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Title: Chiral Graphene Quantum Dots

Abstract

Chiral nanostructures from metals and semiconductors attract wide interest as components for polarization-enabled optoelectronic devices. Similarly to other fields of nanotechnology, graphene-based materials can greatly enrich physical and chemical phenomena associated with optical and electronic properties of chiral nanostructures and facilitate their applications in biology as well as other areas. Here, we report that covalent attachment of l/d-cysteine moieties to the edges of graphene quantum dots (GQDs) leads to their helical buckling due to chiral interactions at the “crowded” edges. Circular dichroism (CD) spectra of the GQDs revealed bands at ca. 210–220 and 250–265 nm that changed their signs for different chirality of the cysteine edge ligands. The high-energy chiroptical peaks at 210–220 nm correspond to the hybridized molecular orbitals involving the chiral center of amino acids and atoms of graphene edges. Diverse experimental and modeling data, including density functional theory calculations of CD spectra with probabilistic distribution of GQD isomers, indicate that the band at 250–265 nm originates from the three-dimensional twisting of the graphene sheet and can be attributed to the chiral excitonic transitions. The positive and negative low-energy CD bands correspond to the left and right helicity of GQDs, respectively. Exposure of liver HepG2 cells to l/d-GQDsmore » reveals their general biocompatibility and a noticeable difference in the toxicity of the stereoisomers. Molecular dynamics simulations demonstrated that d-GQDs have a stronger tendency to accumulate within the cellular membrane than l-GQDs. Finally, emergence of nanoscale chirality in GQDs decorated with biomolecules is expected to be a general stereochemical phenomenon for flexible sheets of nanomaterials.« less

Authors:
 [1];  [2];  [3];  [4];  [5];  [4];  [6];  [7];  [5];  [2];  [8];  [9];  [10]
  1. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemical Engineering; Univ. of Michigan, Ann Arbor, MI (United States). Biointerfaces Inst.; Nara Inst. of Science and Technology, Ikoma, Nara (Japan)
  2. Univ. of Michigan, Ann Arbor, MI (United States). Biointerfaces Inst.; Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Biomedical Engineering
  3. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Biomedical Engineering; Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Mechanical Engineering
  4. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemical Engineering
  5. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemical Engineering; Univ. of Michigan, Ann Arbor, MI (United States). Biointerfaces Inst.
  6. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Mechanical Engineering
  7. Univ. of Michigan, Ann Arbor, MI (United States). Biointerfaces Inst.; Pusan National Univ., Miryang (Korea, Republic of). Dept. of Cogno-Mechatronics Engineering
  8. Pusan National Univ., Miryang (Korea, Republic of). Dept. of Cogno-Mechatronics Engineering
  9. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Biomedical Engineering; Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Mechanical Engineering; Univ. of Michigan, Ann Arbor, MI (United States). Dept.of Macromolecular Science and Engineering, Biophysics Program
  10. Univ. of Michigan, Ann Arbor, MI (United States). Biointerfaces Inst., Dept. of Biomedical Engineering, Dept. of Mechanical Engineering, and Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Univ. of Michigan, Ann Arbor, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1435721
Grant/Contract Number:  
SC0002619; 2510001; DMR-9871177
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 10; Journal Issue: 2; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; biological activity; chiral excitons; chirality; circular dichroism; graphene quantum dots

