
1.Center of Information Optical Technologies, ITMO University, Saint Petersburg, 197101, Russia
2.Research Park, Saint Petersburg State University, Saint Petersburg, 199034, Russia
3.Laboratory of Femtosecond Optics and Femtotechnology, ITMO University, Saint Petersburg, 197101, Russia
4.Laboratory of Quantum Processes and Measurements, ITMO University, Saint Petersburg, 197101, Russia
5.Department of Materials Science and Engineering, and Centre for Functional Photonics (CFP), City University of Hong Kong, Kowloon, Hong Kong SAR, 999077, China
6.Shenzhen Research Institute, City University of Hong Kong, Shenzhen, 518057, China
Ananya Das (dasananyadas@gmail.com)
Elena V. Ushakova (elena.ushakova@itmo.ru)
Published:31 May 2022,
Published Online:11 April 2022,
Received:12 November 2021,
Revised:23 March 2022,
Accepted:27 March 2022
Scan QR Code
Das, A. et al. Revealing the nature of optical activity in carbon dots produced from different chiral precursor molecules. Light: Science & Applications, 11, 855-867 (2022).
Das, A. et al. Revealing the nature of optical activity in carbon dots produced from different chiral precursor molecules. Light: Science & Applications, 11, 855-867 (2022). DOI: 10.1038/s41377-022-00778-9.
Carbon dots (CDs) are light-emitting nanoparticles that show great promise for applications in biology and medicine due to the ease of fabrication
biocompatibility
and attractive optical properties. Optical chirality
on the other hand
is an intrinsic feature inherent in many objects in nature
and it can play an important role in the formation of artificial complexes based on CDs that are implemented for enantiomer recognition
site-specific bonding
etc. We employed a one-step hydrothermal synthesis to produce chiral CDs from the commonly used precursors citric acid and ethylenediamine together with a set of different chiral precursors
namely
L-isomers of cysteine
glutathione
phenylglycine
and tryptophan. The resulting CDs consisted of O
N-doped (and also S-doped
in some cases) carbonized cores with surfaces rich in amide and hydroxyl groups; they exhibited high photoluminescence quantum yields reaching 57%
chiral optical signals in the UV and visible spectral regions
and two-photon absorption. Chiral signals of CDs were rather complex and originated from a combination of the chiral precursors attached to the CD surface
hybridization of lower-energy levels of chiral chromophores formed within CDs
and intrinsic chirality of the CD cores. Using DFT analysis
we showed how incorporation of the chiral precursors at the optical centers induced a strong response in their circular dichroism spectra. The optical characteristics of these CDs
which can easily be dispersed in solvents of different polarities
remained stable during pH changes in the environment and after UV exposure for more than 400 min
which opens a wide range of bio-applications.
Lim, E. K. et al. Nanomaterials for theranostics: recent advances and future challenges.Chem. Rev.115, 327–394 (2015)..
Jiang, Y. Y. et al. A generic approach towards afterglow luminescent nanoparticles for ultrasensitive in vivo imaging.Nat. Commun.10, 2064 (2019)..
Gauger, A. J., Hershberger, K. K.&Bronstein, L. M. Theranostics based on magnetic nanoparticles and polymers: intelligent design for efficient diagnostics and therapy.Front. Chem.8, 561 (2020)..
De, M., Ghosh, P. S.&Rotello, V. M. Applications of nanoparticles in biology.Adv. Mater.20, 4225–4241 (2008)..
Du, J. J. et al. Carbon dots for in vivo bioimaging and theranostics.Small15, 1805087 (2019)..
Ross, S. et al. The analytical and biomedical applications of carbon dots and their future theranostic potential: a review.J. Food Drug Anal.28, 12 (2020)..
Li, W. D. et al. Kilogram-scale synthesis of carbon quantum dots for hydrogen evolution, sensing and bioimaging.Chin. Chem. Lett.30, 2323–2327 (2019)..
Tao, S. Y. et al. Crosslink-enhanced emission effect on luminescence in polymers: advances and perspectives.Angew. Chem.132, 9910–9924 (2020)..
Wang, S. C. et al. Enhanced-fluorescent imaging and targeted therapy of liver cancer using highly luminescent carbon dots-conjugated foliate.Mater. Sci. Eng. C116, 111233 (2020)..
Wang, J. J. et al. Highly luminescent copper iodide cluster based inks with photoluminescence quantum efficiency exceeding 98%.J. Am. Chem. Soc.142, 3686–3690 (2020)..
Das, A. et al. Carbon dot with pH independent near-unity photoluminescence quantum yield in an aqueous medium: electrostatics-induced Forster resonance energy transfer at submicromolar concentration.J. Phys. Chem. Lett.9, 5092–5099 (2018)..
Das, A. et al. On the molecular origin of photoluminescence of nonblinking carbon dot.J. Phys. Chem. C.121, 9634–9641 (2017)..
Wang, B. Y. et al. Rational design of multi-color-emissive carbon dots in a single reaction system by hydrothermal.Adv. Sci.8, 2001453,https://doi.org/10.1002/advs.202001453https://doi.org/10.1002/advs.202001453(2020)..
