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Design, Synthesis, and Supramolecular Surface Chemistry Of DESIGN, SYNTHESIS, AND SUPRAMOLECULAR SURFACE CHEMISTRY OF BI- AND TRIDENTATE SURFACE ANCHORS FOR NANOSCIENCE AND NANOBIOTECHNOLOGY A Dissertation Presented to The Graduate Faculty of the University of Akron In Partial Fulfillment Of the Requirements for the Degree Doctor of Philosophy Hui Wang August, 2007 DESIGN, SYNTHESIS, AND SUPRAMOLECULAR SURFACE CHEMISTRY OF BI- AND TRIDENTATE SURFACE ANCHORS FOR NANOSCIENCE AND NANOBIOTECHNOLOGY Hui Wang Dissertation Approved: Accepted: _______________________ _______________________ Advisor Department Chair Dr. Jun Hu Dr. Kim C. Calvo _______________________ _______________________ Committee Member Dean of the College Dr. Gerald F. Koser Dr. Ronald F. Levant _______________________ _______________________ Committee Member Dean of the Graduate School Dr. David A. Modarelli Dr. George R. Newkome _______________________ _______________________ Committee Member Date Dr. Claire A. Tessier _______________________ Committee Member Dr. Robert R. Mallik ii ABSTRACT This dissertation describes the design, synthesis, and supramolecular surface chemistry of bi- and tri-dentate surface anchors for nanoscience and nanobiotechnology. Molecular electronic device candidates, based on the tridentate surface anchor 2,4,9-trithia-tricyclo[3.3.1.13,7]decane, were used to bridge two ruthenium metal clusters. These well-designed ruthenium complexes were used as nanometer-sized molecular connector/metal cluster models to investigate the surface binding characteristics of tridentate surface anchor-metal junctions. Bi-dentate surface anchors, 1,4-dimercapto-2,3-dimethyl-butane- 2,3-diol and 4,5-dimethyl-2-(4-vinyl-phenyl)-[1,3,2]dioxaborolane-4,5-dithiol, were synthesized. They were used as ligands for stabilizing gold nanoparticles by two methods: direct reduction reaction, and ligand exchange reaction with triphenylphosphine-stabilized gold nanoparticles. The orientation of the bi-dentate surface anchor-based self-assembled monolayers (SAMs) on the flat gold surface was studied by Polarization Modulation Fourier Transform Infrared Reflection Absorption Spectroscopy (PM-FTIRRAS), which showed freestanding surface binding capability of the bi-dentate surface anchors. New methods to conjugate carbohydrates on the surfaces of gold nanoparticles by the tridentate surface anchor, 2,4,9-trithia-tricyclo[3.3.1.13,7]decane, were studied. iii Several derivatives of 7-substituted-2,4,9-trithia-tricyclo[3.3.1.13,7]decane were designed and synthesized for this purpose. Two different functional groups, methoxyamino group and terminal alkyne group, can be used to bind to reductive sugars and azido-sugars respectively. These compounds were used as ligands for stabilizing gold nanoparticles by ligand exchange reaction with triphenylphosphine-stabilized gold nanoparticles. The PM-FTIRRAS characterizations of the tri-dentate surface anchor SAM on flat gold surfaces were also studied. iv DEDICATION To my parents and my wife v ACKNOWLEDGEMENTS I would like to thank my advisor, Dr. Jun Hu, for his guidance and patience during my doctoral study. I would like also to thank my dissertation committee