DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Induced Chirality in QDs Using Thermoresponsive Elastin-like Polypeptides

Journal Article · · Langmuir

Circular dichroism (CD) spectroscopy has emerged as a potent tool for probing chiral small-molecule ligand exchange on natively achiral quantum dots (QDs). In this study, we report a novel approach to identifying QD–biomolecule interactions by inducing chirality in CdS QDs using thermoresponsive elastin-like polypeptides (ELPs) engineered with C-terminal cysteine residues. Our method is based on a versatile two-step ligand exchange process starting from monodisperse oleate-capped QDs in nonpolar media and proceeding through an easily accessed achiral glycine-capped QD intermediate. Successful conjugation of the ELPs onto the QDs is confirmed by the diagnostic CD response corresponding to the QD electronic transitions in the visible range. The resulting ELP:CdS conjugates demonstrate thermally reversible coacervation, as observed through dynamic light scattering, small-angle X-ray scattering, and electron microscopy. Furthermore, this research provides a foundation for using induced chirality in QD electronic transitions to probe QD conjugation to complex peptides and proteins, opening pathways for designing dynamic, stimuli-responsive hybrid nanomaterials.

Research Organization:
University of Washington, Seattle, WA (United States)
Sponsoring Organization:
National Science Foundation (NSF); SINE2020; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0019288
OSTI ID:
2499568
Journal Information:
Langmuir, Journal Name: Langmuir Journal Issue: 1 Vol. 41; ISSN 0743-7463
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (64)

