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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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The solution was allowed to warm to RT. 0.80 g of tetramethylthiuram disulfide was dissolved in 10 mL of freshly distilled dichloromethane and purged with Ar. The Grignard solution was, again, cooled in an ice bath, and the thiuram solution was added cautiously. The solution was filtered, evaporated, and eluted on a silica gel column with DCM/hexanes. 1H NMR 7.78 ppm, d, 2H, J = 8.44 Hz (aromatic close to iodine); 7.19 ppm, d, 2H, J = 8.44 Hz (aromatic close to thiuram); 3.57 ppm, s, 3H, thiuram methyl a);

3.50 ppm, s, 3H, (thiuram methyl b).

Synthesis of p-tetramethylthiurylphenylethynylbenzene (PEPSTMT) via Sonogashira Cross-Coupling of IPhSTMT

0.47 g IPhSTMT from the previous synthesis (1.55 mmol), 121 mg Pd(PPh3)4 (10 mol%), and 29 mg CuI (10 mol %) were dissolved in freshly distilled Hunig’s base (9mL) and THF (4mL), and purged with argon. 186 µL of phenylacetylene was syringed in, and the reaction was stirred for 24 hours at 100 °C. The product was extracted in ether, washed 3x with water, dried over MgSO4, filtered, and evaporated. The product was further purified on a silica gel column with DCM/hexanes. 1H NMR: 7.73 ppm, m, 4H; 7.49 ppm, m, 5H (aromatic); 3.56 ppm, s, 3H (first thiuram methyl); 3.35 ppm, s, 3H (second thiuram methyl). Reaction worked extremely well, but was irreproducible in later trials. This was attributed this to humidity, as every repeat was performed in the summer, and a Schlenk line was not utilized (only argon balloons).

Deprotection of PEPSTMT to p-mercaptophenylethynylbenzene (PEPSH) The product above was deprotected by NaOH (24 mg), Zn (3 mg), H2O 1.8 mL, THF (3 mL) and stirring for 3 hours, followed by quenching and acidifying with HCl. A greenish, semi-crystallin solid was obtained and recrystallized once from iso-octane. 1H NMR 7.71 ppm, m, 2H; 7.59 ppm, m, 2H; 7.51 ppm, m, 3H; 7.07 ppm, m, 2H (aromatic); 2.34 ppm, bs, 1H (thiol). Thiuram-like byproduct present, 3.62 ppm, bs, 6H (in thiuram it is at 3.60 ppm).

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I would like to thank Bryan Ringstrand for his constant and willing help in various aspects of the organic syntheses: devising reaction pathways, preparing solvents, using catalysts, purification, and setting up reactions under inert atmosphere. I would also like to thank Dr. Piotr Kaszynski for recommending the triisopropylsilanethiol as a protected thiolating reagent. I would also like to acknowledge some assistance from Joe Keene during his rotation in the lab.

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Table 14: Characterization data for peptides synthesized by this author. The sequences are labeled as the single letter amino acid abbreviations, the identity of the termini (unlabeled termini indicates that both termini were left as the free amine or carboxylic acid, CONH2 is an amidated C terminus, and Ac is an acetylated N terminus), and (PEG) 6 indicates a hexaethyleneglycol spacer. Retention times are from reverse phase, preparatory scale HPLC and represent the time (rounded to the nearest minute) at which collection of the highest absorbing fraction was began. Calculated m/z values represent the value calculated for the most abundant isotope for reflectron mode, or the average mass for linear mode. The most prevalent ions in the MALDI spectrum of the highest absorbing fraction were recorded. [M + H] and [M + Na] were assumed to be indicative of a successful synthesis, while [M + O] is indicative of an oxidized methionine residue (not generally considered to effect peptide-antibody binding). Mode indicates reflectron (R) or linear (L) time of flight for the MALDI characterization.

