DOCSLIB.ORG

Durham E-Theses

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Durham E-Theses Durham E-Theses NMR Crystallography of Disordered Cocrystals KERR, HANNAH,ELIN How to cite: KERR, HANNAH,ELIN (2017) NMR Crystallography of Disordered Cocrystals, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/12037/ Use policy The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that: • a full bibliographic reference is made to the original source • a link is made to the metadata record in Durham E-Theses • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders. Please consult the full Durham E-Theses policy for further details. Academic Support Oce, Durham University, University Oce, Old Elvet, Durham DH1 3HP e-mail: [email protected] Tel: +44 0191 334 6107 http://etheses.dur.ac.uk NMR CRYSTALLOGRAPHY OF DISORDERED COCRYSTALS By Hannah Elin Kerr A thesis submitted in partial fulfilment of the requirements for the degree of Doctor of Philosophy Department of Chemistry 2016 -Abstract- -i- Abstract Crystallographic disorder is common in the solid state but it is rarely investigated explicitly despite having a fundamental impact on the solid-state structure of a material. In this work, nuclear magnetic resonance (NMR) crystallography methods are utilised to achieve a detailed understanding of the structure and dynamics of solid organic systems containing disorder. Several new cocrystal systems are studied, each containing a topical drug molecule (caffeine, naproxen or furosemide) and each serving to demonstrate how NMR crystallography can be applied to a variety of structural questions. Hydrogen bonding motifs are identified using single crystal X-ray diffraction experiments, where possible, and are subsequently verified by solid-state NMR. Alternative hydrogen bonding models are ruled out by comparison of experimental solid-state NMR data with density functional theory calculated shieldings, and proton transfer can be investigated by monitoring the energy of the system with respect to proton position. In a particularly challenging case, 2D solid-state NMR experiments go some way to identify the hydrogen bonds in a system that cannot be crystallised. Dynamic disorder of fragments and solvent molecules are characterised by variable temperature solid-state NMR, including analysis of relaxation times to establish energy barriers and rates of motion. A mechanism of motion is also proposed for dynamic acetone molecules in a new cocrystal solvate, which is supported by good agreement between experimental and simulated 2H static NMR line shapes. Finally, the current limit of NMR crystallography is identified with respect to the reproducibility of calculated NMR parameters following geometry optimisation. It is shown that the geometry optimisation protocol does not affect standard NMR crystallography investigations pertaining to atom assignment, but it is significant for cases where very subtle structural features are probed, such as NMR linewidths. Overall, NMR crystallography investigations allow a deeper understanding of solid materials to be achieved than would be possible with any single technique and this work highlights the applicability of such methods to complex materials containing disorder. -Abstract- -ii- Acknowledgements First and foremost I would like to thank my supervisor, Paul, for finding the perfect balance between “hands-on” and “hands-off” supervision and for always answering my silly questions with patience. I have learnt so much and will always be grateful for the belief placed in me. My sincere thanks to Ivana for providing a fresh perspective, teaching me about diffraction, and for providing me with most of the systems studied in this work. A special thank you must go to David Apperley, without whom I would not have been able to run a single NMR experiment. Thank you for taking so many hours to help me set up experiments, fix problems (both trivial and serious) and for our long chats during cryogen fills or while watching FIDs slowly acquire. I am grateful to everyone who has been a member of the SSNMR group during my time at Durham; Robin (for sharing his years of experience over coffee), Martin (for teaching me how to run CASTEP and to use a command line for the first time), Eric, Fraser, Ilya, Marcin, Martins and Agris. A special thank you to Cory for keeping me company in the desk room and for all the fun debates we have had over coffee. I hope I can acquire an eye for detail to rival yours one day! Also to Will and Tavleen, for all our procrastination chats and the mountains of cake! Thanks to my family for instilling a love of science in me from the very beginning. Finally, thank you to Kevin for all the love and support you have