Abstract
Using a combination of two amino acids, histidine and N-acetyl-cysteine, to replace the original organic capping groups of (CdSe)ZnS quantum dots, water-soluble and highly luminescent (CdSe)ZnS quantum dots have been successfully prepared at pH 8. Characterization by steady-state and time-resolved photoluminescence spectroscopy, and transient absorption spectroscopy, demonstrate that the electronic properties of these quantum dots exceed those of the original as-synthesized samples dissolved in a more-conventional organic solvent. Furthermore, these amino acid-stabilized quantum dots have been assembled onto a cellulose substrate via cellulose binding proteins that specifically bind to cellulose and was genetically engineered to harbor dual hexahistidine tags at the N- and C-termini to confer binding with the zinc(ii) on the quantum dot surface. The spectroscopic measurements show that the protein-bound quantum dots continue to retain their desirable electronic properties when bound on the substrate. Meanwhile, the specific and very selective binding properties of the proteins have remained effective.
Similar content being viewed by others
References
C. B. Murray, D. J. Norris and M. G. Bawendi, Synthesis And Characterization Of Nearly Monodisperse Cde (E = S, Se, Te) Semiconductor Nanocrystallites, J. Am. Chem. Soc., 1993, 115, 8706–8715.
O. I. Micic, C. J. Curtis, K. M. Jones, J. R. Sprague and A. J. Nozik, Synthesis And Characterization Of Inp Quantum Dots, J. Phys. Chem., 1994, 98, 4966–4969.
M. R. Salvador, M. A. Hines and G. D. Scholes, Exciton-bath coupling and inhomogeneous broadening in the optical spectroscopy of semiconductor quantum dots, J. Chem. Phys., 2003, 118, 9380–9388.
C. Landes, M. A. El-Sayed, Thermodynamic and kinetic characterization of the interaction between N-butylamine and similar to 1 nm CdSe nanoparticles, J. Phys. Chem. A, 2002, 106, 7621–7627.
C. Landes, C. Burda, M. Braun, M. A. El-Sayed, Photoluminescence of CdSe nanoparticles in the presence of a hole acceptor: n-butylamine, J. Phys. Chem. B, 2001, 105, 2981–2986.
P. Guyot-Sionnest, B. Wehrenberg and D. Yu, Intraband relaxation in CdSe nanocrystals and the strong influence of the surface ligands, J. Chem. Phys., 2005, 123, 074709.
H. Mattoussi, J. M. Mauro, E. R. Goldman, G. P. Anderson, V. C. Sundar, F. V. Mikulec and M. G. Bawendi, Self-assembly of CdSe-ZnS quantum dot bioconjugates using an engineered recombinant protein, J. Am. Chem. Soc., 2000, 122, 12142–12150.
W. C. W. Chan, D. J. Maxwell, X. H. Gao, R. E. Bailey, M. Y. Han and S. M. Nie, Luminescent quantum dots for multiplexed biological detection and imaging, Curr. Opin. Biotechnol., 2002, 13, 40–46.
B. Dubertret, P. Skourides, D. J. Norris, V. Noireaux, A. H. Brivanlou and A. Libchaber, vivo imaging of quantum dots encapsulated in phospholipid micelles, Science, 2002, 298, 1759–1762.
M. Bruchez, M. Moronne, P. Gin, S. Weiss and A. P. Alivisatos, Semiconductor nanocrystals as fluorescent biological labels, Science, 1998, 281, 2013–2016.
C. R. Bagshaw and D. Cherny, Blinking fluorophores: what do they tell us about protein dynamics?, Biochem. Soc. Trans., 2006, 34, 979–982.
S. Y. Ding, M. Jones, M. P. Tucker, J. M. Nedeljkovic, J. Wall, M. N. Simon, G. Rumbles and M. E. Himmel, Quantum dot molecules assembled with genetically engineered proteins, Nano Lett., 2003, 3, 1581–1585.
S. Y. Ding, G. Rumbles, M. Jones, M. P. Tucker, J. Nedeljkovic, M. N. Simon, J. S. Wall and M. E. Himmel, Bioconjugation of (CdSe)ZnS quantum dots using a genetically engineered multiple polyhistidine tagged cohesin/dockerin protein polymer, Macromol. Mater. Eng., 2004, 289, 622–628.
S. Hohng and T. Ha, Near-complete suppression of quantum dot blinking in ambient conditions, J. Am. Chem. Soc., 2004, 126, 1324–1325.
M. Jones, S. Y. Ding, M. P. Tucker, Y. H. Kim, S. B. Zhang, M. E. Himmel and G. Rumbles, Stabilization of (CdSe)ZnS Quantum Dots in Water Using Amino Acid Capping Groups, in 205th Meeting of the Electrochemical Society, ed. G. L. Rumbles and T. Murakoshi, Electrochemical Society Inc., San Antonio, Texas, 2006, pp. 340–349.
P. Gockel, H. Vahrenkamp and A. D. Zuberbuhler, Zinc-Complexes Of Cysteine, Histidine, And Derivatives Thereof-Potentiometric Determination Of Their Compositions And Stabilities, Helv. Chim. Acta, 1993, 76, 511–520.
D. Gerion, F. Pinaud, S. C. Williams, W. J. Parak, D. Zanchet, S. Weiss and A. P. Alivisatos, Synthesis and properties of biocompatible water-soluble silica-coated CdSe/ZnS semiconductor quantum dots, J. Phys. Chem. B, 2001, 105, 8861–8871.
S. Y. Ding, E. A. Bayer, D. Steiner, Y. Shoham and R. Lamed, A novel cellulosomal scaffolding from Acetivibrio cellulolyticus that contains a family 9 glycosyl hydrolase, J. Bacteriol., 1999, 181, 6720–6729.