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The Vanderbilt Summer Academy is a collaborative effort within Vanderbilt that invites gifted high school underclassmen to campus in order to learn about nanoscale science and engineering. Every year, the research group of David Cliffel participates and teaches kids about gold nanoparticles through a brief lecture followed by a hands-on experience.

For that section, an article from J.Chem. Ed from Mirkin and coworkers, entitled “Color my Nanoworld” is used, in which the students make citrate stabilized gold nanoparticles and study their properties colorimetrically. In order to enhance this experience, I designed an addendum to the experience where the students study hexanethiol protected

gold nanoparticles from a Brust synthesis. The addendum is as follows:

Brian Turner 6-23-10 Monolayer Protected Cluster Supplement for “Color my Nanoworld” Vanderbilt Summer Academy Chemicals required

–  –  –

4. NaBH4: For a 30 mM solution, dissolve _____g of NaBH4 in _____mL of water. This solution should be prepared immediately before use. It is possible that this solution loses its potency, and requires a new preparation part way through the lab.

Procedure for the Preparation of 3nm Gold Hexanethiol Monolayer Protected Clusters (MPCs)

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2. Option A: Cap and shake the vial vigorously to temporarily mix the layers together. Option B: Use a dropper to mix the layers over and over. Either method should be done until you have 1 red layer and 1 colorless layer (not faintly yellow).

3. Use a pipet to remove the clear aqueous layer (which should be dilute hydrobromic acid). The remaining layer should be toluene with 1mM tris(tetraoctylammonium) gold(III).

4. To the red organic layer, add ____ µL of C6SH (3:1 molar excess).

Subsequent reduction of gold(III) to gold(I) may be observed by a color change from red to colorless.

5. Immediately upon fading of the red color, CAUTIOUSLY add 1 dropper full of NaBH4 solution (in the hood). Continuously mix with the dropper.

Capping and shaking is an option, but should be done carefully while holding the lid on very tightly, and easing the lid off after reduction. This should render a black solution.


1. It should be noted that these particles are more stable than the citrate particles because they are protected by covalently bonded layer of hexanethiolate molecules.

2. Throughout the course of all of the experiments, the children have observed a variety of colors.

–  –  –

3. This is a good time to tell the kids about how scientists can use light to gain details about molecules and particles such as their size.

The numbers are left blank so that the teaching assistants customize to suit the class.

–  –  –

1. Cliffel, D. E., Turner, B. N. and Huffman, B. J. (2009) Nanoparticle-based biologic mimetics. Wiley Interdisciplinary Reviews-Nanomedicine and Nanobiotechnology, 1, 47-59.

2. Faraday, M. (1857) The Bakerian Lecture: Experimental Relations of Gold (and Other Metals) to Light. Philos Trans R Soc London, 147, 145.

3. Turkevich, J., Stevenson, P. C. and Hillier, J. (1951) A Study of the Nucleation and Growth Processes in the Synthesis of Colloidal Gold. Discuss Faraday Soc, 11, 55-75.

4. Brust, M., Walker, M., Bethell, D., Schiffrin, D. J. and Whyman, R. (1994) Synthesis of thiol-derivatized gold nanoparticles in a two-phase liquid-liquid system. Chem Commun, 7, 801-902.

5. Templeton, A. C., Wuelfing, W. P. and Murray, R. W. (2000) MonolayerProtected Cluster Molecules. Acc Chem Res 33, 27-36.

6. Niemeyer, C. M. (2001) Nanoparticles, Proteins, and Nucleic Acids:

Biotechnology Meets Materials Science. Angew Chem Int Ed, 40.

7. Rowe, R. P., Plass, K. E., Kim, K., Kurdak, C., Zellers, E. T. and Matzger, A. J.

(2004) Single-Phase Synthesis of Functionalized Gold Nanoparticles. Chem Mater, 16, 3513-3517.

8. Templeton, A. C., Chen, S., Gross, S. M. and Murray, R. W. (1999) WaterSoluble, Isolable Gold Clusters Protected by Tiopronin and Coenzyme A Monolayers. Langmuir, 15, 66-76.