Citation Formats

Suzuki, Nozomu, Wang, Yichun, Elvati, Paolo, Qu, Zhi-Bei, Kim, Kyoungwon, Jiang, Shuang, Baumeister, Elizabeth, Lee, Jaewook, Yeom, Bongjun, Bahng, Joong Hwan, Lee, Jaebeom, Violi, Angela, and Kotov, Nicholas A. Chiral Graphene Quantum Dots. United States: N. p., 2016. Web. doi:10.1021/acsnano.5b06369.
Suzuki, Nozomu, Wang, Yichun, Elvati, Paolo, Qu, Zhi-Bei, Kim, Kyoungwon, Jiang, Shuang, Baumeister, Elizabeth, Lee, Jaewook, Yeom, Bongjun, Bahng, Joong Hwan, Lee, Jaebeom, Violi, Angela, & Kotov, Nicholas A. Chiral Graphene Quantum Dots. United States. doi:10.1021/acsnano.5b06369.
Suzuki, Nozomu, Wang, Yichun, Elvati, Paolo, Qu, Zhi-Bei, Kim, Kyoungwon, Jiang, Shuang, Baumeister, Elizabeth, Lee, Jaewook, Yeom, Bongjun, Bahng, Joong Hwan, Lee, Jaebeom, Violi, Angela, and Kotov, Nicholas A. Fri . "Chiral Graphene Quantum Dots". United States. doi:10.1021/acsnano.5b06369. https://www.osti.gov/servlets/purl/1435721.
@article{osti_1435721,
title = {Chiral Graphene Quantum Dots},
author = {Suzuki, Nozomu and Wang, Yichun and Elvati, Paolo and Qu, Zhi-Bei and Kim, Kyoungwon and Jiang, Shuang and Baumeister, Elizabeth and Lee, Jaewook and Yeom, Bongjun and Bahng, Joong Hwan and Lee, Jaebeom and Violi, Angela and Kotov, Nicholas A.},
abstractNote = {Chiral nanostructures from metals and semiconductors attract wide interest as components for polarization-enabled optoelectronic devices. Similarly to other fields of nanotechnology, graphene-based materials can greatly enrich physical and chemical phenomena associated with optical and electronic properties of chiral nanostructures and facilitate their applications in biology as well as other areas. Here, we report that covalent attachment of l/d-cysteine moieties to the edges of graphene quantum dots (GQDs) leads to their helical buckling due to chiral interactions at the “crowded” edges. Circular dichroism (CD) spectra of the GQDs revealed bands at ca. 210–220 and 250–265 nm that changed their signs for different chirality of the cysteine edge ligands. The high-energy chiroptical peaks at 210–220 nm correspond to the hybridized molecular orbitals involving the chiral center of amino acids and atoms of graphene edges. Diverse experimental and modeling data, including density functional theory calculations of CD spectra with probabilistic distribution of GQD isomers, indicate that the band at 250–265 nm originates from the three-dimensional twisting of the graphene sheet and can be attributed to the chiral excitonic transitions. The positive and negative low-energy CD bands correspond to the left and right helicity of GQDs, respectively. Exposure of liver HepG2 cells to l/d-GQDs reveals their general biocompatibility and a noticeable difference in the toxicity of the stereoisomers. Molecular dynamics simulations demonstrated that d-GQDs have a stronger tendency to accumulate within the cellular membrane than l-GQDs. Finally, emergence of nanoscale chirality in GQDs decorated with biomolecules is expected to be a general stereochemical phenomenon for flexible sheets of nanomaterials.},
doi = {10.1021/acsnano.5b06369},
journal = {ACS Nano},
number = 2,
volume = 10,
place = {United States},
year = {2016},
month = {1}
}

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Synthesis of a Helical Bilayer Nanographene
journal, March 2018

  • Evans, Paul J.; Ouyang, Jiangkun; Favereau, Ludovic
  • Angewandte Chemie International Edition, Vol. 57, Issue 23
  • DOI: 10.1002/anie.201800798

Hexapole [9]Helicene
journal, December 2018

  • Wang, Yonggen; Yin, Zhibo; Zhu, Yanpeng
  • Angewandte Chemie International Edition, Vol. 58, Issue 2
  • DOI: 10.1002/anie.201811706

Enhanced intersystem crossing in core-twisted aromatics
journal, January 2017

  • Nagarajan, Kalaivanan; Mallia, Ajith R.; Muraleedharan, Keerthi
  • Chemical Science, Vol. 8, Issue 3
  • DOI: 10.1039/c6sc05126j

Quantum dots in proteomic studies and medical diagnostics
journal, April 2018

  • Gladyshev, P. P.; Tumanov, Yu. V.; Ibragimova, S. A.
  • Russian Chemical Bulletin, Vol. 67, Issue 4
  • DOI: 10.1007/s11172-018-2114-7

A review on graphene-based nanocomposites for electrochemical and fluorescent biosensors
journal, January 2019

  • Krishnan, Siva Kumar; Singh, Eric; Singh, Pragya
  • RSC Advances, Vol. 9, Issue 16
  • DOI: 10.1039/c8ra09577a

