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Selective benzylic carbon hydrogen bond activation of toluenes and aromatic carbon halogen bond activation of halobenzenes by rhodium(III) porphyrins.January 2006 (has links)
by Chiu Peng Fai. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references (leaves 82-87). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgements --- p.iv / Abbreviations --- p.v / Abstract --- p.vi / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Definition of Carbon Hydrogen Bond Activation (CHA) by Transition Metal Comple --- p.1 x / Chapter 1.2 --- The Importance of Alkane CHA and its Potential Use --- p.1 / Chapter 1.3 --- Difficulties in Alkane CHA --- p.3 / Chapter 1.4 --- The Use of Transition Metal Complexes in CHA Reactions --- p.4 / Chapter 1.5 --- Classification of CHA Reactions --- p.6 / Chapter 1.6 --- The Importance of Toluene and Benzene CHA --- p.11 / Chapter 1.7 --- Difficulties and Challenges in CHA of Toluene --- p.11 / Chapter 1.8 --- Selectivity Control and Rate Promotion --- p.12 / Chapter 1.9 --- Structural Features of Rhodium Porphyrins --- p.17 / Chapter 1.10 --- CHA by Rhodium Porphyrins --- p.19 / Chapter 1.11 --- Objective of Work --- p.21 / Chapter Chapter 2 --- CHA Reactions of Toluenes by Rhodium Porphyrin Chlorides / Chapter 2.1 --- Synthesis of Rhodium Porphyrin Chlorides --- p.22 / Chapter 2.2 --- Temperature Effects of CHA in Toluene --- p.22 / Chapter 2.3 --- Inter and Intra Molecular Exchange of Alkyl Rhodium Porphyrin Complexes --- p.24 / Chapter 2.4 --- Electronic Effect of Rhodium Porphyrin Chlorides --- p.24 / Chapter 2.5 --- Electronic Effect of Toluene Towards CHA --- p.25 / Chapter 2.6 --- X-Ray Data --- p.26 / Chapter 2.7 --- Mechanistic Studies --- p.30 / Chapter 2.8 --- Ligand and Base Effects --- p.32 / Chapter 2.9 --- Optimization of Reaction Conditions --- p.35 / Chapter 2.10 --- Electronic Effect of Toluenes --- p.36 / Chapter 2.11 --- Concentraction Effects of Toluenes (Reactions in Benzene) --- p.38 / Chapter 2.12 --- Porphyrin Effects in CHA of Toluene --- p.39 / Chapter 2.13 --- Mechanistic Studies --- p.40 / Chapter 2.14 --- Conclusion --- p.42 / Chapter 2.15 --- Reaction between Rh(ttp)Me and Toluenes --- p.42 / Chapter 2.16 --- Selective Benzylic CHA --- p.42 / Chapter 2.17 --- Isotope Effect --- p.44 / Chapter 2.18 --- Discussion --- p.44 / Chapter 2.19 --- Exploratory Studies of Other Base-Promoted Reactions --- p.45 / Chapter 2.20 --- Benzylic CHA and Aromatic Carbon Halogen Bond Activation (CXA) Reactions --- p.45 / Chapter 2.21 --- Base-Enhanced Aromatic CXA --- p.48 / Chapter 2.22 --- X-Ray Data --- p.49 / Chapter 2.23 --- Base-Enhanced Benzylic Carbon Carbon Bond Activation (CCA) Reactions --- p.51 / Chapter 2.24 --- Summary --- p.52 / Chapter Chapter 3 --- Experimental Sections --- p.53 / References --- p.82 / Appendix I Crystal Data and Processing Parameters --- p.88 / Appendix II List of Spectra --- p.123 / Spectra --- p.125
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Multicomponent Cocrystals and Solid Solutions based on a Two-Point Hydrogen Bond SynthonEmery, Paul Ralph 15 January 2009 (has links)
Herein we describe a straight-forward and reproducible method for the preparation of homogeneous, multicomponent cocrystals and supramolecular solid solutions. We prepared these multicomponent materials based on small organic molecules that employ a two-point supramolecular hydrogen bond synthon. We report the creation and characterization of two, three, four, five, and seven component crystals containing a variety of 2-aminopyridines and monosubstituted benzoic acids. These systems exhibit the ability to accommodate multiple components in varying proportions while coordinating into an identical packing structure. The flexibility of the system to incorporate multiple components also gives rise to gradual modulation of physical properties.
