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«Kinetic Investigations of Thiolate Protected Gold Nanoparticles: Protein Interactions, Electron Transfer, and Precursor Formation By Brian N. Turner ...»

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Kinetic Investigations of Thiolate Protected Gold Nanoparticles: Protein Interactions,

Electron Transfer, and Precursor Formation

By

Brian N. Turner

Dissertation

Submitted to the Faculty of the

Graduate School of Vanderbilt University

in partial fulfillment of the requirements

for the degree of

Doctor of Philosophy

in

Chemistry

December, 2011

Nashville, Tennessee

Approved:

Professor David E. Cliffel

Professor John A. McLean

Professor James E. Crowe, Jr.

Professor David W. Wright In Memory of Sharon Rose Turner and Ruth Shelton Turner A special thanks to Mom, Dad, April, Eric, Gramps, Keith, and Patti Lovingly dedicated to Mary Pat ii

ACKNOWLEDGEMENTS

Acknowledgements of people who helped along the way are included at the end of each chapter, but I would like to reserve this section to thank people who helped in unique ways.

As for my committee, I will open with Dr. David Cliffel. I have always appreciated your knowledge and creativity in generating new ideas. I have also appreciated the freedom I have had to go in my own direction with research that seems very unique to this lab. Also, I really appreciate your humanistic approach to leaves of absence, and never once interfering in personal business. This was especially appreciated as many personal crises and family crises seemed to continually arise over the last six years, and I am not sure I would have been able to deal with them appropriately in a lot of other situations. On a lighter note, it was a pleasant surprise to work for someone who would have the group over to play strategy games, volleyball, and generously provided wonderful food to a somewhat larger research group. Finally, thanks for having the patience to allow me to work here over a six year period, all the while providing financial support.

Dr. Wright, I have always secretly appreciated your no-holds-barred attitude, and tellit-like-it-is approach to committee meetings. I think this is a very important trait when it comes to making sure that the science we practice is legitimate. My favorite part about your approach is your intensity about the science because I believe that it should be exciting and meaningful to the researchers instead of just a means to a job. Until I saw

–  –  –

design really is in terms of practical potential and elegance.

Dr. McLean, I would like to thank you for some of the most interesting science conversations I have had during my stay here. My personal favorite was the discussion about how to weigh an electron accurately. I always looked forward to your classes, because you have a unique gift of making complicated topics seem approachable and exciting. I also enjoyed hanging out with you socially in Atlanta during Pittcon. We will have to meet at another conference and play that shuffleboard game again.

Finally, Dr. Jim Crowe, until I met you, I had not met somebody who works on such a high level in their field that is as approachable as you are. Additionally, I appreciate that you are always very thoughtful with your questions.

It would take me way too long to thank everybody individually in my research group for sitting through my practice exams and the like. Thank you to everyone, as it was much appreciated.

Graduate school can be a difficult time, so I would like to thank Bill Evans, Vanessa Phelan, Dr. Victor Ghidu, Easton Selby, Danielle “Watkins” Kimmel, the volleyball crew, the soccer crew, the old Magic the Gathering crew (ignore that), and the current strategy gaming crew for keeping things light when times were not. I would also like to thank all of my old friends back home and elsewhere for staying in touch, offering encouragement, and giving me an excuse to leave town every here and again, especially Mike Pateras, Lora Robinson, Greg Raffio, Alicia DiMarco, Mykola Bilokonsky, and Ryan Stolte-Sawa.

–  –  –

suffice it to say that when things got tough here, I would not have continued along if not for your encouragement and belief. I love you all.

And Mary Pat, I just want you to know that I would not have finished this if you hadn’t pushed me. And Dad, I never would have gotten into this in the first place without your constant support and help.

I would like to acknowledge the following sources of funding: the National Institutes of Health Sections on General Medicine [NIH/NIGMS (R01 GM 076479)] and Allergies and Infections Disease- Southeastern Regional Center for Excellence in Biodefense [NIH/NIAID/SERCEB (U54 AI057157)], the Defense Threat Reduction Agency, the Research Coporation, the Vanderbilt University Graduate School and their Travel Grant Program (which provided for trips to Pittcon 2007 and ACS National Meeting Fall 2010), Oak Ridge National Laboratory Center for Nanophase Materials Science and the Vanderbilt University Department of Chemistry Teaching Assistant Program.