Synthesis of a Helical Bilayer Nanographene
journal, March 2018

  • Evans, Paul J.; Ouyang, Jiangkun; Favereau, Ludovic
  • Angewandte Chemie International Edition, Vol. 57, Issue 23
  • DOI: 10.1002/anie.201800798

Hexapole [9]Helicene
journal, December 2018

  • Wang, Yonggen; Yin, Zhibo; Zhu, Yanpeng
  • Angewandte Chemie International Edition, Vol. 58, Issue 2
  • DOI: 10.1002/anie.201811706

Quantum dots in proteomic studies and medical diagnostics
journal, April 2018

  • Gladyshev, P. P.; Tumanov, Yu. V.; Ibragimova, S. A.
  • Russian Chemical Bulletin, Vol. 67, Issue 4
  • DOI: 10.1007/s11172-018-2114-7

Enhanced intersystem crossing in core-twisted aromatics
journal, January 2017

  • Nagarajan, Kalaivanan; Mallia, Ajith R.; Muraleedharan, Keerthi
  • Chemical Science, Vol. 8, Issue 3
  • DOI: 10.1039/c6sc05126j

Graphene quantum dots: multifunctional nanoplatforms for anticancer therapy
journal, January 2017

  • Iannazzo, Daniela; Ziccarelli, Ida; Pistone, Alessandro
  • Journal of Materials Chemistry B, Vol. 5, Issue 32
  • DOI: 10.1039/c7tb00747g

A review on graphene-based nanocomposites for electrochemical and fluorescent biosensors
journal, January 2019

  • Krishnan, Siva Kumar; Singh, Eric; Singh, Pragya
  • RSC Advances, Vol. 9, Issue 16
  • DOI: 10.1039/c8ra09577a

Synthesis of a Helical Bilayer Nanographene
journal, March 2018

  • Evans, Paul J.; Ouyang, Jiangkun; Favereau, Ludovic
  • Angewandte Chemie, Vol. 130, Issue 23
  • DOI: 10.1002/ange.201800798

Chirality-Based Biosensors
journal, November 2018

  • Ma, Wei; Xu, Liguang; Wang, Libing
  • Advanced Functional Materials, Vol. 29, Issue 1
  • DOI: 10.1002/adfm.201805512

Controlled Fabrication of 3D Chiral Microwrinkles via Asymmetrical and Biaxial Bucklings
journal, April 2019

  • Hwang, Myonghoo; Kim, Changho; Kim, Jinwoo
  • Advanced Functional Materials, Vol. 29, Issue 29
  • DOI: 10.1002/adfm.201808979

Chiral Nanoparticle as a New Efficient Antimicrobial Nanoagent
journal, December 2016

  • Xin, Qi; Liu, Qian; Geng, Lingling
  • Advanced Healthcare Materials, Vol. 6, Issue 4
  • DOI: 10.1002/adhm.201601011

A Singlet Oxygen Generating Agent by Chirality-dependent Plasmonic Shell-Satellite Nanoassembly
journal, February 2017


Plasmonic Chirality and Circular Dichroism in Bioassembled and Nonbiological Systems: Theoretical Background and Recent Progress
journal, September 2018

  • Kong, Xiang‐Tian; Besteiro, Lucas V.; Wang, Zhiming
  • Advanced Materials, Vol. 32, Issue 41
  • DOI: 10.1002/adma.201801790

Artificial Chiral Probes and Bioapplications
journal, January 2019


Recent Advances on Graphene Quantum Dots: From Chemistry and Physics to Applications
journal, March 2019


Supramolecular Chiral 2D Materials and Emerging Functions
journal, February 2020


Chiral Surface and Geometry of Metal Nanocrystals
journal, December 2019

  • Im, Sang Won; Ahn, Hyo‐Yong; Kim, Ryeong Myeong
  • Advanced Materials, Vol. 32, Issue 41
  • DOI: 10.1002/adma.201905758

Chiral Carbon Dots Synthesized on Cellulose Nanocrystals
journal, December 2019

  • Chekini, Mahshid; Prince, Elisabeth; Zhao, Lily
  • Advanced Optical Materials, Vol. 8, Issue 4
  • DOI: 10.1002/adom.201901911

Evolution and Synthesis of Carbon Dots: From Carbon Dots to Carbonized Polymer Dots
journal, September 2019


Highly Fluorescent Chiral N-S-Doped Carbon Dots from Cysteine: Affecting Cellular Energy Metabolism
journal, February 2018


