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Molecular gas properties of a lensed star-forming galaxy at z ~ 3.6: a case studyDessauges-Zavadsky, M., Zamojski, M., Rujopakarn, W., Richard, J., Sklias, P., Schaerer, D., Combes, F., Ebeling, H., Rawle, T. D., Egami, E., Boone, F., Clément, B., Kneib, J.-P., Nyland, K., Walth, G. 14 September 2017 (has links)
We report on the galaxy MACSJ0032-arc at z(CO) = 3.6314 discovered during the Herschel Lensing snapshot Survey of massive galaxy clusters, and strongly lensed by the cluster MACSJ0032.1+1808. The successful detections of its rest-frame ultraviolet (UV), optical, far-infrared (FIR), millimeter, and radio continua, and of its CO emission enable us to characterize, for the first time at such a high redshift, the stellar, dust, and molecular gas properties of a compact star-forming galaxy with a size smaller than 2.5 kpc, a fairly low stellar mass of 4.8(-1.0)(+0.5) x 10(9) M circle dot, and a moderate IR luminosity of 4.8(-0.6)(+1.2) x 10(11) L circle dot. By combining the stretching effect of the lens with the high angular resolution imaging of the CO(10) line emission and the radio continuum at 5 GHz, we find that the bulk of the molecular gas mass and star formation seems to be spatially decoupled from the rest-frame UV emission. About 90% of the total star formation rate is undetected at rest-frame UV wavelengths because of severe obscuration by dust, but is seen through the thermal FIR dust emission and the radio synchrotron radiation. The observed CO(43) and CO(65) lines demonstrate that high-J transitions, at least up to J = 6, remain excited in this galaxy, whose CO spectral line energy distribution resembles that of high-redshift submm galaxies, even though the IR luminosity of MACSJ0032-arc is ten times lower. This high CO excitation is possibly due to the compactness of the galaxy. We find evidence that this high CO excitation has to be considered in the balance when estimating the CO-to-H-2 conversion factor. Indeed, the respective CO-to-H-2 conversion factors as derived from the correlation with metallicity and the FIR dust continuum can only be reconciled if excitation is accounted for. The inferred depletion time of the molecular gas in MACSJ0032-arc supports the decrease in the gas depletion timescale of galaxies with redshift, although to a lesser degree than predicted by galaxy evolution models. Instead, the measured molecular gas fraction as high as 6079% in MACSJ0032-arc favors the continued increase in the gas fraction of galaxies with redshift as expected, despite the plateau observed between z similar to 1.5 and z similar to 2.5.
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The 12C/ 13C Ratio in Sgr B2(N): Constraints for Galactic Chemical Evolution and Isotopic ChemistryHalfen, D. T., Woolf, N. J., Ziurys, L. M. 22 August 2017 (has links)
A study has been conducted of 12C/13C ratios in five complex molecules in the Galactic center. H2CS, CH3CCH,
NH2CHO, CH2CHCN, and CH3CH2CN and their 13C-substituted species have been observed in numerous
transitions at 1, 2, and 3 mm, acquired in a spectral-line survey of Sgr B2(N), conducted with the telescopes of the
Arizona Radio Observatory (ARO). Between 22 and 54 individual, unblended lines for the 12C species and 2–54
for 13C-substituted analogs were modeled in a global radiative transfer analysis. All five molecules were found
to consistently exhibit two velocity components near VLSR ∼ 64 and 73 km s−1, with column densities ranging
from Ntot ∼ 3 × 1014 − 4 × 1017 cm−2 and ∼2 × 1013 − 1 × 1017 cm−2 for the 12C and 13C species, respectively.
Based on 14 different isotopic combinations, ratios were obtained in the range 12C/13C = 15 ± 5 to 33 ± 13, with
an average value of 24 ± 7, based on comparison of column densities. These measurements better anchor the 12C/13C ratio at the Galactic center, and suggest a slightly revised isotope gradient of 12C/13C = 5.21(0.52) DGC +
22.6(3.3). As indicated by the column densities, no preferential 13C enrichment was found on the differing carbon
sites of CH3CCH, CH2CHCN, and CH3CH2CN. Because of the elevated temperatures in Sgr B2(N), 13C isotopic
substitution is effectively “scrambled,” diminishing chemical fractionation effects. The resulting ratios thus reflect
stellar nucleosynthesis and Galactic chemical evolution, as is likely the case for most warm clouds.