given me, as well as the late night chemistry debates and all your wonderful cooking. The copyright of this thesis rests with the author. No quotation from it should be published without the author's prior written consent and information derived from it should be acknowledged. -Abbreviations- -iii- Abbreviations ABMS Anisotropy of the bulk magnetic susceptibility ADPs Anisotropic displacement parameters AL Alanine APD 4-aminopyridine API Active pharmaceutical ingredient BABA Back-to-back BPY Bipyridine CAF-CA 1:1 caffeine citric acid CAF-2CA Caffeine-citric acid 1:2 cocrystal hydrate 2CAF-HBA bis(caffeine) 4-hydroxybenzoic acid CAF-HNA caffeine 6-hydroxy-2-naphthoic acid 2CAF-PCA bis(caffeine) p-coumeric acid hydrate CASTEP Cambridge Serial Total Energy Package CBZ Carbamazepine CBZ-TFA Carbamazepine trifluoroacetic acid CP Cross polarization CRAMPS Combined rotation and multiple pulse spectroscopy CSA Chemical shift anisotropy CSD Crystal Structure Database CSP Crystal structure prediction CW Continuous wave CYT Cytosine DFT Density functional theory DMSO Dimethyl sulfoxide DMU-OA Dimethylurea-oxalic acid DNP Dynamic nuclear polarisation DQ/SQ Double quantum/single quantum DSC Differential scanning calorimetry DUMBO Decoupling using mind-boggling optimisation DVS Dynamic vapour sorption EAFUS Everything added to food in the United States -Abbreviations- -iv- EFG Electric field gradient EXPRESS Exchange program for relaxing spin systems FDA Food and Drug Administration FID Free induction decay FS Furosemide 2FS-INA Furosemide-isonicotinamide 2:1 cocrystal FSLG Frequency-switched Lee-Goldberg FS-PA Furosemide-picolinamide 1:1 cocrystal FT Fourier Transform FWHM Full width at half maximum GIPAW Gauge-included projector augmented wave GRAS Generally regarded as safe HETCOR Heteronuclear correlation HMQC Heteronuclear multiple quantum correlation INADEQUATE Incredible natural abundance double quantum transfer experiment INA-N-O isonicotinamide-N-oxide IND-NA Indomethacin-nicotinamide IR Infra-red spectroscopy LAG Liquid-assisted grinding LG-CP Lee-Goldberg cross polarization lph Litres per hour MAS Magic angle spinning MD Molecular dynamics MQ Multiple quantum MU-TCA N-methylurea trichloroacetic acid NMR Nuclear magnetic resonance spectroscopy NPX Naproxen NPX-PA Naproxen-picolinamide 1:1 cocrystal NQR Nuclear quadrupole resonance NQS Non-quaternary suppression OGL N-octylglucamine OTFG On-the-fly-generated PABA p-aminobenzoic acid PBE Perdew, Burke and Ernzerhof -Abbreviations- -v- ppm Parts-per-million PPZ Piperazine PR Proline PXRD Powder X-ray diffraction RF Radiofrequency rINADEQUATE Refocused INADEQUATE RMSDs Root-mean-square differences SCXRD Single crystal X-ray diffraction SOLA Solids line shape analysis SSNMR Solid-state nuclear magnetic resonance spectroscopy TBPE Trans-1,2-bis(4-pyridyl)ethylene TEM Transmission electron microscopy TMS Tetramethylsilane TOSS Total sideband suppression TP Tryptophan TY Tyrosine USP Ultra-soft pseudopotential XRD X-ray diffraction -Table of Contents- -vi- Table of Contents Abstract ..................................................................................................................................... i Acknowledgements .................................................................................................................. ii Abbreviations .......................................................................................................................... iii Table of Contents .................................................................................................................... vi Chapter 1: Introduction General remarks ................................................................................................................. 1 Nuclear magnetic resonance spectroscopy ....................................................................... 2 Vector model ........................................................................................................... 2 Rotating frame ........................................................................................................ 4 Relaxation ................................................................................................................ 6 NMR interactions .................................................................................................... 7 NMR in the solid state ............................................................................................. 9 Linewidths in SSNMR ............................................................................................. 11 NMR crystallography .......................................................................................................