Chiral Semiconductor Nanoparticles for Protein Catalysis and Profiling
journal, April 2019


Chirality‐Embedded Nanographenes
journal, November 2019

  • Nishitani, Shohei; Sekiya, Ryo; Haino, Takeharu
  • Angewandte Chemie, Vol. 132, Issue 2
  • DOI: 10.1002/ange.201910040

Tuning the Morphology and Chiroptical Properties of Discrete Gold Nanorods with Amino Acids
journal, November 2018

  • Zheng, Guangchao; Bao, Zhiyong; Pérez-Juste, Jorge
  • Angewandte Chemie International Edition, Vol. 57, Issue 50
  • DOI: 10.1002/anie.201810693

β-Cyclodextrin Functionalized Nanoporous Graphene Oxides for Efficient Resolution of Asparagine Enantiomers
journal, August 2018

  • Qie, Fengxiang; Guo, Jiahui; Tu, Bin
  • Chemistry - An Asian Journal, Vol. 13, Issue 19
  • DOI: 10.1002/asia.201800970

High-Performance Biosensing Systems Based on Various Nanomaterials as Signal Transducers
journal, August 2018

  • Lee, Jaewook; Adegoke, Oluwasesan; Park, Enoch Y.
  • Biotechnology Journal, Vol. 14, Issue 1
  • DOI: 10.1002/biot.201800249

Enantioselective cytotoxicity of ZnS:Mn quantum dots in A549 cells
journal, June 2017

  • Kuznetsova, V. A.; Visheratina, A. K.; Ryan, A.
  • Chirality, Vol. 29, Issue 8
  • DOI: 10.1002/chir.22713

Memristive Devices with Highly Repeatable Analog States Boosted by Graphene Quantum Dots
journal, March 2017


Specific Oxygenated Groups Enriched Graphene Quantum Dots as Highly Efficient Enzyme Mimics
journal, February 2018


Maltase Decorated by Chiral Carbon Dots with Inhibited Enzyme Activity for Glucose Level Control
journal, May 2019


Graphene quantum dots-based nano-biointerface platform for food toxin detection
journal, September 2018

  • Bhardwaj, Hema; Singh, Chandan; Kotnala, R. K.
  • Analytical and Bioanalytical Chemistry, Vol. 410, Issue 28
  • DOI: 10.1007/s00216-018-1341-y

Enantioselective addition of diethylzinc to aromatic aldehydes catalyzed by chiral BINOL-functionalized nanoporous graphene oxides
journal, January 2019


Transmission of chirality through space and across length scales
journal, May 2017

  • Morrow, Sarah M.; Bissette, Andrew J.; Fletcher, Stephen P.
  • Nature Nanotechnology, Vol. 12, Issue 5
  • DOI: 10.1038/nnano.2017.62

Design principles of chiral carbon nanodots help convey chirality from molecular to nanoscale level
journal, August 2018

  • Ðorđević, Luka; Arcudi, Francesca; D’Urso, Alessandro
  • Nature Communications, Vol. 9, Issue 1
  • DOI: 10.1038/s41467-018-05561-2

Tailoring the chirality of light emission with spherical Si-based antennas
journal, January 2016

  • Zambrana-Puyalto, Xavier; Bonod, Nicolas
  • Nanoscale, Vol. 8, Issue 19
  • DOI: 10.1039/c6nr00676k

A self-assembled chiral-aptasensor for ATP activity detection
journal, January 2016


One-step synthesis of chiral carbon quantum dots and their enantioselective recognition
journal, January 2016


The toxicity of graphene quantum dots
journal, January 2016

  • Wang, Shujun; Cole, Ivan S.; Li, Qin
  • RSC Advances, Vol. 6, Issue 92
  • DOI: 10.1039/c6ra16516h

Magneto-optically active magnetoplasmonic graphene
journal, January 2017

  • Lee, Jaewook; Lee, Jaebeom
  • Chemical Communications, Vol. 53, Issue 43
  • DOI: 10.1039/c7cc01207a

Recent progress in two-dimensional inorganic quantum dots
journal, January 2018

  • Xu, Yuanhong; Wang, Xiaoxia; Zhang, Wen Ling
  • Chemical Society Reviews, Vol. 47, Issue 2
  • DOI: 10.1039/c7cs00500h