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Collagen XIII in cardiovascular development and tumorigenesisTahkola, J. (Jenni) 25 November 2008 (has links)
Abstract
Collagen XIII is a type II transmembrane protein, which has a short intracellular domain and a large, mainly collagenous ectodomain. It is located at many cell-matrix junctions and in focal adhesions in cultured cells and it has a function in cell adhesive processes.
Overexpression of collagen XIII molecules with an 83 amino acid deletion in part of the ectodomain leads to fetal lethality in Col13a1del transgenic mice. Doppler ultrasonography was performed at 12.5 days of gestation on fetuses resulting from heterozygous matings and matings between heterozygous and wild-type mice. Some fetuses had atrioventricular valve regurgitation (AVVR) and all of them were transgene positive. In addition, fetuses had pathological changes in functional parameters. Histological analysis showed the trabeculation of the ventricles to be reduced and the myocardium to be thinner in the fetuses with AVVR. Based on in situ hybridization (ISH), collagen XIII mRNA are normal constituents of these structures. Overexpression of mutant collagen XIII results in mid-gestation cardiac dysfunction in fetuses, and these disturbances in cardiac function may lead to death in utero. The heterozygous mice that were initially of normal appearance had an increased susceptibility to develop B cell lymphomas, which originated in the mesenteric lymph node. Collagen XIII protein was not detected in normal lymph nodes or in the lymphomas. The incidence of lymphomas was higher in conventional conditions than in a specific pathogen-free facility. In addition, the expression of collagen XIII was localized in the intestine and the basement membrane was highly abnormal. These findings suggest that collagen XIII is a critical determinant of lymphanogenesis.
Using ISH, antibody staining and RT-PCR techniques collagen XIII expression was analyzed during carcinogenesis in mice and in man. Collagen XIII expression increased during carcinogenesis in mice and in man. In the malignant process collagen XIII mRNA localized in the basal epithelium and in the invasive cells. According to antibody staining malignant invasive cells were positive. Results may reflect the disturbed adhesion of epithelial cells and ECM and that may affect the behaviour of the malignant cells, suggesting that collagen XIII has a significant role in the initiation of the invasion.
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Molecular gas during the post-starburst phase: low gas fractions in green-valley Seyfert post-starburst galaxiesYesuf, Hassen M., French, K. Decker, Faber, S. M., Koo, David C. 08 1900 (has links)
Post-starbursts (PSBs) are candidate for rapidly transitioning from starbursting to quiescent galaxies. We study the molecular gas evolution of PSBs at z similar to 0.03-0.2. We undertook new CO (2-1) observations of 22 Seyfert PSB candidates using the Arizona Radio Observatory Submillimeter Telescope. This sample complements previous samples of PSBs by including green-valley PSBs with Seyfert-like emission, allowing us to analyse for the first time the molecular gas properties of 116 PSBs with a variety of AGN properties. The distribution of molecular gas to stellar mass fractions in PSBs is significantly different from normal star-forming galaxies in the CO Legacy Database (COLD) GASS survey. The combined samples of PSBs with Seyfert-like emission line ratios have a gas fraction distribution that is even more significantly different and is broader (similar to 0.03-0.3). Most of them have lower gas fractions than normal star-forming galaxies. We find a highly significant correlation between the WISE 12 and 4.6 mu m flux ratios and molecular gas fractions in both PSBs and normal galaxies. We detect molecular gas in 27 per cent of our Seyfert PSBs. Taking into account the upper limits, the mean and the dispersion of the distribution of the gas fraction in our Seyfert PSB sample are much smaller (mu = 0.025, sigma = 0.018) than previous samples of Seyfert PSBs or PSBs in general (mu similar to 0.1-0.2, sigma similar to 0.1-0.2).