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Hydrogen-bonding and halogen-arene interactionsDominelli Whiteley, Nicholas January 2017 (has links)
Non-covalent interactions are fundamental to molecular recognition processes that underpin the structure and function of chemical and biological systems. Their study is often difficult due to the interplay of multiple interactions and solvent effects common in complex systems. Herein, chapter one provides some general background on the area before presenting a literature review of key, contemporary developments on the use of folding molecules for the quantification of non-covalent interactions. Chapter two investigates the magnitude and extent of energetic cooperativity in H-bond chains. Utilising supramolecular complexes and synthetic molecular torsion balances, direct measurements of energetic cooperativity are presented in an experimental system in which the geometry and number of H-bonds in a chain were systematically controlled. Strikingly, it was found that adding a second H-bond donor to form a chain can almost double the strength of the terminal H-bond, while further extension had very little effect. Computations provide insights into this strong, short-range cooperative effect in a range of H-bonding contexts. Chapters three and four build on the concepts and molecular models discussed in chapter two. Chapter three discusses the effects of interplay and competition between strong H-bond acceptors such as formyl groups and the weaker organofluorine H-bond acceptor. There has been some debate in recent literature about the latter’s ability to accept H-bonds, the work presented shows that although organofluorine is a weak H-bond acceptor, it can have a significant modulating effect on stronger interactions when in direct competition. Chapter four investigates deuterium isotope effects on conformational equilibria governed by non-covalent interactions. The results show that any deuterium isotope effect which exists is less than the margins of experimental error. Finally, chapter five discusses a molecular torsion balance designed to investigate halogen∙∙∙arene interactions. The interaction energies were investigated in a range of solvents and mixtures in order to dissect out the dispersive and solvophobic components of folding. Overall, these interactions were found to be weak. Nonetheless, a model was used to dissect trends in solvophobic and electronic contributions to the binding using multiple linear regression based upon the cohesive energy density and polarisabilities of the solvents.
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New inclusion compounds with carboxylate and guanidinium ions as host components.January 2007 (has links)
Yau, Chung Wah. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (leaves 55-57). / Abstracts in English and Chinese. / Acknowledgement --- p.i / Abstract --- p.ii / Table of Contents --- p.iv / Index of Compounds --- p.v / Chapter 1. --- Introduction / Chapter 1.1 --- Fundamentals of inclusion chemistry --- p.1 / Chapter 1.2 --- Hydrogen bonding in supramolecular chemistry and crystal engineering --- p.3 / Chapter 1.3 --- Hydrogen-bonded rosette system --- p.4 / Chapter 1.4 --- Research plan --- p.7 / Chapter 2. --- Descriptions of crystal structures / Chapter 2.1 --- Supramolecular rosette layer and rosette ribbon constructed from guanidinium cations and hydrogen carbonate dimers /carbonate anions / Chapter 2.1.1 --- (Et4N+)[C(NH2)3+]7(C032-)3[C3N2H2(C00-)2] (1) --- p.11 / Chapter 2.1.2 --- [(n-Bu)4N+]3[C(NH2)3+]4(HC03-)4[H+{C3N2H-(C00-)(C00H)}2] (2) --- p.14 / Chapter 2.1.3 --- [(n-Bu)4N+]2[C(NH2)3+]2(HC03-)2[NCC6H4(C00-)]2 ´Ø 2H20 (3)…… --- p.16 / Chapter 2.1.4 --- "[(n-Bu)4+]8[C(NH2)3+]8(HCO3-)8[4,4'-C12H8(C00-)2]4 ´Ø 8H20 ´″…" --- p.17 / Chapter 2.2 --- Channel- and layer-type anionic host structures constructed from benzene