Load more

Recommended publications
  • Arxiv:0801.0028V1 [Physics.Atom-Ph] 29 Dec 2007 § ‡ † (People’S China Metrology, Of) of Lic Institute Canada National Council, Zhang, Research Z
    CODATA Recommended Values of the Fundamental Physical Constants: 2006∗ Peter J. Mohr†, Barry N. Taylor‡, and David B. Newell§, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-8420, USA (Dated: March 29, 2012) This paper gives the 2006 self-consistent set of values of the basic constants and conversion factors of physics and chemistry recommended by the Committee on Data for Science and Technology (CODATA) for international use. Further, it describes in detail the adjustment of the values of the constants, including the selection of the final set of input data based on the results of least-squares analyses. The 2006 adjustment takes into account the data considered in the 2002 adjustment as well as the data that became available between 31 December 2002, the closing date of that adjustment, and 31 December 2006, the closing date of the new adjustment. The new data have led to a significant reduction in the uncertainties of many recommended values. The 2006 set replaces the previously recommended 2002 CODATA set and may also be found on the World Wide Web at physics.nist.gov/constants. Contents 3. Cyclotron resonance measurement of the electron relative atomic mass Ar(e) 8 Glossary 2 4. Atomic transition frequencies 8 1. Introduction 4 1. Hydrogen and deuterium transition frequencies, the 1. Background 4 Rydberg constant R∞, and the proton and deuteron charge radii R , R 8 2. Time variation of the constants 5 p d 1. Theory relevant to the Rydberg constant 9 3. Outline of paper 5 2. Experiments on hydrogen and deuterium 16 3.
    [Show full text]
  • NMR Chemical Shifts of Common Laboratory Solvents As Trace Impurities
    7512 J. Org. Chem. 1997, 62, 7512-7515 NMR Chemical Shifts of Common Laboratory Solvents as Trace Impurities Hugo E. Gottlieb,* Vadim Kotlyar, and Abraham Nudelman* Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel Received June 27, 1997 In the course of the routine use of NMR as an aid for organic chemistry, a day-to-day problem is the identifica- tion of signals deriving from common contaminants (water, solvents, stabilizers, oils) in less-than-analyti- cally-pure samples. This data may be available in the literature, but the time involved in searching for it may be considerable. Another issue is the concentration dependence of chemical shifts (especially 1H); results obtained two or three decades ago usually refer to much Figure 1. Chemical shift of HDO as a function of tempera- more concentrated samples, and run at lower magnetic ture. fields, than today’s practice. 1 13 We therefore decided to collect H and C chemical dependent (vide infra). Also, any potential hydrogen- shifts of what are, in our experience, the most popular bond acceptor will tend to shift the water signal down- “extra peaks” in a variety of commonly used NMR field; this is particularly true for nonpolar solvents. In solvents, in the hope that this will be of assistance to contrast, in e.g. DMSO the water is already strongly the practicing chemist. hydrogen-bonded to the solvent, and solutes have only a negligible effect on its chemical shift. This is also true Experimental Section for D2O; the chemical shift of the residual HDO is very NMR spectra were taken in a Bruker DPX-300 instrument temperature-dependent (vide infra) but, maybe counter- (300.1 and 75.5 MHz for 1H and 13C, respectively).
