Demonstrated use of relatively easy analytical models for investigating different scenarios of bender element testing is another aspect that should be further looked into. This paper presents laboratory experiments and dynamic finite element analyses to determine a suitable wave for use in bender element tests in the laboratory to measure small strain shear stiffness (Gmax). The suitability of a distorted sine wave over a continuous sine wave for tests is observed from laboratory experiments and dynamic finite element analyses. The use of simple finite element models for assessing a number of aspects in relation to bender element testing is demonstrated.Department of Civil Engineering, University of Dublin, Trinity CollegeNishimatsu Construction Co., LtdThe Geotechnical Trust Fund of the Institution of Engineers of Irelan

Anti-Infective Metabolites of a Newly Isolated KL1 Associated with Kalmegh ( Nees.), a Traditional Medicinal Herb

This study was conducted to isolate endophytic bacteria possessing anti-infective property from Kalmegh ( Andrographis paniculata Nees.), a well-known medicinal plant. A total of 23 strains were isolated from this plant among which the strain KL1, isolated from surface-sterilized leaf of this medicinal herb, showed broad-spectrum antagonism against an array of Gram-positive and -negative bacterial pathogens. Ethyl acetate extract of KL1-fermented media yielded a greenish amorphous substance retaining anti-infective property. Solvent-extracted crude material was separated by thin-layer chromatography, and the active ingredient was located by autobiogram analysis. The purified anti-infective compound was found as anthracene derivative as analyzed by ultraviolet and Fourier transform infrared spectroscopy. The strain was identified as Bacillus thuringiensis KL1 from cultural, physiochemical, and molecular aspects. The above results indicate the pharmaceutical potential of the candidate isolate

Proton-conducting supramolecular metallogels from the lowest molecular weight assembler ligand: A quote for simplicity

Oxalic acid has been proven to be the lowest molecular weight organic ligand able to form robust supramolecular metallogel networks in the presence of metal salts. In particular, two novel multifunctional metallogels were readily prepared at room temperature by simple mixing of stock solutions of Cu II acetate monohydrate or CuII perchlorate hexahydrate and oxalic acid dihydrate. Formation of different polymorphs and unprecedented proton conduction under anhydrous conditions were also demonstrated with some of these materials.S.S. acknowledges CSIR, New Delhi, India, for SRF. R.B. acknowledges CSIR, DST, and BRNS for funding. D.D.D. acknowledges CSIC (project PIE 200980I059) and the University of Regensburg (Anschubfinanzierung von Wissenschaftlichen Projekten-2011) for funding. C.C. acknowledges CC Ministerio de Ciencia e Innovación—FEDER (project CTQ2010–17436) for funding.Peer Reviewe