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Trapping and Manipulating Single Molecules of DNAShon, Min Ju 25 February 2014 (has links)
This thesis presents the development and application of nanoscale techniques to trap and / Chemistry and Chemical Biology
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Crystallographic and thermal investigation of coordination and ionic compounds of metal halides and 4-aminobenzoic acid and related moleculesOverbeek, Gerhard Ewout 28 October 2011 (has links)
In organic-inorganic hybrid compounds an organic and an inorganic component are combined to form either a coordination or an ionic material. Relevant to the current study are hybrid materials composed of an organic part that contains one or more functional groups, for example amine, amide or carboxylic acid functional groups, and a metal halide inorganic portion. These functional materials display a range of interesting and desired properties, as evidenced from numerous literature reports on their properties. In order to utilise these properties in applications, a detailed understanding of the way that the crystal structure influences the properties of a material is required. However, before this step can be achieved, it is necessary to obtain information on the structural trends of the materials, and to use the approach of crystal engineering to identify robust supramolecular synthons that may afford structural control and prediction. The aim of the current study was to investigate the synthesis and crystal structures of hybrid materials, both ionic and coordination, composed of divalent transition metal halides and the organic components 4-aminobenzoic acid, 4-aminobenzamide and isonicotinic acid, and to identify the structural trends and crystal engineering synthons displayed by these materials. A secondary objective was the preliminary identification of properties exhibited by selected materials, in order to decide on the suitability of the materials for detailed future property investigations. Part of the work describes the investigation of the structural characteristics of coordination materials prepared by the combination of the organic and inorganic components. Five novel crystal structures of coordination materials were determined, and these are compared with six related coordination structures reported in the literature. Two of the novel structures display interesting one-dimensional coordination polymers, one of which has never been reported previously in the literature. The molecular and structural characteristics of both the novel and the literature coordination structures are presented in detail, and this discussion includes a description of the coordination geometry, the molecular geometry, packing trends, hydrogen bonding interactions and aromatic interactions. A comparison study across the three families of organic components in which the structural trends, hydrogen bonding interactions, aromatic interactions, ligand geometry and coordination modes are compared, is included. The results of the synthesis of the coordination materials by means of a mechanochemical method are presented, and the products afforded by this method are compared with those prepared via solution crystallisation. Finally, the results of preliminary studies of the thermal and electronic propertries of the materials are presented and interpreted. The combination of the hybrid components as cations and anions to form ionic materials yielded nine novel structures, and these were compared with five related ionic structures reported in the literature. The novel structures include three polar structures that contain the 4-ammoniumbenzamide cation, and to our knowledge no structures containing this cation have ever been reported in the literature, hence a significant contribution to the structural knowledge of perhalometallate salts of 4-ammoniumbenzamide is made by this study. In addition two novel structures display interesting one-dimensional and two-dimensional polymeric anions, respectively, are reported. The discussion of the novel and literature ionic structures includes a description of the molecular geometry of each of the components, the identification of packing trends, and an analysis of the hydrogen bonding and aromatic interactions occurring in the structures. The structures of all three families of organic components are compared, and trends in structural type, anion geometry, water inclusion, hydrogen bonding and functional group recognition are presented. In addition, a detailed analysis of robust crystal engineering synthons occurring in these structures is presented. Lastly the results of preliminary property investigations of the thermal and electronic properties of the materials are presented and discussed / Dissertation (MSc)--University of Pretoria, 2011. / Chemistry / unrestricted
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Two-in-one Pincer Type Ligands and Their Metal Complexes for Catalysis / Two-in-one Pincer Type Ligands and Their Metal Complexes for CatalysisGers-Barlag, Alexander 24 November 2016 (has links)
No description available.
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Benzimidazole Based Novel Ligands For Specific Recognition Of Duplex And G-Quadruplex DNAPaul, Ananya 02 1900 (has links) (PDF)
The thesis entitled “Benzimidazole based Novel Ligands for Specific Recognition of Duplex and G-Quadruplex DNA” deals with the design, synthesis and modeling of several benzimidazole based molecules and their interaction with duplex and G-quadruplex DNA structures. It also elucidates the inhibition effect of the ligands on the activity of Topoisomerase I and Telomerase. The work has been divided into six chapters.