    [Show full text]
  • NMR Spectroscopy Introduction NMR Spectroscopy Is an Analytical Method for Determining the Structure of Organic Compounds
    NMR Spectroscopy Introduction NMR Spectroscopy is an analytical method for determining the structure of organic compounds. Specifically, NMR spectroscopy provides information about the carbon skeleton of an organic molecule. Only elements with an odd number of protons or neutrons in its nucleus can be analyzed by NMR spectroscopy. The most useful type of NMR analyses are proton (1H) and carbon-13 (13C) NMR spectroscopy (Carbon-13 is an isotope of the more naturally abundant carbon 12). We will only study proton NMR spectroscopy. In proton NMR spectroscopy, only H atoms give rise to peaks in the spectrum. Sample Preparation Samples (both solids and liquids) for one-dimensional NMR spectroscopic analysis are usually dissolved in a solvent. Only organic solvents which do not contain H atoms can be used in NMR spectroscopy, otherwise peaks from the solvent will appear in the spectrum. Frequently, deuterated organic solvents are used, which means all of the H atoms of those solvents are replaced by deuterium, the 2H isotope of H, which is not detectable in NMR spectroscopy. Some common solvents that are used for NMR spectroscopic analysis are listed in Table 6.3. Compounds must be completely soluble in the solvent for NMR analysis. Solvent Molecular Formula Carbon tetrachloride CCl4 Deuterated chloroform CDCl3 Deuterated acetone CD6O Deuterated dimethylsulfoxide (DMSO) CD6SO Deuterated methanol CD3OD Table 6.3: Common Solvents Used for NMR Analysis Appearance of the Proton NMR Spectrum Shown below in Figure 6.1 is a typical, one-dimensional proton NMR spectrum. (The term “spectrum” is the singular form of the word; “spectra” is the plural form of the word.) Two-dimensional spectra or NMR spectra of other atoms (i.e., 13C ) look different.
    [Show full text]
  • Proton Nuclear Magnetic Resonance ( H NMR)
    Proton Nuclear Magnetic Resonance (1H NMR) Proton nuclear magnetic resonance (proton NMR, hydrogen-1 NMR, or 1H NMR) is the application of nuclear magnetic resonance in NMR spectroscopy with respect to hydrogen-1 nuclei within the molecules of a substance, in order to determine the structure of its molecules. In samples where natural hydrogen (H) is used, practically all the hydrogen consists of the isotope 1H. A full 1H atom is called protium. Solvents used in NMR., Deuterated solvents especially for use in NMR are preferred, e.g. deuterated water, D2O, deuterated acetone, (CD3)2CO, deuterated methanol, CD3OD, deuterated dimethyl sulfoxide, (CD3)2SO, and deuterated chloroform, CDCl3. However, a solvent without hydrogen, such as carbon tetrachloride, CCl4 or carbon disulfide, CS2, may also be used. Proton NMR spectra of most organic compounds are characterized by chemical shifts in the range +14 to -4 ppm and by spin-spin coupling between protons. The integration curve for each proton reflects the abundance of the individual protons. Simple molecules have simple spectra. The spectrum of ethyl chloride consists of a triplet at 1.5 ppm and a quartet at 3.5 ppm in a 3:2 ratio. The spectrum of benzene consists of a single peak at 7.2 ppm due to the diamagnetic ring current. Multiplicity Multiplicity or coupling is useful because it reveals how many hydrogens are on the next carbon in the structure. That information helps to put an entire structure together piece 1 by piece. In ethanol, CH3CH2OH, the methyl group is attached to a methylene group. The H spectrum of ethanol shows this relationship through the shape of the peaks.
    [Show full text]
  • GC-MS) Techniques and Selected Ion Flow Tube Mass Spectrometry (SIFT-MS) Assessment of Volatiles Produced from Nitric Oxide Producing Smart Dressings
    The detection of trace volatiles from complex matrices using gas chromatography mass spectrometry (GC-MS) techniques and selected ion flow tube mass spectrometry (SIFT-MS) assessment of volatiles produced from nitric oxide producing smart dressings Oliver John Gould A thesis submitted in partial fulfilment of the requirements of the University of the West of England, Bristol for the degree of Doctor of Philosophy Faculty of Health and Applied Sciences, University of the West of England, Bristol 2019 Copyright declaration This copy has been supplied on the understanding that it is copyright material and that no quotation from the thesis may be published without proper acknowledgment. i Acknowledgements I would like to thank my supervisors Professor Norman Ratcliffe, and Associate Professor Ben de Lacy Costello for all their help, guidance, and support over the course of this work, and for their co-authorship on the published versions of chapters 2 and 3. I would also like to thank Dr Hugh Munro and Edixomed Ltd for financial support and scientific guidance with chapter 4. I would like to thank my co-authors on the publication of chapter 2 Tom Wieczorek, Professor Raj Persad. Also thank you to my co-authors on the publication of chapter 3, Amy Smart, Dr Angus Macmaster, and Dr Karen Ransley; and express my appreciation to Givaudan for funding the work undertaken in chapter 3. Thank you also to my colleagues and fellow post graduate research students at the University of the West of England for always being on hand for discussion and generation of ideas. A special mention to Dr Peter Jones who has been mentoring me on mass spectrometry for a number of years.