hexacarboxylic acid and guanidinium cation / Chapter 2.2.1 --- [C6(COO-)6][C(NH2)3]6 ´Ø H20 (5) --- p.20 / Chapter 2.2.2 --- [C6(COOH)3(COO´ؤ)3][C(NH2)3+]3 ´Ø 2H20 (6) --- p.23 / Chapter 2.2.3 --- [(n-Pr)4N+][C6(COOH)5(COO-)] ´Ø 3H20 (7) --- p.27 / Chapter 2.2.4 --- [(n-Bu)4N+]4[C6(COOH)5(COO-)]2[C6(COOH)4(COO-)2]2 [C(NH2)3+]2.8H2O(8) --- p.30 / Chapter 2.2.5 --- (Et4N+)2[C6(COOH)4(COO-)2]2[C(NH2)3+]2 ´Ø 2H20 (9) --- p.35 / Chapter 2.2.6 --- (Me4N+)[C6(COOH)3(COO-)3][C(NH2)3+]2 ´Ø H20 (10) --- p.37 / Chapter 3. --- Summary and discussion / Chapter 3.1 --- Robustness of hydrogen-bonded supramolecular rosette networks --- p.40 / Chapter 3.2 --- Versatile hydrogen bonding modes of guanidinium with mellitate anions --- p.43 / Chapter 4. --- Experimental / Chapter 4.1 --- Preparation methods --- p.48 / Chapter 4.2 --- X-ray crystallography --- p.52 / Chapter 5. --- References --- p.55 / "Appendix A: Tables of atomic coordinates, thermal parameters, bond lengths and angles and hydrogen bonds" --- p.58
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Hydrogen Bonding Between the Carbonyl Group and Wyoming BentoniteKohl, Robert A. 01 May 1960 (has links)
The vibrational frequencies of atom to atom bonds within a molecule are a function of the bond energies. Each bond has its characteristic frequency, and most of these frequencies can be detected with the infrared spectrophotometer. When one compound reacts with another or is adsorbed on the surface of a solid, detectable frequency changes or shifts may occur. These changes or shifts yield valuable information about the bonds which are formed or broken.
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Physical-chemical properties of complex natural fluidsMoskau 25 September 2001 (has links) (PDF)
No description available.
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Computational and experimental investigations of forces in protein foldingSchell, David Andrew 17 February 2005 (has links)
Properly folded proteins are necessary for all living organisms. Incorrectly folded proteins can lead to a variety of diseases such as Alzheimers Disease or Bovine Spongiform Encephalitis (Mad Cow Disease). Understanding the forces involved in protein folding is essential to the understanding and treatment of protein misfolding diseases. When proteins fold, a significant amount of surface area is buried in the protein interior. It has long been known that burial of hydrophobic surface area was important to the stability of the folded structure. However, the impact of burying polar surface area is not well understood. Theoretical results suggest that burying polar groups decreases the stability, but experimental evidence supports the belief that polar group burial increases the stability. Studies of tyrosine to phenylalanine mutations have shown the removal of the tyrosine OH group generally decreases stability. Through computational investigations into the effect of buried tyrosine on protein stability, favorable van der Waals interactions are shown to correlate with the change in stability caused by replacing the tyrosine with phenylalanine to remove the polar OH group. Two large-scale studies on nearly 1000 high-resolution x-ray structures are presented. The first investigates the electrostatic and van der Waals interactions, analyzing the energetics of burying various atom groups in the protein interior. The second large-scale study analyzes the packing differences in the interior of the protein and shows that hydrogen bonding increases packing, decreasing the volume of a hydrogen bonded backbone by about 1.5 Å3 per hydrogen bond. Finally, a structural comparison between RNase Sa and a variant in which five lysines replaced five acidic groups to reverse the net charge is presented. It is shown that these mutations have a marginal impact on the structure, with only small changes in some loop regions.