Chapter 1. DNA Interacting Small Organic Molecules: Target for Cancer Therapy
This first chapter presents an overview on the various types of small molecules that interact with duplex and G-quadruplex structures of DNA or interfere with the activity of DNA targeted enzymes like topoisomerase and telomerase. The importance of such molecules as chemotherapeutic agents is highlighted.
Chapter 2. DNA Recognition: Conformational Switching of Duplex DNA by Mg2+ ion Binding to Ligand
Bis-benzimidazoles like Hoechst 33258 are well known ligands that bind to duplex DNA (ds-DNA) minor grooves. Here a series of dimeric bisbenzimidazole based ligands in which two Hoechst units are connected via oxyethylene based hydrophilic [Ho-4ox-Ho (1), Ho-3ox-Ho (2)] or via hydrophobic oligomethylene [Ho-(CH2)8-Ho (3)](Figure 1) spacers have been synthesized. The aim of this investigation is to examine the binding property of these dimers on the ds-DNA to explore whether the variation in the length of the spacer has any effect on DNA binding properties particularly in presence of selected metal ions. The changes of individual dimers in DNA binding efficiency was studied in detail by fluorescence, circular dichroism spectral titrations and thermal denaturation experiment with selected duplex DNA formed from appropriate oligonucleotides. We have also examined the changes that occur in geometry of the molecules from linear to hairpin motif in presence of Mg2+ ion. A large difference was observed in [ligand]/ [DNA] ratio and binding efficiency with ds-DNA upon change in the ligand geometry from linear to hairpin motif. The experimental results were then substantiated using docking and molecular dynamics simulations using a model ds-DNA scaffold. Both experimental and theoretical studies indicate that the DNA binding is highly dependent on the spacer type and length between the two monomeric Hoechst units. The spacer length actually helps to achieve shape complimentarity with the double-helical DNA axis.
Figure1: Chemical structures of the dimeric ligands Ho-4ox-Ho, Ho-3ox-Ho, Ho-(CH2)8-Ho and Hoechst 33258 (Ho) used in this study.
Chapter 3. DNA Binding and Topoisomerase I Inhibiting Properties of New Benzimidazole Substituted Polypyridyl Ruthenium (II) Mixed-Ligand Complexes
In this study, we have synthesized and fully characterized three new Ru(II)
based polypyridyl and benzimidazole mixed complexes: (1) [Ru(bpy)2(PMI)], 2+
(2) [Ru(bpy)2(PBI)]2+ and (3) [Ru(bpy)2(PTI)]2+ (Figure 2) . The affinities of these complexes toward duplex DNA were investigated. In addition, the photocleavage reaction of DNA and topoisomerase I inhibition properties of these metal complexes were also studied. The DNA binding efficiency of individual complexes was studied in detail by absorbance, fluorescence spectral titrations and thermal denaturation experiment using natural calf-thymus DNA. Upon irradiation at 365 nm, all three Ru(II) complexes were found to promote the cleavage of plasmid DNA from negatively supercoiled to nicked circular and subsequently to linear DNA. The inhibition of topoisomerase I mediated by these Ru(II) complexes was also examined. These experiments demonstrate that each complex serves as an efficient inhibitor toward topoisomerase I and such inhibition activity is consistent with interference with the DNA religation step catalyzed by topoisomerase.
Figure 2. Chemical structures of the metal complexes used in this present study.
Chapter 4. Synthesis and Evaluation of a Novel Class of G-Quadruplex-Stabilizing small molecules based on the 1,3-Phenylene-bis (piperazinyl benzimidazole) syatem
Achieving stabilization of telomeric DNA in the G-quadruplex conformation by various organic compounds is an important goal for the medicinal chemists seeking to develop new anticancer agents. Several compounds are known to stabilize the G-quadruplexes. However, relatively few are known to induce their formation and/or alter the topology of the pre-formed G-quadruplex DNA.