    [Show full text]
  • Thesis Hsf 2020 Watson Daniel John.Pdf
    Screening of actinobacteria for novel antimalarial compounds Town Daniel John Watson (WTSDAN003) Cape Submitted to the University of Cape Town In fulfilment of the requirementof for the degree: PhD Clinical Pharmacology Faculty of Health Sciences UNIVERSITY OF CAPE TOWN UniversityFebruary 2020 Supervisor: A/Prof Lubbe Wiesner Co-supervisor: Dr Paul Meyers The copyright of this thesis vests in theTown author. No quotation from it or information derived from it is to be published without full acknowledgement of the source. The thesis is to be used for private study or non- commercial research purposes only.Cape Published by the Universityof of Cape Town (UCT) in terms of the non-exclusive license granted to UCT by the author. University DECLARATION It is herewith declared that the work represented in this dissertation/thesis is the independent work of the undersigned (except where acknowledgements indicate otherwise) and has not been submitted at any other University for a degree. In addition, copyright of this thesis is hereby ceded in favour of the University of Cape Town. t5/z/2-02v Date Acknowledgements This thesis is dedicated to my friends and family who gave me the opportunities and support that allowed me to fulfil my dream. Firstly, I would like to thank the NRF and UCT for funding me through my MSc and PhD. Without it, none of this would have been possible. To my supervisor Prof Lubbe Wiesner, thank you for providing me with the opportunity to pursue my interests and passions. Your faith in me and this project kept me going even when I was not sure I could.
    [Show full text]
  • SECONDARY METABOLITES COMPOSITION and GEOGRAPHICAL DISTRIBUTION of MARINE SPONGES of the GENUS Dysidea
    COMPONENT 2C – PROJECT 2C4 Bioprospection & Active Marine Substances Training of Pacifi c students June 2009 MASTER THESIS SECONDARY METABOLITES COMPOSITION AND GEOGRAPHICAL DISTRIBUTION OF MARINE SPONGES OF THE GENUS Dysidea Author: Mayuri Chandra Photo: ©IRD – Eric FOLCHER Photo: ©IRD The CRISP Coordinating Unit was integrated into the Secretariat of the Pacifi c Community in April 2008 to insure maximum coordination and synergy in work relating to coral reef management in the region. The CRISP Programme is implemented as part of the policy developped by the Secretariat of the Pacifi c Regional Environment Programme to contribute to the conservation and sustainable development of coral reefs in the Pacifi c. he Initiative for the Protection and Management of Coral Reefs in the Pacifi c (CRISP), T sponsored by France and prepared by the French Development Agency (AFD) as part of an inter-ministerial project from 2002 onwards, aims to develop a vision for the future of these unique eco-systems and the communities that depend on them and to introduce strategies and projects to conserve their biodiversity, while developing the economic and environmental services that they provide both locally and globally. Also, it is designed as a factor for integration between developed countries (Australia, New Zealand, Japan, USA), French overseas territories and Pacifi c Island developing countries. The CRISP Programme comprises three major components, which are: Component 1A: Integrated Coastal Management and watershed management - 1A1: Marine biodiversity
    [Show full text]
  • Development of Novel Therapeutic and Diagnostic Approaches Utilizing Tools from the Physical Sciences
    DEVELOPMENT OF NOVEL THERAPEUTIC AND DIAGNOSTIC APPROACHES UTILIZING TOOLS FROM THE PHYSICAL SCIENCES by ARUNI PEIRIS MALALASEKERA B.Sc. (Hons), University of Colombo, Sri Lanka 2009 AN ABSTRACT OF A DISSERTATION Submitted in partial fulfillment of the requirements for the degree DOCTOR OF PHILOSOPHY Department of Chemistry College of Arts and Sciences KANSAS STATE UNIVERSITY Manhattan, Kansas 2016 Abstract Numerous Proteases are implicated in cancer initiation, survival, and progression. Therefore, it is important to diagnose the levels of protease expression by tumors and surrounding tissues, which are reflected in blood and tissue samples. Nanoplatforms for Cathepsin(CTS) B and L, matrix metalloproteinases(MMP) 1, 2, 3, 7, 9, 13 and urokinase plasminogen activator(uPA) detection have been synthesized. Nanoplatforms feature a central dopamine-coated core/shell Fe/Fe3O4 nanoparticle. Cyanine 5.5 is permanently tethered to the dopamine ligands via amide bonds. Tetrakis(4-carboxy-phenyl)porphyrin (TCPP) is co-tethered to Fe/Fe3O4/dopamine by means of protease consensus sequences. In the presence of a relevant protease sequence, it is cleaved, releasing TCPP from the nanoplatform. In contrast, Cy 5.5 will remain permanently tethered to the nanoparticle. Therefore, an extensive increase of emission intensity of the fluorescence signal from TCPP is observed. This permits the detection of the activity of proteases at femtomolar levels in biospecimens by fluorescence spectroscopy. 