Yang, X. et al. Red-emitting, self-oxidizing carbon dots for the preparation of white LEDs with super-high color rendering index.Sci. China Chem.64, 1547–1553 (2021)..
Shi, X. X. et al. Far-red to near-infrared carbon dots: preparation and applications in biotechnology.Small15, 1901507 (2019)..
Zhou, B. et al. Recent insights into near-infrared light-responsive carbon dots for bioimaging and cancer phototherapy.Inorg. Chem. Front.6, 1116–1128 (2019)..
Li, D. et al. Optical properties of carbon dots in the deep-red to near-infrared region are attractive for biomedical applications.Small17, 2102325 (2021)..
Dhenadhayalan, N., Lin, K. C.&Saleh, T. A. Recent advances in functionalized carbon dots toward the design of efficient materials for sensing and catalysis applications.Small16, 1905767 (2020)..
Ali, H., Ghosh, S.&Jana, N. R. Fluorescent carbon dots as intracellular imaging probes.Wiley Interdiscip. Rev. Nanomed. Nanobiotechnol.12, e1617 (2020)..
Wang, B. Y. et al. Near-infrared emissive carbon dots with 33.96% emission in aqueous solution for cellular sensing and light-emitting diodes.Sci. Bull.64, 1285–1292 (2019)..
Li, B. L. et al. Recent advances and prospects of carbon dots in phototherapy.Chem. Eng. J.408, 127245 (2021)..
Kuznetsova, V. et al. Ligand-induced chirality and optical activity in semiconductor nanocrystals: theory and applications.Nanophotonics10, 797–824 (2021)..
Chekini, M. et al. Chiral carbon dots synthesized on cellulose nanocrystals.Adv. Opt. Mater.8, 1901911 (2020)..
Liu, S. et al. One-step hydrothermal synthesis of chiral carbon dots with high asymmetric catalytic activity for an enantioselective direct aldol reaction.Chem. Commun.57, 3680–3683 (2021)..
Ma, W. Y. et al. Photoluminescent chiral carbon dots derived from glutamine.Chin. Chem. Lett.31, 3916–3920,https://doi.org/10.1016/j.cclet.2021.05.021https://doi.org/10.1016/j.cclet.2021.05.021(2021)..
Ostadhossein, F. et al. Chirality inversion on the carbon dot surface via covalent surface conjugation of cyclic α-amino acid capping agents.Bioconjugate Chem.29, 3913–3922 (2018)..
Zhang, M. L. et al. Chiral control of carbon dots via surface modification for tuning the enzymatic activity of glucose oxidase.ACS Appl. Mater. Interfaces13, 5877–5886 (2021)..
Das, A. et al. Chiral carbon dots based on L/D-cysteine produced via room temperature surface modification and one-pot carbonization.Nanoscale13, 8058–8066 (2021)..
Ragazzon, G. et al. Optical processes in carbon nanocolloids.Chem7, 606–628 (2021)..
Liu, Y. F. et al. Rational synthesis of highly efficient ultra-narrow red-emitting carbon quantum dots for NIR-II two-photon bioimaging.Nanoscale12, 1589–1601 (2020)..
Wang, Z. W. et al. A quenchable superhard carbon phase synthesized by cold compression of carbon nanotubes.Proc. Natl Acad. Sci. USA101, 13699–13702 (2004)..
Ferrari, A. C.&Robertson, J. Interpretation of Raman spectra of disordered and amorphous carbon.Phys. Rev. B61, 14095–14107 (2000)..
Stepanidenko, E. A. et al. Influence of the solvent environment on luminescent centers within carbon dots.Nanoscale12, 602–609 (2020)..
Pandit, S. et al. In situ synthesis of amino acid functionalized carbon dots with tunable properties and their biological applications.ACS Appl. Bio Mater.2, 3393–3403 (2019)..
Xiong, Y. et al. Influence of molecular fluorophores on the research field of chemically synthesized carbon dots.Nano Today23, 124–139 (2018)..
Schneider, J. et al. Molecular fluorescence in citric acid-based carbon dots.J. Phys. Chem. C121, 2014–2022 (2017)..
Song, Y. B. et al. Investigation from chemical structure to photoluminescent mechanism: a type of carbon dots from the pyrolysis of citric acid and an amine.J. Mater. Chem. C3, 5976–5984 (2015)..
Liu, R. F., Zhu, G. X.&Zhang, G. N-substitution of acridone with electron-donating groups: crystal packing, intramolecular charge transfer and tuneable aggregation induced emission.RSC Adv.10, 7092–7098 (2020)..
Xiong, Y. et al. Carbonization conditions influence the emission characteristics and the stability against photobleaching of nitrogen doped carbon dots.Nanoscale9, 11730–11738 (2017)..
Sun, M. H. et al. Realization of the photostable intrinsic core emission from carbon dots through surface deoxidation by ultraviolet irradiation.J. Phys. Chem. Lett.10, 3094–3100 (2019)..