Herein, four compounds having the 1,3-phenylene-bis(piperazinyl benzimidazole) (Figure 3) unit as a basic skeleton have been synthesized, and their interactions with the 24-mer telomeric DNA sequences from Tetrahymena thermophilia d(T2G4)4 have been investigated using high-resolution techniques such as circular dichroism (CD) spectropolarimetry, CD melting, emission spectroscopy, and polyacrylamide gel electrophoresis. The data obtained, in the presence of one of three ions (Li+, Na+ or K+), indicate that all the new compounds have a high affinity for G-quadruplexDNA, and the strength of the binding with G-quadruplex depends on (i) phenyl ring substitution, (ii) the piperazinyl side chain, and (iii) the type of monovalent cation present in the buffer. Results further suggest that these compounds are able to abet the conversion of the intramolecular G-quadruplex DNA into parallel stranded intermolecular G-quadruplex DNA. Notably, these compounds are also capable of inducing and stabilizing the parallel stranded G-quadruplex DNA from randomly structured DNA in the absence of any stabilizing cation. The kinetics of the structural changes induced by these compounds could be followed by recording the changes in the CD signal as a function of time.
Figure 3. Chemical structures of the ligands used in this study.
Chapter 5A. The Spacer Segment in the Dimeric 1,3-phenylene-bis (piperazinyl benzimidazole) has a Dramatic Influence on the Binding and Stabilization of Human Telomeric G-Quadruplex DNA
Ligand-induced stabilization of G-quadruplex structures formed by human telomeric DNA is an active area of basic and clinical research. The compounds which stabilize the G-quadruplex structures lead to suppression of telomerase activity. Herein, we present the interaction of a series of monomeric and dimeric compounds having 1,3-phenylene-bis(piperazinyl benzimidazole) (Figure 4) as basic pharmacophore unit with G-quadruplex DNA formed by human telomeric repeat d[(G3T2A)3G3]. These new compounds provide an excellent stabilization property to the pre-formed G-quadruplex DNA in the presence of one of three ions (100 mM Li+, Na+ or K+ ions). Also the G-quadruplex DNA formed in the presence of low concentrations of ligands in 100 mM K+, adopts a parallel-stranded conformation which attains an unusual thermal stability. The dimeric ligands having oxyethylene based spacer provide much higher stability to the pre-formed G-quadruplex DNA and the G-quadruplexes formed in presence of the dimeric compounds than the corresponding monomeric counterparts. Consistent with the above observation, the dimeric compounds exert significantly higher telomerase inhibition activity than the monomeric compounds. The ligand induced G-quadruplex DNA complexes were further investigated by computational molecular modeling, which provide useful information on their structure-activity relationship.
Figure 4. Chemical structures of the monomeric and dimeric ligands used in this study.
Chapter 5B. Role of Spacer in Symmetrical Gemini bisbenzimidazole based Ligands on the Binding and Stabilization of Dimeric G-Quadruplex DNA derived from Human Telomeric Repeats
The design and development of anticancer agents that act via stabilization of the telomeric G-quadruplex DNA is an active area of research because of its importance in the negative regulation of telomerase activity. Several classes of G-quadruplex DNA binding ligands have been developed so far, but they mainly act on the DNA sequences which are capable of forming a single Gquadruplex unit. In the present work, we have developed few new dimeric (Gemini) bisbenzimidazole ligands (Figure 5), in which the spacer joining the two bisbenzimidazole units have been varied using oligooxyethylene units of different length. Herein we show the interaction of each of these ligands, with the G-quadruplex DNA, derived from oligodeoxynucleotides d(T2AG3)4 and d(T2AG3)8, which fold into a monomeric and dimeric (having two folded G-tetrad units) G-quadruplex DNA, respectively. We also present evidence that the G-quadruplex DNA structure formed by these sequences in K+ solution in presence of the ligands is parallel, with unusual stability, and the spacer length between the two bisbenzimidazole units has critical role on the G-quadruplex stability, particularly on the G-quadruplex structures formed by the 48-mer sequence. The computational aspects of the ligand-G-quadruplex DNA association have also been analyzed. Interestingly, the gemini ligand having longer spacer was highly potent in the inhibition of telomerase activity than the corresponding gemini ligands having shorter spacer or the monomeric ligand. Also, the dimeric ligands are more cytotoxic toward the cancer cells than normal cells.