Fabrication of CdSe‐Nanofibers with Potential for Biomedical Applications journal March 2010
Small angle scattering of X‐rays. A. Guinier and G. Fournet. Translated by C. B. Wilson and with a bibliographical appendix by K. L. Yudowitch. Wiley, New York, 1955. 268 pp. $7.50. journal March 1956
The synthetic polypentapeptide of elastin coacervates and forms filamentous aggregates journal December 1974
Free energy transduction in polypeptides and proteins based on inverse temperature transitions journal January 1992
How Hofmeister ion interactions affect protein stability journal October 1996
Applications of elastin-like polypeptides in tissue engineering journal December 2010
Quantum dots as a platform for nanoparticle drug delivery vehicle design journal May 2013
Elastin-like polypeptides in drug delivery journal February 2016
Biocompatible Quantum Dots for Biological Applications journal January 2011
‘Zur Lehre von der Wirkung der Salze’ (about the science of the effect of salts): Franz Hofmeister's historical papers journal August 2004
One-pot synthesis of pH and temperature sensitive gold clusters mediated by a recombinant elastin-like polymer journal April 2010
Elastin-like polypeptides as models of intrinsically disordered proteins journal August 2015
NIR-quantum dots in biomedical imaging and their future journal March 2021
Purification of proteins using peptide-ELP based affinity precipitation journal February 2020
Threonine functionalized colloidal cadmium sulfide (CdS) quantum dots: The role of solvent and counterion in ligand induced chiroptical properties journal July 2023
Enzymatic Product-Mediated Stabilization of CdS Quantum Dots Produced In Situ: Application for Detection of Reduced Glutathione, NADPH, and Glutathione Reductase Activity journal May 2013
Quantum Dot–Peptide Conjugates as Energy Transfer Probes for Sensing the Proteolytic Activity of Matrix Metalloproteinase-14 journal January 2023
A Multifunctional Polypeptide via Ugi Reaction for Compact and Biocompatible Quantum Dots with Efficient Bioconjugation journal March 2018
Precision Loading and Delivery of Molecular Cargo by Size-Controlled Coacervation of Gold Nanoparticles Functionalized with Elastin-like Peptides journal March 2024
Hierarchical Materials from High Information Content Macromolecular Building Blocks: Construction, Dynamic Interventions, and Prediction journal October 2022
Dynamic Optical Switching of Polymer/Plasmonic Nanoparticle Hybrids with Sparse Loading journal January 2017
Optical Activity and Excitonic Characteristics of Chiral CdSe Quantum Dots journal March 2024
Probing the Interaction of Quantum Dots with Chiral Capping Molecules Using Circular Dichroism Spectroscopy journal November 2016
Impact of Nanoparticle Size and Surface Chemistry on Peptoid Self-Assembly journal April 2022
Chirality Inversion of CdSe and CdS Quantum Dots without Changing the Stereochemistry of the Capping Ligand journal February 2016
CdSe Quantum Dots Functionalized with Chiral, Thiol-Free Carboxylic Acids: Unraveling Structural Requirements for Ligand-Induced Chirality journal October 2017
Circular Dichroism of CdSe Nanocrystals Bound by Chiral Carboxylic Acids journal October 2016
Effect of Chiral Ligand Concentration and Binding Mode on Chiroptical Activity of CdSe/CdS Quantum Dots journal November 2019
Protonation Equilibria of N-Acetylcysteine journal August 2020
Capping Structure of Ligand–Cysteine on CdSe Magic-Sized Clusters journal February 2019
Recursive Directional Ligation by Plasmid Reconstruction Allows Rapid and Seamless Cloning of Oligomeric Genes journal April 2010
A New Family of Pyridine-Appended Multidentate Polymers As Hydrophilic Surface Ligands for Preparing Stable Biocompatible Quantum Dots journal September 2014
Characterization of peptide-coated cadmium-sulfide crystallites journal April 1990
X-ray Photoelectron Spectroscopy of CdSe Nanocrystals with Applications to Studies of the Nanocrystal Surface journal April 1994
Synthesis and characterization of nearly monodisperse CdE (E = sulfur, selenium, tellurium) semiconductor nanocrystallites journal September 1993
Formation of High-Quality CdTe, CdSe, and CdS Nanocrystals Using CdO as Precursor journal January 2001
The Relative Nucleophilic Character of Several Mercaptans toward Ethylene Oxide1 journal May 1960
Interfacial Phase Transition of an Environmentally Responsive Elastin Biopolymer Adsorbed on Functionalized Gold Nanoparticles Studied by Colloidal Surface Plasmon Resonance journal July 2001
Ligand Exchange and the Stoichiometry of Metal Chalcogenide Nanocrystals: Spectroscopic Observation of Facile Metal-Carboxylate Displacement and Binding
  • Anderson, Nicholas C.; Hendricks, Mark P.; Choi, Joshua J.
  • Journal of the American Chemical Society, Vol. 135, Issue 49, p. 18536-18548 https://doi.org/10.1021/ja4086758
journal November 2013
Similar Topological Origin of Chiral Centers in Organic and Nanoscale Inorganic Structures: Effect of Stabilizer Chirality on Optical Isomerism and Growth of CdTe Nanocrystals journal May 2010
Multidentate Polymer Coatings for Compact and Homogeneous Quantum Dots with Efficient Bioconjugation journal March 2016
Physical Chemistry of Biological Free Energy Transduction As Demonstrated by Elastic Protein-Based Polymers journal December 1997
Genetically Programmable Thermoresponsive Plasmonic Gold/Silk-Elastin Protein Core/Shell Nanoparticles journal April 2014
DNA-Passivated CdS Nanocrystals:  Luminescence, Bioimaging, and Toxicity Profiles journal December 2007
Optically Responsive Gold Nanorod−Polypeptide Assemblies journal November 2008
Tunable Biopolymers for Heavy Metal Removal journal March 2001
Chiral Shells and Achiral Cores in CdS Quantum Dots journal August 2008
Ligand Induced Circular Dichroism and Circularly Polarized Luminescence in CdSe Quantum Dots journal November 2013
Site-specific adsorption of gold nanoparticles coated with thermo-responsive peptides journal December 2012
Site-selective photoinduced cleavage and profiling of DNA by chiral semiconductor nanoparticles journal July 2018
Development of truncated elastin-like peptide analogues with improved temperature-response and self-assembling properties journal November 2022
Short elastin-like peptide-functionalized gold nanoparticles that are temperature responsive under near-physiological conditions journal January 2018
Precursor reaction kinetics control compositional grading and size of CdSe 1−x S x nanocrystal heterostructures journal January 2019
Peptoid-directed assembly of CdSe nanoparticles journal January 2021
The effect of molecular isomerism on the induced circular dichroism of cadmium sulfide quantum dots journal January 2021
Chiral highly luminescent CdS quantum dots journal January 2007
A quantum-dot based protein module for in vivo monitoring of protease activity through fluorescence resonance energy transfer journal January 2011
Cadmium(ii) N-acetylcysteine complex formation in aqueous solution journal January 2011
Achiral CdSe quantum dots exhibit optical activity in the visible region upon post-synthetic ligand exchange with d- or l-cysteine journal January 2013
Light-induced actuating nanotransducers journal May 2016
Identification of β,β-turns and unordered conformations in polypeptide chains by vacuum ultraviolet circular dichroism journal August 1977
McSAS : software for the retrieval of model parameter distributions from scattering patterns journal May 2015
Self-assembly/disassembly hysteresis of nanoparticles composed of marginally soluble, short elastin-like polypeptides journal February 2018
Facile Synthesis of Peptide-Conjugated Gold Nanoclusters with Different Lengths journal November 2021