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Mass Transfer in Multi-Phase Single Particle SystemsSu, Jonathan T. January 2011 (has links)
<p>This thesis addresses mass transfer in multi-phase single particle systems. By using a novel technique based upon the micropipette, the dissolution of liquid and gas droplets in a liquid medium can be observed. Three classes of experimental systems are observed: pure liquid droplet dissolution in a pure liquid environment, miscible mixture liquid droplet dissolution in a pure liquid environment, and solute-containing liquid droplet dissolution in a pure liquid environment. Experiments on the dissolution of pure droplets of water in n-alcohols and n-alkanes showed that water droplets dissolved ten times faster in the alcohols as compared to in the alkanes. When solubility was taken into account, however, and diffusion coefficients calculated using the Epstein-Plesset equation, diffusion constants for alkanes were twenty five times higher in alkanes than for the corresponding alcohol (for example 12.5 vs 0.5 x 10-8 cm2/s for pentane and pentanol). This difference in rates of diffusion of the single molecules reflects the effect of hydrogen bonding on small solute diffusion, which is expounded upon in Chapter 2.</p><p> A model for the dissolution of a droplet containing a mixture, each component of which is soluble in the surrounding liquid medium is presented in Chapter 3. The model is based upon a reduced surface area approximation and the assumption of ideal homogenous mixing : Mass flux (dm_i)/dt=〖Afrac〗_i D_i (c_i-c_s){1/R+1/√(πD_i t)}, where Afraci is the area fraction of component i, ci and cs are the initial and saturation concentrations of the droplet material in the surrounding medium, respectively, R is the radius of the droplet, t is time, and Di is the coefficient of diffusion of component i in the surrounding medium. This model was tested for the dissolution of ethyl acetate and butyl acetate in water and the dissolution of butyl acetate and amyl acetate in water, and was found to provide a good fit. In Chapter 4, a partial differential equation, R^2/D ├ ∂c/∂t┤|_η=(∝η)/D ∂c/∂η+(∂^2 c)/〖∂η〗^2 +2/η ∂c/∂η, is presented for the dissolution of a solute containing droplet in a liquid medium, and shell or bead formation is predicted. In Chapter 5, an application of the solute containing droplet dissolution is presented in which suspensions of glassified protein microspehres are used to improve the injectability of protein based pharmaceuticals. Injectability is related to viscosity, and the viscosity of a suspension may be predicted to follow the Krieger Dougherty equation: (η(Φ))/η_0 =(1-Φ/Φ_m )^(-2.5Φ_m ) , where Φ is the volume fraction of the suspensate, η is the viscosity of the overall suspension, η0 is the viscosity of the suspending fluid, and Φm is the maximum possible volume fraction. Finally, in Chapter 6, various experimental methods used to generate droplets are addressed.</p> / Dissertation
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Enantioselective Conjugate Additions to Meldrum’s Acid Acceptors for the Synthesis of Quaternary Centres and Studies on Persistent Intramolecular C–H•••X (X = O, S, Br, Cl, and F) Hydrogen Bonds Involving Benzyl Meldrum’s AcidsWilsily, Ashraf 20 August 2009 (has links)
The construction of benzylic quaternary stereocentres via the enantioselective copper-catalyzed 1,4-addition of dialkylzinc reagents to Meldrum’s acid acceptors in the presence of a phosphoramidite ligand is reported. Meldrum’s acid acceptors can be easily accessed and numerous derivatives have been prepared to investigate the scope of the enantioselective 1,4-addition. The reaction is tolerant to a wide range of heteroaromatic and functional groups. The significance of substituting the position para, meta, and ortho to the electrophilic centre is also highlighted. Primary and secondary organozinc reagents are shown to be compatible in this reaction.