Figure 5. Chemical structures of the monomeric and gemini ligands used in this study.
Chapter 6. Stabilization and Structural Alteration of G-Quadruplex DNA made from Human Telomeric Repeat Mediated by Novel Benzimidazole Derivatives based on Tröger’s Base
Ligand-induced stabilization of G-quadruplex formation by the telomeric DNA single stranded 3'-overhang is a nice strategy to inhibit telomerase from catalyzing telomeric DNA synthesis and form capping telomeric ends. Herein we present the first report of the interactions of two novel bisbenzimidazoles (TBBz1 and TBBz2)(Figure 6) based on the Tröger’s base skeleton with the G-quadruplex DNA. These molecules stabilize the G-quadruplex DNA derived from a human telomeric sequence. Significantly strong binding affinity of these molecules to G-quadruplex DNA relative to duplex DNA was observed by CD spectroscopy, thermal denaturation and UV-vis titration studies. The above results obtained are in excellent agreement with the biological activity, measured in vitro using a modified TRAP assay. Additionally exposure of cancer cells to these compounds showed a remarkable decrease in the population growth. Also, it has been observed that the ligands are selectively more cytotoxic toward the cancerous cells than the corresponding noncancerous cells. To understand further, the ligand-G-quadruplex DNA complexes were investigated by computational molecular modeling. This provided additional insights on the structure activity relationship. Computational studies suggest that the adaptive scaffold not only allows these ligands to occupy the G-quartet but also binds with the grooves of the G-quadruplex DNA.
Figure 6. Chemical structures of the ligands, TBBz1 and TBBz2 used in this study,
(For structural formula pl see the abstact.pdf file.)
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Structure, Dynamics And Thermodynamics Of Confined Water MoleculesKumar, Hemant 10 1900 (has links) (PDF)
This thesis deals with several aspects of the structure and dynamics of water molecules confined in nanoscopic pores. Water molecules confined in hydrophobic nanocavities exhibit unusual structural and dynamic properties. Confining walls of single-wall carbon nanotubes (SWCNTs) promote strong inter-water hydrogen bonding which in turn leads to several novel structural, dynamic and thermodynamic features not found in bulk water. Confined water molecules form ordered hydrogen-bonded networks, exhibit exceptionally high flow rates as compared to conventional flow in pipes, allow fast proton conduction and exhibit various other anomalous properties. Proteins are known to exploit some of the properties of confined water to perform certain physiological functions. Various properties of confined water can also be exploited in the design of nanofludic devices such as those for desalination and flow sensors. In addition, water molecules confined in SWCNTs and near graphene sheets serve as model systems to study various effects of confinement on the properties of liquids. In this thesis, we present the results of detailed molecular dynamics simulation studies of confined water molecules.
In chapter 1, we summarize the findings of existing simulations and experimental studies of bulk and confined water molecules. We also highlight the significance of studying the structure and dynamics of confined water molecules in biological and biotechnological applications. Chapter 2 provides a brief ac-count of the methods and techniques used to perform the simulations described in subsequent chapters of the thesis. We also present a brief overview of the methods used to extract physical properties of water molecules from simulation data, with emphasis on the Two Phase Thermodynamics (2PT) method which we have used to compute the entropy of confined and bulk water molecules.
In chapter 3, we discuss the thermodynamics of water entry in SWCNTs of various diameters. Experiments and computer simulations demonstrate that water spontaneously fills the interior of a carbon nanotube. Given the hydrophobic nature of the interior of carbon nanotubes and the strong confinement produced by narrow nanotubes, the spontaneous entry of water molecules in the pores of such nanotubes is surprising. To gain a quantitative thermodynamic understanding of this phenomenon, we use the recently developed Two Phase Thermodynamics (2PT) method to compute translational and rotational entropies of water molecules confined in SWCNTs and show that the increase in energy of a water molecule inside the nanotube is compensated by the gain in its rotational entropy. The confined water is in equilibrium with the bulk water and the Helmholtz free energy per water molecule of confined water is the same as that in the bulk within the accuracy of the simulation results. A comparison of translational and rotational spectra of water molecules confined in carbon nanotubes with those of bulk water shows significant shifts in the positions of spectral peaks that are directly related to the tube radius. These peaks are experimentally accessible and can be used to characterize water dynamics from spectroscopy experiments. We have also computed the free-energy transfer when a bulk water molecule enters a SWCNT for various temperatures and carbon-water interactions. We show that for reduced carbon-oxygen interaction, the free energy transfer is unfavourable and the SWCNT remains unoccupied for significant periods of time. As the temperature is increased, the free energy of confined water becomes unfavourable and reduced occupancy of water is observed.
