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Choi JK, Haynie BE, Tohgha U, et al. Chirality Inversion of CdSe and CdS Quantum Dots without Changing the Stereochemistry of the Capping Ligand. ACS Nano. 2016;10(3):3809-15doi: 10.1021/acsnano.6b00567.
Choi, J. K., Haynie, B. E., Tohgha, U., Pap, L., Elliott, K. W., Leonard, B. M., Dzyuba, S. V., Varga, K., Kubelka, J., & Balaz, M. (2016). Chirality Inversion of CdSe and CdS Quantum Dots without Changing the Stereochemistry of the Capping Ligand. ACS nano, 10(3), 3809-15. https://doi.org/10.1021/acsnano.6b00567
Choi, Jung Kyu, et al. "Chirality Inversion of CdSe and CdS Quantum Dots without Changing the Stereochemistry of the Capping Ligand." ACS nano vol. 10,3 (2016): 3809-15. doi: https://doi.org/10.1021/acsnano.6b00567
Choi JK, Haynie BE, Tohgha U, Pap L, Elliott KW, Leonard BM, Dzyuba SV, Varga K, Kubelka J, Balaz M. Chirality Inversion of CdSe and CdS Quantum Dots without Changing the Stereochemistry of the Capping Ligand. ACS Nano. 2016 Mar 22;10(3):3809-15. doi: 10.1021/acsnano.6b00567. Epub 2016 Mar 07. PMID: 26938741.
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ACS Nano. 2016 Mar 22;10(3):3809-15. doi: 10.1021/acsnano.6b00567. Epub 2016 Mar 07.

Chirality Inversion of CdSe and CdS Quantum Dots without Changing the Stereochemistry of the Capping Ligand.

ACS nano

Jung Kyu Choi, Benjamin E Haynie, Urice Tohgha, Levente Pap, K Wade Elliott, Brian M Leonard, Sergei V Dzyuba, Krisztina Varga, Jan Kubelka, Milan Balaz

Affiliations

  1. Department of Chemistry, University of Wyoming , Laramie, Wyoming 82071, United States.
  2. Department of Chemistry and Biochemistry, Texas Christian University , Fort Worth, Texas 76129, United States.
  3. Underwood International College, Integrated Science & Engineering Division, Yonsei University , Seoul 03722, Republic of Korea.

PMID: 26938741 DOI: 10.1021/acsnano.6b00567

Abstract

L-cysteine derivatives induce and modulate the optical activity of achiral cadmium selenide (CdSe) and cadmium sulfide (CdS) quantum dots (QDs). Remarkably, N-acetyl-L-cysteine-CdSe and L-homocysteine-CdSe as well as N-acetyl-L-cysteine-CdS and L-cysteine-CdS showed "mirror-image" circular dichroism (CD) spectra regardless of the diameter of the QDs. This is an example of the inversion of the CD signal of QDs by alteration of the ligand's structure, rather than inversion of the ligand's absolute configuration. Non-empirical quantum chemical simulations of the CD spectra were able to reproduce the experimentally observed sign patterns and demonstrate that the inversion of chirality originated from different binding arrangements of N-acetyl-L-cysteine and L-homocysteine-CdSe to the QD surface. These efforts may allow the prediction of the ligand-induced chiroptical activity of QDs by calculating the specific binding modes of the chiral capping ligands. Combined with the large pool of available chiral ligands, our work opens a robust approach to the rational design of chiral semiconducting nanomaterials.

Keywords: chiral semiconductor nanocrystals; circular dichroism; density functional theory; ligand-induced optical activity; nanoparticles; quantum chemical simulations; quantum dots

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