46 breast cancer and 20 healthy human blood serum samples were analyzed. Based on the expression pattern of analyzed enzymes, human breast cancer can be detected at stage I. By monitoring CTS B and L stage 0 detection may be achieved.
    [Show full text]
  • Molecular Diffusive Dynamics in Complex Liquids
    This document is downloaded from Outstanding Academic Papers by Students (OAPS), Run Run Shaw Library, City University of Hong Kong. Title Molecular diffusive dynamics in complex liquids Author(s) Tsang, Yuk Wai (曾郁惠) Tsang, Y. W. (2018). Molecular diffusive dynamics in complex liquids Citation (Outstanding Academic Papers by Students (OAPS), City University of Hong Kong). Issue Date 2018 URL http://dspace.cityu.edu.hk/handle/2031/9126 This work is protected by copyright. Reproduction or distribution of Rights the work in any format is prohibited without written permission of the copyright owner. Access is unrestricted. CITY UNIVERSITY OF HONG KONG DEPARTMENT OF PHYSICS AND MATERIALS SCIENCE BACHELOR OF SCIENCE (HONS) IN APPLIED PHYSICS 2017-2018 DISSERTATION Molecular diffusive dynamics in complex liquids by TSANG Yuk Wai April 2018 ____________________________________________________________________________________________________________________________________________________ This document is downloaded from Outstanding Academic Papers by Students (OAPS), Run Run Shaw Library, City University of Hong Kong. Molecular diffusive dynamics in complex liquids by TSANG Yuk Wai Submitted in partial fulfilment of the requirements for the degree of BACHELOR OF SCIENCE (HONS) IN APPLIED PHYSICS from City University of Hong Kong April 2018 Project Supervisor : Dr. Mavila C Suresh ii ____________________________________________________________________________________________________________________________________________________ This document
    [Show full text]
  • Metabolite Profiling of the Microalgal Diatom Chaetoceros Calcitrans And
    marine drugs Article Metabolite Profiling of the Microalgal Diatom Chaetoceros Calcitrans and Correlation with Antioxidant and Nitric Oxide Inhibitory Activities via 1H NMR-Based Metabolomics Awanis Azizan 1, Muhammad Safwan Ahamad Bustamam 1, M. Maulidiani 1, Khozirah Shaari 1,2, Intan Safinar Ismail 1,2, Norio Nagao 3 and Faridah Abas 1,4,* ID 1 Laboratory of Natural Products, Institute of Bioscience, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia; [email protected] (A.A.); [email protected] (M.S.A.B.); [email protected] (M.M.); [email protected] (K.S.); safi[email protected] (I.S.I.) 2 Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia 3 Laboratory of Marine Biotechnology, Institute of Bioscience, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia; [email protected] 4 Department of Food Science, Faculty of Food Science and Technology, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia * Correspondence: [email protected]; Tel.: +603-8946-8343 Received: 13 April 2018; Accepted: 3 May 2018; Published: 7 May 2018 Abstract: Microalgae are promising candidate resources from marine ecology for health-improving effects. Metabolite profiling of the microalgal diatom, Chaetoceros calcitrans was conducted by using robust metabolomics tools, namely 1H nuclear magnetic resonance (NMR) spectroscopy coupled with multivariate data analysis (MVDA). The unsupervised data analysis, using principal component analysis (PCA), resolved the five types of extracts made by solvents ranging from polar to non-polar into five different clusters. Collectively, with various extraction solvents, 11 amino acids, cholesterol, 6 fatty acids, 2 sugars, 1 osmolyte, 6 carotenoids and 2 chlorophyll pigments were identified.