–  –  –

DEDICATION

ACKNOWLEDGEMENTS

LIST OF TABLES

LIST OF FIGURES

INTRODUCTION: SYNTHESIS AND CHARACTERIZATION OF VARIOUS

I.

THIOLATE PROTECTED GOLD NANOPARTICLES AS PREPARED BY





MODIFIED BRUST METHODS

Introduction

Background

Synthetic Routes

Functionalization of Thiolate Protected Gold Nanoparticles.......5 Characterization Methods for MPCs

Methods

Instrumentation for Routine Nanoparticle Characterization...... 14

LINEAR EPITOPE MAPPING APPROACH TO LOCATE BINDING “HOT

II.

SPOTS” IN THE CONFORMATIONAL ANTIGENIC SITE A OF HUMAN

RESPIRATORY SYNCYTIAL VIRUS (HRSV) FUSION PROTEIN (F)......... 15 Introduction

Background

Human Respiratory Syncytial Virus

Epitope Mapping

Quartz Crystal Microbalance (QCM)

Methods

Instrumentation

Materials

Peptide Synthesis

Formation of peptide SAMs

ELISA Stepwise linear epitope mapping of the full length RSV F Antigenic Site A

–  –  –

GOLD NANOPARTICLES PRESENTING PEPTIDES AS BIOMIMCS

III.

OF HRSV F PROTEIN ANTIGENIC FUNCTION

Introduction

Background

Nanoparticles Presenting Peptides as Antigenic Mimics........... 54 Quartz Crystal Microbalance Immunosensing

Methods

Materials

Peptide Synthesis

Synthesis of Au216Tiopronin129 Nanoparticles

Synthesis of Au118Tiopronin71 Nanoparticles

Synthesis of Au696Tiopronin265 Nanoparticles

Place Exchange to Form Series 3 Peptide-Nanoparticle Conjugates

QCM Immunosensor Construction and Detection of HRSV..... 67 Adaptation of the QCM Immunosensor to Detect Peptide Presenting Gold Nanoparticles

Results and Discussion

QCM Immunosensor for HRSV

Development of Peptide Presenting Gold Nanoparticles........... 73 Detection of Peptide Presenting Gold Nanoparticles with the QCM Immunosensor for HRSV

Acknowledgements

SECM OF “WIRED” GOLD NANOPARTICLES TO DETERMINE

IV.

ELECTRON TRANSFER KINETICS: PROOF OF CONCEPT FOR

POTENTIAL COMPONENTS IN NANOMOLECULAR CIRCUITS............... 87 Introduction

Background

Molecular Electronics

Electrochemical Properties of Gold Nanoparticles

Molecular Wire Molecules

Scanning Electrochemical Microscope

Methods

Materials

Synthesis of Au1120 Dodecanthiolate690

Synthesis of Au228Octanethiol92

–  –  –

KINETIC INVESTIGATION OF TIOPRONIN PROTECTED GOLD

V.

NANOPARTICLE PRECURSOR FORMATION

Introduction

Background

Methods

Materials

UV-Visible Spectroscopy Kinetics Experiments

Results and Discussion

Preliminary Observations

UV-Visible Spectroscopy

Acknowledgements

SUMMARY OF CONCLUSIONS AND SUGGESTIONS FOR FUTUREVI. WORK

Summary of Conclusions

Suggestions for Future Work

Biomimetic Nanoparticles

Wired Nanoparticles

Nanoparticle Precursor Formation

Appendix

A. THERMAL GRAVIMETRY-MASS SPECTROMETRY AND

ELEMENTAL ANALYSIS OF TIOPRONIN PROTECTED GOLD

NANOPARTICLES

–  –  –

D. PURIFICATION AND CHARACTERIZATION DATA FOR PEPTIDES

USED IN THIS STUDY OR OTHERWISE DESIGNED AND PURIFIED..... 158

ADDENDUM TO “COLOR MY NANOWORLD” EXERCISE USED AT

E.

THE VANDERBILT SUMMER ACADEMY

REFERENCES

CURRICULUM VITAE

–  –  –

1. Summary of reported HRSV escape mutations in HRSV F antigenic site A............. 21

2. Tabulated characterization data for peptides purified by this author.

3. Peptides designed to be evaluated by the QCM step-wise linear epitope mapping method.

4. Peptides evaluated against palivizumab in an ELISA assay.

Student’s t-tests for peptide ELISA

5.