members, Dr. Gerald F. Koser, Dr. David A. Modarelli, Dr. Claire A. Tessier, and Dr. Robert R. Mallik for their comments and suggestions. Dr. Ziegler and Youngs research groups are acknowledged for obtaining and solving the X-ray crystallography presented in this work. Dr. Venkat Dudipala is acknowledged for the 2D gHSQC NMR measurement. Dr. Mallik’s group is acknowledged for obtaining the conductance-voltage data of Al/CdS/tridentate surface anchor/Pb tunnel junctions. I also want to thank Yubiao Liu, Chalermchai Khemtong, Serhan Boduroglu, Debanjan Sarkar, Jacob Weingart, and all members of my research group. They have created an effective working atmosphere and helped me in different ways. I want to thank my parents and family members for their love, support and encouragement. I also want to express my special thanks to my wife, Yao, for her love, patience, and everything she has done for me. vi TABLE OF CONTENTS Page LIST OF FIGURES………………………………………………………………. xiv LIST OF SCHEMES…………….……………………………………………..… xvii LIST OF TABLES…………….………………………………………………… xviii CHAPTER I INTRODUCTION……………………………………………………………... 1 1.1 Background of Molecular Surface Anchors…………………..………….. 1 1.2 Plan of Research …..………………………………………………….….. 3 1.3 Layout of Dissertation .……………………………………………….….. 5 II CONSTRUCTION OF TRIPODAL MOLECULAR SURFACE ANCHOR- BASED MOLECULAR TUNNELING JUNCTIONS…………………………. 6 2.1 Introduction…………………….…………………………………….…… 6 2.1.1 Design of the Nanometer-Sized Molecular Connector/Metal Cluster System………………………………………………...….. 9 2.1.2 Electronic Properties of the Nanometer-Sized Molecular Connector………………………………………………………..... 10 2.1.3 Ruthenium Clusters at the End of the Nanometer-Sized Molecular Connector………………………………………………………..... 15 2.2 Results and Discussion…..………………………………………………... 16 2.2.1 Synthesis of Molecular Devices…….…….…………………..….. 16 2.2.2 Fabrication of Nanometer-Sized Molecular Connector-Metal Cluster System………………………………….……………..….. 20 vii 2.2.3 Characterizations of Nanometer-Sized Molecular Connector- Metal Cluster System……………….…….…………………..….. 21 2.2.4 NMR and UV-Vis Analysis of Nanometer-Sized Molecular Connector-Metal Cluster System…….…….……………………... 30 2.3 Experimental Section……………………………………………………... 34 2.3.1 General Procedures………………………. .……………………... 34 2.3.2 Synthesis of 2,4,9-Trithia-tricyclo[3.3.1.13,7]decane-7-yl- methanol…………….……………………. .……………………... 34 2.3.3 Synthesis of 2,4,9-Trithia-tricyclo[3.3.1.13,7]decane-7- carbaldehyde…………………..…………. .……………………... 35 2.3.4 Synthesis of 2,4,9-Trithia-tricyclo[3.3.1.13,7]decane-7-yl- ethyne……………….……………………. .……………………... 36 2.3.5 Synthesis of 1,4-Bis((7-2,4,9-trithiaadamantyl)ethynyl) Benzene…………………………………... .……………………... 37 2.3.6 Synthesis of 1,4-Bis(7-2,4,9-trithiaadamantyl) Butadiyne….......... 37 2.3.7 Preparation of Complex 5 ………………………………………... 38 2.3.8 Preparation of Complex 7 ………..…………………………….... 38 2.3.9 Preparation of Complex 9 ……………………………………....... 39 2.4 Conclusions………………………………………………………………... 39 III STABLIZE GOLD NANOPARTICLES WITH DITHIOL LIGANDS………... 40 3.1 Introduction..……………………………………………………………… 40 3.1.1 Stabilization of Metal Nanoparticles…………………………….. 40 3.1.1.1 Charge Stabilization…………………………………. 41 viii 3.1.1.2 Steric Stabilization……….……………………………. 