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Molecular recognition using corona phase complexes made of synthetic polymers adsorbed on carbon nanotubes

Nature Nanotechnology volume 8, pages 959–968 (2013)Cite this article

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Abstract

Understanding molecular recognition is of fundamental importance in applications such as therapeutics, chemical catalysis and sensor design. The most common recognition motifs involve biological macromolecules such as antibodies and aptamers. The key to biorecognition consists of a unique three-dimensional structure formed by a folded and constrained bioheteropolymer that creates a binding pocket, or an interface, able to recognize a specific molecule. Here, we show that synthetic heteropolymers, once constrained onto a single-walled carbon nanotube by chemical adsorption, also form a new corona phase that exhibits highly selective recognition for specific molecules. To prove the generality of this phenomenon, we report three examples of heteropolymer–nanotube recognition complexes for riboflavin, L-thyroxine and oestradiol. In each case, the recognition was predicted using a two-dimensional thermodynamic model of surface interactions in which the dissociation constants can be tuned by perturbing the chemical structure of the heteropolymer. Moreover, these complexes can be used as new types of spatiotemporal sensors based on modulation of the carbon nanotube photoemission in the near-infrared, as we show by tracking riboflavin diffusion in murine macrophages.

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Figure 1: Schematic of the molecular recognition concept.
Figure 2: Construct that selectively recognizes oestradiol, and non-selective mutants.
Figure 3: Construct that selectively recognizes L-thyroxine, and non-selective mutants.
Figure 4: Construct that selectively recognizes riboflavin, and non-selective mutants.
Figure 5: Two-dimensional equation of state model for describing molecular recognition.
Figure 6: Tunability of BA-PhO-Dex–SWNT sensor, and application in spatial and temporal chemical imaging in live Raw 264.7 macrophage cells.

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Acknowledgements

The authors thank L. Trudel for her assistance with cell culture. The authors thank D. Wittrup, C. Love and V. Sresht for discussions. This work made use of the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation (grant no. OCI-1053575). M.S.S. acknowledges a grant from the Army Research Office and support via award no. 64655-CH-ISN to the Institute for Solider Nanotechnologies. D.A.H. acknowledges the Damon Runyon Cancer Research Foundation. A.A.B. is funded by the National Defense Science & Engineering Graduate Fellowship. A.J.H. acknowledges funding from the Department of Energy SCGF programme (contract no. DE-AC05-06OR23100). Z.W.U. acknowledges support from the Department of Energy CSGF (DOE grant DE-FG02-97ER25308). M.P.L. acknowledges an NSF postdoctoral research fellowship (award no. DBI-1306229). S.K. was supported by a fellowship from the Deutsche Forschungsmeinschaft (DFG).

Author information

Author notes

  1. Mia A. Shandell, Nitish Nair, Kyungsuk Yum, Jin-Ho Ahn & Hong Jin

    Present address: Present address: Department of Pharmacology, Graduate School of Arts & Sciences at Columbia University Medical Center, 630 West 168th Street, PH 7W 318, New York, New York 10032, USA (M.A.S.), Computational Centre of Expertise, Shell India Markets Private Limited, Bangalore, India 560 048 (N.N.), Samsung Advanced Institute of Technology, Samsung Electronics Co, Yongin-Si, Gyeonggi-Do, Korea 446-712 (J-H.A.), Department of Materials Science and Engineering, University of Texas at Arlington, 501 West First Street, Arlington, Texas 76019, USA (K.Y.), National Institute of Clean-and-Low-Carbon Energy (NICE), PO Box 001 Shenhua NICE, Future Science and Technology City, Changping District, Beijing 102209, China (H.J.),

  2. Jingqing Zhang, Markita P. Landry, Paul W. Barone and Jong-Ho Kim: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Jingqing Zhang, Markita P. Landry, Paul W. Barone, Jong-Ho Kim, Shangchao Lin, Zachary W. Ulissi, Bin Mu, Ardemis A. Boghossian, Andrew J. Hilmer, Alina Rwei, Allison C. Hinckley, Sebastian Kruss, Nitish Nair, Steven Blake, Fatih Şen, Selda Şen, Kyungsuk Yum, Jin-Ho Ahn, Hong Jin, Daniel A. Heller, Daniel Blankschtein & Michael S. Strano

  2. Department of Chemical Engineering, Hanyang University, Ansan, 426-791, Republic of Korea

    Jong-Ho Kim

  3. Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Shangchao Lin

  4. Department of Electrical Engineering and Computer Science, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Dahua Lin

  5. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Mia A. Shandell, Robert G. Croy, Deyu Li & John M. Essigmann

  6. Department of Chemistry, Dumlupinar University, Kutahya, 43020, Turkey

    Fatih Şen

  7. Department of Chemistry, Middle East Technical University, Ankara, 06531, Turkey

    Selda Şen

  8. Department of Biological Engineering, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Robert G. Croy, Deyu Li & John M. Essigmann

  9. Molecular Pharmacology and Chemistry Program, Memorial Sloan-Kettering Cancer Center, New York, New York, 10065, USA

    Daniel A. Heller

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Contributions

M.S.S. conceived and developed the recognition concept, with input from P.W.B. and D.A.H. Authors J.Z., M.P.L., P.W.B. and J.K. contributed equally to this work. J.Z., P.W.B. and M.S.S. analysed the data and co-wrote the manuscript, with contributions from S.B. and M.P.L. J.Z., P.W.B. and J.K. synthesized various polymers, suspended SWNTs with them, conducted the high-throughput screening assay and additional experiments, with contributions from A.R., A.C.H., M.A.S., K.Y. and J.A. J.Z. and A.J.H. performed the radiolabelling experiment and collaborated with R.G.C., D.Li and J.M.E. on the experimental protocol. J.Z. performed the in vitro cell experiments for riboflavin detection and processed images generated from the dual-channel microscope with D.Lin. M.P.L. built the near-infrared/visible dual-channel total-internal reflection fluorescence microscope and processed the generated images. A.J.H. contributed to the automation of single-molecule image analysis. S.L. and D.B. conducted molecular dynamics simulation and analysed the results. M.S.S. and D.B. conceived and designed the two-dimensional equation of state model with Z.W.U. and J.Z., while Z.W.U. performed the necessary molecular simulations. B.M. and J.Z. worked on polymer–SWNT complex characterization. S.K. performed additional TEM experiments. M.S.S. and D.A.H. conceived, designed and built the dual-channel microscope and performed additional analyte screening. J.Z. and D.Lin developed the imaging-processing algorithm for the images generated during the dual-channel microscope experiment. A.A.B. and H.J. developed the single-particle tracking algorithm. F.S., S.S. and M.P.L. conducted additional single-molecule experiments and performed data analysis. P.W.B. and N.N. developed the automated spectrum deconvolution program, which was further improved by J.Z. and A.J.H.

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Correspondence to Michael S. Strano.

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Zhang, J., Landry, M., Barone, P. et al. Molecular recognition using corona phase complexes made of synthetic polymers adsorbed on carbon nanotubes. Nature Nanotech 8, 959–968 (2013). https://doi.org/10.1038/nnano.2013.236

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