6. Peptides that were conjugated to nanoparticles in this study.

7. Nanoparticle mimics studied with the QCM HRSV immunosensor.

8. Summary of mimic A detection at various concentrations, along with sensor characterization data

9. electron transfer kinetic constants determined for Au228Octanethiol92-nPEPEPSn.... 123 Rate data for the reaction of Au(III)Cl4 - with tiopronin in MeOH at unfixed ionic 10.

strength.

11. Rate data at fixed [RSH] and [Au(III)] with variable [H+] (adjusted with perchloric acid/MeOH solution) and [Cl-] (adjusted with sodium chloride/MeOH solution)... 145

12. Rate data for conditions designed to test saturation kinetics of the tiopronin/tetrachloroaurate system.

13. Elemental analysis-calculation compared to two different TGA-TEM calculations of molecular formula.

14. Characterization data for peptides synthesized by this author.

–  –  –

15. Modified Brust reaction scheme for polar ligands.

16. Examples of thiolate ligands used in the synthesis of water soluble Au MPCs............4

17. Scheme of the solution phase place-exchange reaction.

18. The stoichiometry of incoming to exiting ligand is 1:1.

19. Chart of the different relative rates at which place-exchange and (possibly) migration occur

The non-covalent interaction based place-exchange reaction.49

20.

21. Cartoon schematic of an HRSV virion.

22. HRSV F protein, showing the head, neck, and stalk structure.

23. ELISA study of synthetic peptides from Rutledge and coworkers

24. QCM graph illustrating the binding of BSA to bare gold and PZ to a mixed SAM of peptide 2 and tiopronin.

25. QCM graph illustrating the binding of BSA to bare gold and PZ to a mixed SAM of peptide 8 and tiopronin.

26. QCM graph illustrating the binding of BSA to bare gold and PZ to a mixed SAM of peptide 10 and tiopronin.

27. Results of the optimized peptide ELISA

28. A conceptual interpretation of PZ approaching the synthetic peptide epitope........... 47

29. Motavizumab peptide epitope of HRSV F (gray) interacting with the light chain (blue) and heavy chain (green).

30. Comparison of the glutathione (top) and tiopronin (bottom) ligands

31. 10-amino acid HA peptide on a 3-D gold tiopronin nanoparticle

32. Loop presenting MPCs (left) shown compared to the native protein

–  –  –

34. Detection of HRSV with the QCM-PZ immunosensor.

35. Detection and control experiments for the QCM-PZ immunonosensor.

36. H NMR, with double water-gate solvent suppression, of a peptide-nanoparticle conjugate

37. Detection of Au696Tiopronin255Peptide(3-F)10 by the QCM immunosensor with and without PZ.

38. Representative QCM mass versus time curves at various concentrations of mimic A during the detection step.

39. Plot to determine the time constant for mimic A binding to the Palivizumab sensor. 80

40. Plot of individual time constants determined for each concentration.

41. Plot to determine binding coefficients using the four lowest concentration samples.. 83

42. Nanoparticle-bipyridine redox switch

43. Cowpea mosaic virus-gold nanoparticle-molecular wire conjugate molecular electronic nanosensor.

44. Square wave voltammogram of AuHexanethiolate nanoparticles.

45. The molecular wire ligand

46. Current-voltage profiles of molecular wires sandwiched between gold wires........... 97

47. Read-write computing system with gold electrodes sandwiching molecular wires.... 98

48. SECM as a useful imaging technique in biological and materials applications........ 101

49. SECM experimental design

50. SECM approach curves of AuAlkanethiolate nanoparticles

Proof of concept experiments to confirm whether “wired” AuDodecanethiol 51.

nanoparticles (left) exhibit faster electron transfer than their “unwired” precursors (right)

52. MALDI-IM mass spectrum of AuDodecanethiolate nanoparticles functionalized with the molecular wire.

–  –  –

SECM approach curve with 1V Pt UME through larger “wired” AuDodecanethiolate 54.

nanoparticles

Comparison of 1H NMR spectra of dodecanethiol gold nanoparticles synthesized by 55.

the Brust method (blue), and by the method of Rowe and coworkers (red)............. 120

56. SECM approach curve through Au228Octanethiol90PEPEPS2, Au228Octanethiol90PEPEPS2.6, and Au228Octanethiol92.

57. Nanoparticle and ring complex structures

Time resolved UV-Vis spectra of AuCl4 - undergoing reduction by tiopronin.......... 134 58.

59. UV-Vis region containing the saddle at 289 nm for the gold(III)/tiopronin system. 135



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