A highly enantioselective synthesis of carboxylic acid derivatives having an -quaternary centre through copper-catalyzed 1,4-addition of dialkylzinc reagents to aryl acetate derivatives is also described. This method employs a commercially available phosphoramidite ligand and readily accessible Meldrum’s acid acceptors. A brief insight into the observed selectivity is also discussed. The significance of this method was established by the expedient preparation of chiral diesters, succinimides, γ-butyrolactones, and isocyanates from highly functionalized benzyl Meldrum’s acids.
In addition to 1,4-addition, the enantioselective asymmetric synthesis of benzylic tertiary and quaternary stereogenic centres via 1,6-addition of dialkylzinc reagents to Meldrum’s acid acceptors is outlined. This work represents one of the early examples of 1,6-asymmetric conjugate addition reactions and discussions on the regioselectivity of the process are disclosed.
On a different subject matter, the occurrence and persistence of C–H•••X (O, S, Br, Cl, and F) bond in solution using 1H NMR spectroscopy is discussed for a large number of benzyl Meldrum’s acids. The latter are novel and reliable probes for the evaluation of this type of non-classical interactions in solution. The persistence of the C–H•••X bond in solution is demonstrated to be dependent upon structural features present on the aromatic moiety and the benzylic position of the benzyl Meldrum’s acid derivatives. The observations presented highlight the large potential of Meldrum’s acid in developing an understanding of the function and nature of C–H•••X interactions.
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Enantioselective Conjugate Additions to Meldrum’s Acid Acceptors for the Synthesis of Quaternary Centres and Studies on Persistent Intramolecular C–H•••X (X = O, S, Br, Cl, and F) Hydrogen Bonds Involving Benzyl Meldrum’s AcidsWilsily, Ashraf 20 August 2009 (has links)
The construction of benzylic quaternary stereocentres via the enantioselective copper-catalyzed 1,4-addition of dialkylzinc reagents to Meldrum’s acid acceptors in the presence of a phosphoramidite ligand is reported. Meldrum’s acid acceptors can be easily accessed and numerous derivatives have been prepared to investigate the scope of the enantioselective 1,4-addition. The reaction is tolerant to a wide range of heteroaromatic and functional groups. The significance of substituting the position para, meta, and ortho to the electrophilic centre is also highlighted. Primary and secondary organozinc reagents are shown to be compatible in this reaction.
A highly enantioselective synthesis of carboxylic acid derivatives having an -quaternary centre through copper-catalyzed 1,4-addition of dialkylzinc reagents to aryl acetate derivatives is also described. This method employs a commercially available phosphoramidite ligand and readily accessible Meldrum’s acid acceptors. A brief insight into the observed selectivity is also discussed. The significance of this method was established by the expedient preparation of chiral diesters, succinimides, γ-butyrolactones, and isocyanates from highly functionalized benzyl Meldrum’s acids.
In addition to 1,4-addition, the enantioselective asymmetric synthesis of benzylic tertiary and quaternary stereogenic centres via 1,6-addition of dialkylzinc reagents to Meldrum’s acid acceptors is outlined. This work represents one of the early examples of 1,6-asymmetric conjugate addition reactions and discussions on the regioselectivity of the process are disclosed.
On a different subject matter, the occurrence and persistence of C–H•••X (O, S, Br, Cl, and F) bond in solution using 1H NMR spectroscopy is discussed for a large number of benzyl Meldrum’s acids. The latter are novel and reliable probes for the evaluation of this type of non-classical interactions in solution. The persistence of the C–H•••X bond in solution is demonstrated to be dependent upon structural features present on the aromatic moiety and the benzylic position of the benzyl Meldrum’s acid derivatives. The observations presented highlight the large potential of Meldrum’s acid in developing an understanding of the function and nature of C–H•••X interactions.
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