42 3.1.1.3 Electrosteric Stabilization ….…………………..……... 43 3.1.1.4 Stabilization by Ligands………………………………. 44 3.1.2 Preparation and Purification of Gold Nanoparticles……………… 45 3.1.2.1 Triphenylphosphine-Stabilized Gold Nanoparticles...... 45 3.1.2.2 The Brust-Schiffrin Method………………………........ 46 3.1.2.3 Gold Nanoparticles Stabilized by Other Sulfur- Containing Ligands……………………….………........ 47 3.1.2.4 Purification of Gold Nanoparticles………………......... 48 3.1.3 The Surface Plasmon Band of Gold Nanoparticles and Ultraviolet- Visible Spectroscopy…………………............................................ 49 3.1.4 Size, Shape and Size Distribution of Gold Nanoparticles………… 50 3.1.5 Polarization Modulation Fourier Transform Infrared Reflection Absorption Spectroscopy (PM-FTIRRAS) Characterization of Self-Assembled Monolayers (SAMs) on the Gold Surface……..… 50 3.1.6 Preparation and Characterization of Dithiol Ligand-Stablized Gold Nanoparticles……………………………………………..……..… 52 3.2 Results and Discussion .…………………………………………………… 54 3.2.1 Synthesis of 1,4-Dimercapto-2,3-dimethyl-butane-2,3-diol.……… 54 3.2.2 Synthesis of 4,5-Dimethyl-2-(4-vinyl-phenyl)-[1,3,2] dioxaborolane-4,5-dithiol…………………………………………. 57 3.2.3 Preparation and PM-FTIRRAS Characterization of Self-Assemble Monolayers (SAM) of 1,4-Dimercapto-2,3-dimethyl-butane-2,3- diol (dioldithiol) on the Flat Gold Surface.……………………….. 59 ix 3.2.4 Ligand Exchange Reaction Between 1,4-Dimercapto-2,3- dimethyl-butane-2,3-diol (dioldithiol) and Triphenylphosphine- stabilized Gold Nanoparticles…………..…………………………. 61 3.2.5 Preparation of Gold Nanoparticles Stabilized by 1,4-Dimercapto- 2,3-dimethyl-butane-2,3-diol …...………………………………… 67 3.3 Experimental Section……………………………………………………… 70 3.3.1 General Procedures ………..…………………………….……... 70 3.3.2 Synthesis of 1,4-dibromo-2,3-dimethyl-2-butene …….………... 70 3.3.3 Synthesis of 2,2’-Dimethyl-[2,2’]-bioxiranyl ………...………... 71 3.3.4 Synthesis of S-(4-Acetylsulfanyl-2,3-dihydroxy-2,3- dimethylbutyl) Thioacetate …………………………….……... 72 3.3.5 Synthesis of 1,4-Dimercapto-2,3-dimethylbutane-2,3-diol ….…. 73 3.3.6 Synthesis of 4,5-Dimethyl-[1,2]dithiane-4,5-diol ………………. 74 3.3.7 Synthesis of S-[5-Acetylsulfanyl-4,5-dimethyl-2-(4- vinylphenyl)-[1,3,2]dioxaborolan-4-yl] Thioacetate ………….. 75 3.3.8 Synthesis of 4,5-Dimethyl-2-(4-vinylphenyl)- [1,3,2]dioxaborolane-4,5-dithiol …………………………….... 76 3.3.9 General Procedure of Preparing Self-Assemble Monolayers (SAM) on the Flat Gold Surface ………………........................... 77 3.3.10 PM-FTIRRAS Characterization of 1,4-Dimercapto-2,3- dimethyl-butane-2,3-diol SAM on the Gold Surface …................ 78 3.3.11 Ligand Exchange Reaction Between 1,4-Dimercapto-2,3- dimethyl-butane-2,3-diol and Triphenylphosphine-stabilized Gold Nanoparticles ……………................................................... 78 3.3.12 Preparation of 1,4-Dimercapto-2,3-dimethyl-butane-2,3-diol- Stabilized Gold Nanoparticles by Direct Reduction Reaction ….. 78 x 3.3.13 Ultraviolet Visible Spectroscopy of Gold Nanopartcles ……… 79 3.4 Summary …..…………………………………………………………… 79 IV GOLD NANOPARTICLES WITH MOLECULAR RECOGNITION SITES ON THE SURFACE………………………………………………………….. 80 4.1 Introduction .…………………………………………………………….
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