H. Jung, D. B. Wilson and L. P. Walker, Binding and reversibility of thermobifida fusca Cel5A, Cel6B, and Cel48A and their respective catalytic domains to bacterial microcrystalline cellulose, Biotechnol. Bioeng., 2003, 84, 151–159.
R. J. Ellingson, J. L. Blackburn, J. Nedeljkovic, G. Rumbles, M. Jones, H. X. Fu and A. J. Nozik, Theoretical and experimental investigation of electronic structure and relaxation of colloidal nanocrystalline indium phosphide quantum dots, Phys. Rev. B, 2003, 67, 075308.
S. Y. Ding, Q. Xu, M. K. Ali, J. O. Baker, E. A. Bayer, Y. Barak, R. Lamed, J. Sugiyama, G. Rumbles and M. E. Himmel, Versatile derivatives of carbohydrate-binding modules for imaging of complex carbohydrates approaching the molecular level of resolution, Biotechniques, 2006, 41, 435.
Q. Xu, X. Ai, P. Ahrenkiel, M. Jones, M. P. Tucker, G. Rumbles, M. E. Himmel and S. Y. Ding, Bioengineered Carbohydrate-Binding Protein Modules designed to Assemble Linear Arrays of Quantum Dots on Cellulose Nanocrystals, to be submitted.
P. R. Yu, J. M. Nedeljkovic, P. A. Ahrenkiel, R. J. Ellingson and A. J. Nozik, Size dependent femtosecond electron cooling dynamics in CdSe quantum rods, Nano Letters, 2004, 4, 1089–1092.
V. I. Klimov, D. W. McBranch, C. A. Leatherdale and M. G. Bawendi, Electron and hole relaxation pathways in semiconductor quantum dots, Phys. Rev. B, 1999, 60, 13740–13749.
V. I. Klimov, Optical nonlinearities and ultrafast carrier dynamics in semiconductor nanocrystals, J. Phys. Chem. B, 2000, 104, 6112–6123.
C. B. Murray, C. R. Kagan and M. G. Bawendi, Synthesis and characterization of monodisperse nanocrystals and close-packed nanocrystal assemblies, Ann. Rev. Mater. Sci., 2000, 30, 545–610.
T. Takagahara, Effects Of Dielectric Confinement And Electron-Hole Exchange Interaction On Excitonic States In Semiconductor Quantum Dots, Phys. Rev. B, 1993, 47, 4569–4585.
C. A. Leatherdale and M. G. Bawendi, Observation of solvatochromism in CdSe colloidal quantum dots, Phys. Rev. B, 2001, 6316, 165315.
T. Jin, F. Fujii, E. Yamada, Y. Nodasaka and M. Kinjo, Control of the optical properties of quantum dots by surface coating with calix[n]arene carboxylic acids, J. Am. Chem. Soc., 2006, 128, 9288–9289.
G. Kalyuzhny and R. W. Murray, Ligand effects on optical properties of CdSe nanocrystals, J. Phys. Chem. B, 2005, 109, 7012–7021.
I. L. Medintz, A. R. Clapp, H. Mattoussi, E. R. Goldman, B. Fisher and J. M. Mauro, Self-assembled nanoscale biosensors based on quantum dot FRET donors, Nat. Mater., 2003, 2, 630–638.
S. Y. Ding, G. Rumbles, M. Jones, M. P. Tucker, J. Nedeljkovic, M. N. Simon, J. S. Wall and M. E. Himmel, Bioconjugation of (CdSe)ZnS quantum dots using a genetically engineered multiple polyhistidine tagged cohesin/dockerin protein polymer, Macromol. Mater. Eng., 2004, 289, 622.
C. Bullen and P. Mulvaney, The effects of chemisorption on the luminescence of CdSe quantum dots, Langmuir, 2006, 22, 3007–3013.
J. A. Kloepfer, S. E. Bradforth and J. L. Nadeau, Photophysical properties of biologically compatible CdSe quantum dot structures, J. Phys. Chem. B, 2005, 109, 9996–10003.
B. Noszal, D. Visky and M. Kraszni, Population, acid–base, and redox properties of N-acetylcysteine conformers, J. Med. Chem., 2000, 43, 2176–2182.
S. Jeong, M. Achermann, J. Nanda, S. Lvanov, V. I. Klimov and J. A. Hollingsworth, Effect of the thiol-thiolate equilibrium on the photophysical properties of aqueous CdSe/ZnS nanocrystal quantum dots, J. Am. Chem. Soc., 2005, 127, 10126–10127.
R. G. Pearson, Acids and Bases, Science, 1966, 151, 172–177.
J. M. Berg and H. A. Godwin, Lessons from zinc-binding peptides, Ann. Rev. Biophys. Biomol. Struct., 1997, 26, 357–371.
J. Tormo, R. Lamed, A. J. Chirino, E. Morag, E. A. Bayer, Y. Shoham and T. A. Steitz, Crystal structure of a bacterial family-III cellulose-binding domain: A general mechanism for attachment to cellulose, EMBO J., 1996, 15, 5739–5751.
Author information
Authors and Affiliations
Corresponding author
Additional information
This paper was published as part of the special issue in honour of David Phillips.
Rights and permissions
About this article
Cite this article
Ai, X., Xu, Q., Jones, M. et al. Photophysics of (CdSe)ZnS colloidal quantum dots in an aqueous environment stabilized with amino acids and genetically-modified proteins. Photochem Photobiol Sci 6, 1027–1033 (2007). https://doi.org/10.1039/b706471c
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1039/b706471c