Bulk water exhibits many anomalous properties. No single water model is able to reproduce all properties of bulk water. Different empirical water models have been developed to reproduce different properties of water. In chapter 4, a comparative study of the structure, dynamics and thermodynamic proper-ties of water molecules confined in narrow SWCNTs, obtained from simulations using several water models including polarizable ones, is presented. We show that the inclusion of polarizability quantitatively affects the nature of hydro-gen bonding which governs different properties of water molecules. The SPC/E water model is shown to reproduce results in close agreement with those from polarizable water models with much less computational cost.
In chapter 5, we report results obtained from simulations of the properties of water confined in the space between two planar surfaces. We consider three cases: two graphene surfaces, two Boron Nitride (BN) surfaces and one graphene and one BN surface. This is the first detailed study of the behaviour of water near extended BN surfaces. We show that the hydrophilic nature of the BN surface leads to several interesting effects on the dynamics of water molecules near it. We have observed a change in the activation energy, extracted from the temperature dependence of the translational and rotational dynamics, near 280K. This change in activation energy coincides with a change in the structure of the confined sheet of water, indicated by a sudden change in energy. We have also found signatures of glassy dynamics at low temperatures for all three cases, the glassy effects being the strongest for water molecules confined between two BN sheets. These results are similar to those of earlier studies in which novel phases of water have been found for water molecules confined between other surfaces at high pressure.
In chapter 6, we have described our observation of a novel phenomenon exhibited by water molecules flowing through a SWCNT under a pressure gradient. We have shown that the flow induces changes in the orientation of the water molecules flowing through the nanotube. In particular, the dipole moments of the water molecules inside the nanotube get aligned along the axis of the nanotube under the effect of the flow. With increasing flow velocities, the net dipole moment first increases and eventually saturates to a constant value. This behaviour is similar to the Langevin theory of paramagnetism with the flow velocity acting as an effective aligning field. Preferential entry of water molecules with dipole moments pointing inward is shown to be the main cause of this effect. This observation provides a way to control the dipolar alignment of water molecules inside nano-channels, with possible applications in nanofluidic devices. Chapter 7 contains a summary of our main results and a few concluding re-marks.
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Star Shaped Thieno- and Thienylaryls as Multifunctional MaterialsRobertson, Sean January 2015 (has links)
The work in this thesis was undertaken to explore both the effect of heteroatoms on the semiconducting properties of star-shaped thienoacenes, and to expand the scope of these materials to fields outside of organic semiconductors. Overall, new star-shaped molecules were prepared with a view towards applications such as thin film transistors, as the organic linker component in metal-organic frameworks, and as ligands that could coordinate to transition metals through the sulfur atom.
The first chapter describes the properties of star-shaped molecules, the theory underlying their semiconducting behaviour, and the previous work that motivated the research contained herein. The second chapter of this thesis outlines the synthetic methodology that was utilized to achieve the molecular targets, as well as the characterization techniques that are used to reveal the properties of organic semiconductors.
The third chapter of this thesis describes the synthesis and optoelectronic properties of novel nitrogen-containing semiconductor molecules called thienoacridines, and their comparison to carbon-and-sulfur based analogues, thienoanthracenes.
The fourth and fifth chapters concern the synthesis of functionalized star shaped thienylbenzene molecules. In Chapter 4, these molecules are decorated with carboxylic acid groups so that they may act as tetrapodal MOF linkers. In Chapter 5, they are equipped with N-aryl(azomethine)thiophene moieties to explore sulfur coordination and act as ligands. The sixth chapter provides conclusion to this work, and possible future directions of the research conducted herein.
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