Unraveling the cooperative synergy of zero-dimensional graphene quantum dots and metal nanocrystals enabled by layer-by-layer assembly
journal, January 2018

  • Zeng, Zhiping; Xiao, Fang-Xing; Phan, Hung
  • Journal of Materials Chemistry A, Vol. 6, Issue 4
  • DOI: 10.1039/c7ta09119b

Synthesis of distorted nanographenes containing seven- and eight-membered carbocycles
journal, January 2018

  • Márquez, Irene R.; Castro-Fernández, Silvia; Millán, Alba
  • Chemical Communications, Vol. 54, Issue 50
  • DOI: 10.1039/c8cc02325e

Chiral modulation of amyloid beta fibrillation and cytotoxicity by enantiomeric carbon dots
journal, January 2018

  • Malishev, Ravit; Arad, Elad; Bhunia, Susanta Kumar
  • Chemical Communications, Vol. 54, Issue 56
  • DOI: 10.1039/c8cc03235a

Charge transfer in graphene quantum dots coupled with tetrathiafulvalenes
journal, January 2019

  • Scharl, Tobias; Ferrer-Ruiz, Andrés; Saura-Sanmartín, Adrián
  • Chemical Communications, Vol. 55, Issue 22
  • DOI: 10.1039/c8cc09990a

Novel properties and applications of carbon nanodots
journal, January 2018


Novel carbon quantum dots for fluorescent detection of phenol and insights into the mechanism
journal, January 2018

  • Xue, Hong; Yan, Yang; Hou, Yong
  • New Journal of Chemistry, Vol. 42, Issue 14
  • DOI: 10.1039/c8nj01611a

Investigation on the chirality mechanism of chiral carbon quantum dots derived from tryptophan
journal, January 2019

  • Wei, Yingying; Chen, Lin; Wang, Junli
  • RSC Advances, Vol. 9, Issue 6
  • DOI: 10.1039/c8ra09649j

A universal strategy to obtain chiroptical carbon quantum dots through the optically active surface passivation procedure
journal, January 2019

  • Rao, Xinyue; Yuan, Mengke; Jiang, Huan
  • New Journal of Chemistry, Vol. 43, Issue 35
  • DOI: 10.1039/c9nj03434j

Carbon dots: advances in nanocarbon applications
journal, January 2019


Frontiers in carbon dots: design, properties and applications
journal, January 2019

  • Li, Zeyu; Wang, Ling; Li, Yu
  • Materials Chemistry Frontiers, Vol. 3, Issue 12
  • DOI: 10.1039/c9qm00415g

Synthesis of graphene quantum dot-stabilized gold nanoparticles and their application
journal, January 2019

  • Chen, Weifeng; Shen, Jialu; Chen, Shaona
  • RSC Advances, Vol. 9, Issue 37
  • DOI: 10.1039/c9ra02758k

Phosphorus-doped porous carbon nitride for efficient sole production of hydrogen peroxide via photocatalytic water splitting with a two-channel pathway
journal, January 2020

  • Cao, Jingjing; Wang, Hui; Zhao, Yajie
  • Journal of Materials Chemistry A, Vol. 8, Issue 7
  • DOI: 10.1039/c9ta13929j

Dielectric nanoantennas to manipulate solid-state light emission
journal, September 2019

  • Bidault, Sébastien; Mivelle, Mathieu; Bonod, Nicolas
  • Journal of Applied Physics, Vol. 126, Issue 9
  • DOI: 10.1063/1.5108641

Synthesis, Optical, and Magnetic Properties of Graphene Quantum Dots and Iron Oxide Nanocomposites
journal, January 2018

  • Sajjad, M.; Makarov, V.; Sultan, M. S.
  • Advances in Materials Science and Engineering, Vol. 2018
  • DOI: 10.1155/2018/3254081

Graphene Quantum Dots Electrochemistry and Sensitive Electrocatalytic Glucose Sensor Development
journal, September 2017

  • Gupta, Sanju; Smith, Tyler; Banaszak, Alexander
  • Nanomaterials, Vol. 7, Issue 10
  • DOI: 10.3390/nano7100301

The Chirality Induction and Modulation of Polymers by Circularly Polarized Light
journal, April 2019