    [Show full text]
  • Synthesis and Optimization of Novel Amides Using the Ugi Reaction For
    Synthesis and optimization of novel amides using the Ugi reaction for anti-malarial screening A Thesis Submitted to the Faculty Of Drexel University by Khalid Baig S Mirza in partial fulfillment of the requirements for the degree of Doctor of Philosophy May 2010 © Copyright 2010 Khalid Baig S Mirza. All Rights Reserved ii Dedications This thesis is dedicated to my parents Naser Baig Salmani and Mrs. Sirajunnisa, my sister Ayesha Fatima and my brother Hafeez Baig. Their love, support and encouragement have made this possible. iii Acknowledgements First, I would like to thank Almighty God for helping me complete a task I had initiated. I would like to thank my research advisor, Dr. Jean-Claude Bradley, for his guidance and supervision. I would also like to thank my committee members, Prof. Frank Ji, Prof (Chair), Prof. Sally Solomon, Prof. Peter Wade, Prof. Louis Scerbo, Prof. Jun Xi and Prof. Susan Jansen-Varnum (Temple University) for providing their valuable input, reviewing my thesis and participating in the final defense. I would like to thank late Prof. Robert Hutchins who served as the Chair for my candidacy proposal committee. He had being an incredible mentor and teacher to me. I would like to thank Prof. Anthony Wambsgans for his support as a teacher and a friend. I would also like to thank Prof. Daniel King for serving on my proposal committee. I want to thank Prof. Lynn Penn for helping me every time I needed. I really appreciated your pragmatism and advice. I also want to thank Ed Doherty, Virginia Nesmith, Tina Lewinsky and Ed Thorn for providing the administrative support.
    [Show full text]
  • Supporting Information Synthesis of Mono-Functionalized S-Diazocines
    Supporting Information for Synthesis of mono-functionalized S-diazocines via intramolecular Baeyer–Mills reactions Miriam Schehr1, Daniel Hugenbusch1, Tobias Moje1, Christian Näther2 and Rainer Herges*1 Address: 1Otto Diels-Institute for Organic Chemistry, Christian-Albrechts-University, Otto- Hahn-Platz 4, 24118 Kiel, Germany and 2Institute for Inorganic Chemistry, Christian- Albrechts-University, Max-Eyth-Str. 2, 24118 Kiel, Germany Email: Rainer Herges* - [email protected] * Corresponding author Analytical equipment, experimental procedures, spectral data and crystallographic data Table of contents I. Analytical equipment∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S2–S3 II. Syntheses∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S4–S27 III. Isolated byproduct reductive azo coupling∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S28–S29 IV. UV–vis switching experiments∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S30 V. Crystallographic data compound 3 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S31–S33 I. Analytical equipment NMR spectroscopy NMR spectra were measured in deuterated solvents (Deutero). To reference the NMR spectra the following solvent signals were used [1]: solvent degree of deuteration 1H signal 13C signal acetone-d6 99.8 % 2.05 (quintet) 29.84 (septet) chloroform-d1 99.8 % 7.26 (s) 77.16 (triplet) DMSO-d6 99.8 % 2.50 (s) 39.52 (septet) NMR measurements
    [Show full text]