9. Templeton, A. C., Cliffel, D. E. and Murray, R. W. (1999) Redox and Fluorophore Functionalization of Water-Soluble, Tiopronin-Protected Gold Clusters. J Am Chem Soc, 121, 7081-7089.

10. Yee, C., Scotti, M., Ulman, A., White, H., Rafailovich, M. and Sokolov, J. (1999) One-Phase Synthesis of Thiol-Functionalized Platinum Nanoparticles. Langmuir, 15, 4314-4316.

11. Yee, C. K., Jordan, R., Ulman, A., White, H., King, A., Rafailovich, M. and Sokolov, J. (1999) Novel One-Phase Synthesis of Thiol-Functionalized Gold Palladium and Iridium Nanoparticles Using Superhydride. Langmuir, 15, 3486Croce, T. A., Hamilton, S. K., Chen, M. L., Muchalski, H. and Harth, E. (2007) Alternative o-Chinodimethane Crosslinking Precursors for Intramolecular Chain Collapse Nanoparticles. Macromolecules, 40, 6028-6031.

13. Ahmed, F., Photos, P. J. and Discher, D. E. (2006) Polymersomes as Viral Capsid Mimics. Drug Dev Res, 67, 4-14.

14. Joralemon, M. J., Smith, N. L., Holowka, D., Baird, B. and Wooley, K. L. (2005) Antigen-Decorated Shell Cross-Linked Nanoparticles: Synthesis, Characterization, and Antibody Interactions. Bioconjugate Chem, 16, 1246-1256.

15. Taubert, A., Napoli, A. and Meier, W. (2004) Self-assembly of reactive amphiphlic block copolymers as mimetics for biological membranes. Curr Opin Chem Bio, 8, 598-603.

16. Bosio, C. M., Moore, B. D., Warfield, K. L., Ruthel, G., Mohamadzadeh, M., Aman, M. J. and Bavari, S. (2004) Ebola and Marburg virus-like particles activate human myeloid dendritic cells. Virology, 326, 280-287.

17. Noad, R. and Roy, P. (2003) Virus-like particles as immunogens. Trends Microbiol, 11, 438-444.

18. Ogasawara, Y., Amexis, G., Yamaguchi, H., Kajigaya, S., Leppla, S. H. and Young, N. S. (2006) Recombinant Viral-like Particles of Parvovirus B19 as Antigen Carriers of Anthrax Protective Antigen. in vivo, 20.

19. Raja, K. S., Wang, Q. and Finn, M. G. (2003) Icosahedral Virus Particles as Polyvalent Carbohydrates Display Platforms. ChemBioChem, 4, 1348-1351.

20. Szécsi, J., Boson, B., Johnsson, P., Dupeyrot-Lacs, P., Matrosovich, M., Klenk, H.-D., Klatzmann, D., Volchkov, V. and Cosset, F.-L. (2006) Induction of Neutralising antibodies by virus-like particles harbouring surface proteins from highly pathogenic H5N1 and H7N1 influenza viruses. Virol J, 3.

21. Wang, Q., Lin, T., Tang, L., Johnson, J. E. and Finn, M. G. (2002) Icosahedral Virus Particles as Addressable Nanoscale Building Blocks. Angew Chem Int Ed 41, 459-462.

22. Jahanshahi, M., Williams, S., Lyddiatt, A. and Shojaosadati, S. A. (2004) Preparation and purification of synthetic protein nanoparticles. IEE ProcNanobiotechnol, 151, 176-182.

23. Gole, A., Vyas, S., Phadtare, S., Lachke, A. and Sastry, M. (2002) Studies on the formation of bioconjugates of Endoglucanase with colloidal gold. Colloids Surf, B, 25, 129-138.

24. Lyon, L. A., Peña, D. J. and Natan, M. J. (1999) Surface Plasmon Resonance of Au Colloid-Modified Au Films: Particle Size Dependence. J Phys Chem B, 103, 5826-5831.

25. Matsuya, T., Tashiro, S., Hoshino, N., Shibata, N., Nagasaki, Y. and Kataoka, K.

(2003) A Core-Shell Type Fluorescent Nanosphere Possessing Reactive Poly(ethylene glycol) Tethered Chains on the Surface of Zeptomole Detection of Protein in Time-Resolved Fluorometric Immunoassay. Anal Chem, 75.

26. Whetten, R. L., Shafigullin, M. N., Khoury, J. T., Schaaff, T. G., Vezmar, I., Alvarez, M. M. and Wilkinson, A. (1999) Crystal Structures of Molecular Gold Nanocrystal Arrays. Acc Chem Res, 32, 397-406.

27. Gies, A. P., Hercules, D. M., Gerdon, A. E. and Cliffel, D. E. (2007) Electrospray mass spectrometry study of tiopronin monolayer-protected gold nanoclusters. J Am Chem Soc, 129, 1095-1104.

28. Schaaff, T. G., Knight, G., Shafigullin, M. N., Borkman, R. F. and Whetten, R. L.

(1998) Isolation and selected properties of a 10.4 kDa Gold : Glutathione cluster compound. J Phys Chem B, 102, 10643-10646.

29. Johnson, S. R., Evans, S. D. and Brydson, R. (1998) Influence of a terminal functionality on the physical properties of surfactant-stabilized gold nanoparticles.

Langmuir, 14, 6639-6647.

30. Ackerson, C. J., Jadzinsky, P. D. and Kornberg, R. D. (2005) Thiolate ligands for synthesis of water-soluble gold clusters. J Am Chem Soc, 127, 6550-6551.

31. Cliffel, D. E., Zamborini, F. P., Gross, S. M. and Murray, R. W. (2000) Mercaptoammonium-monolayer-protected, water-soluble gold, silver, and palladium clusters. Langmuir, 16, 9699-9702.

32. Hostetler, M. J., Green, S. J., Stokes, J. J. and Murray, R. W. (1996) Monolayers in three dimensions: Synthesis and electrochemistry of omega-functionalized alkanethiolate-stabilized gold cluster compounds. J Am Chem Soc, 118, 4212Hostetler, M. J., Templeton, A. C. and Murray, R. W. (1999) Dynamics of PlaceExhange Reactions on Monolayer-Protected Gold Cluster Molecules. Langmuir, 15, 3782-3789.

34. Kassam, A., Bremner, G., Clark, B., Ulibarri, G. and Lennox, R. B. (2006) Place exchange reactions of alkyl thiols on gold nanoparticles. J Am Chem Soc, 128, 3476-3477.

35. Montalti, M., Prodi, L., Zaccheroni, N., Baxter, R., Teobaldi, G. and Zerbetto, F.

(2003) Kinetics of place-exchange reactions of thiols on gold nanoparticles.

Langmuir, 19, 5172-5174.

36. Hong, R., Fernandez, J. M., Nakade, H., Arvizo, R., Emrick, T. and Rotello, V.

M. (2006) In situ observation of place exchange reactions of gold nanoparticles.

Correlation of monolayer structure and stability. Chem Commun, 2347-2349.

37. Häkkinen, H., Barnett, R. N. and Landman, U. (1999) Electronic structure of passivated Au-38(SCH3)(24) nanocrystal. Phys Rev Lett, 82, 3264-3267.

38. Donkers, R. L., Song, Y. and Murray, R. W. (2004) Substituent effects on the exchange dynamics of ligands on 1.6 nm diameter gold nanoparticles. Langmuir, 20, 4703-4707.

39. Song, Y. and Murray, R. W. (2002) Dynamics and extent of ligand exchange depend on electronic charge of metal nanoparticles. J Am Chem Soc, 124, 7096Myung, N., Bae, Y. and Bard, A. J. (2003) Effect of surface passivation on the electrogenerated chemiluminescence of CdSe/ZnSe nanocrystals. Nano Lett, 3, 1053-1055.

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