Su, W. et al. Carbon dots: a booming material for biomedical applications.Mater. Chem. Front.4, 821–836 (2020)..
Lakowicz, J. R.Principles of Fluorescence Spectroscopy. 3rd edn (Springer, 2006).
Nad, S.&Pal, H. Unusual photophysical properties of coumarin-151.J. Phys. Chem. A105, 1097–1106 (2001)..
Yi, Z. H. et al. High quantum yield photoluminescent N-doped carbon dots for switch sensing and imaging.Talanta222, 121663 (2021)..
Wang, H. et al. Wide emission shifts and high quantum yields of solvatochromic carbon dots with rich pyrrolic nitrogen.Nano Res.13, 2492–2499 (2020)..
Phillips, C. L. et al. Circular differential scattering and circular differential absorption of DNA-protein condensates and of dyes bound to DNA-protein condensates.Biochemistry25, 7803–7811 (1986)..
Castiglioni, E. et al. Wavelength shifts in solid-state circular dichroism spectra: a possible explanation.Chirality19, 491–496 (2007)..
Deka, M. J.&Chowdhury, D. Chiral carbon dots and their effect on the optical properties of photosensitizers.RSC Adv.7, 53057–53063 (2017)..
Harada, N.&Berova, N. 8.24 spectroscopic analysis: exciton circular dichroism for chiral analysis.Compr. Chirality8, 449–477 (2012)..
Ma, W. et al. Chiral inorganic nanostructures.Chem. Rev.117, 8041–8093 (2017)..
Berova, N., Ellestad, G. A.,&Harada, N. InComprehensive Chiroptical Spectroscopy, Volume 1: Instrumentation, Methodologies, and Theoretical Simulations (eds Berova N., PolavarapuP. L., NakanishiK., WoodyR. W.)Ch. 8.24 (Elsevier, 2012)..
Superchi, S., Giorgio, E.&Rosini, C.Structural determinations by circular dichroism spectra analysis using coupled oscillator methods: an update of the applications of the DeVoe polarizability model.Chirality16, 422–451 (2004)..
Ben-Moshe, A. et al. Probing the interaction of quantum dots with chiral capping molecules using circular dichroism spectroscopy.Nano Lett.16, 7467–7473 (2016)..
Rivera-Fuentes, P. et al. Amplification of chirality in monodisperse, enantiopure alleno-acetylenic oligomers.Angew. Chem. Int. Ed.49, 2247–2250 (2010)..
Ma, K. et al. Boosting the circularly polarized luminescence of small organic molecules via multi-dimensional morphology control.Chem. Sci.10, 6821–6827 (2019)..
Gao, X. Q. et al. Excitonic circular dichroism of chiral quantum rods.J. Am. Chem. Soc.139, 8734–8739 (2017)..
Gao, X. Q. et al. Distinct excitonic circular dichroism between wurtzite and zincblende CdSe nanoplatelets.Nano Lett.18, 6665–6671 (2018)..
Zhang, M. L. et al. Maltase decorated by chiral carbon dots with inhibited enzyme activity for glucose level control.Small15, 1901512 (2019)..
Rodger, A.&Marshall, D. Beginners guide to circular dichroism.Biochemist43, 58–64 (2021)..
Liu, K. K. et al. Efficient red/near-infrared-emissive carbon nanodots with multiphoton excited upconversion fluorescence.Adv. Sci.6, 1900766 (2019)..
Lan, M. H. et al. Two-photon-excited near-infrared emissive carbon dots as multifunctional agents for fluorescence imaging and photothermal therapy.Nano Res.10, 3113–3123 (2017)..
Li, D. et al. Near-infrared excitation/emission and multiphoton-induced fluorescence of carbon dots.Adv. Mater.30, 1705913 (2018)..
Xu, C.&Webb, W. W. Measurement of two-photon excitation cross sections of molecular fluorophores with data from 690 to 1050 nm.J. Optical Soc. Am. B13, 481–491 (1996)..
Nag, A.&Goswami, D. Solvent effect on two-photon absorption and fluorescence of rhodamine dyes.J. Photochem. Photobiol. A Chem.206, 188–197 (2009)..
Zhang, Y. L. et al. Solvent effect and two-photon optical properties of triphenylamine-based donor–acceptor fluorophores.J. Phys. Chem. C119, 27630–27638 (2015)..
Zhang, Q. et al. Lighting the way to see inside two-photon absorption materials: structure–property relationship and biological imaging.Materials10, 223 (2017)..
Becke, A. D. Density-functional thermochemistry. III. The role of exact exchange.J. Chem. Phys.98, 5648–5652 (1993)..
Caldeweyher, E. et al. A generally applicable atomic-charge dependent London dispersion correction.J. Chem. Phys.150, 154122 (2019)..
Van Lenthe, E.&Baerends, E. J. Optimized Slater-type basis sets for the elements 1-118.J. Comput. Chem.24, 1142–1156 (2003)..
Te Velde, G. et al. Chemistry with ADF.J. Comput. Chem.22, 931–967 (2001)..
0
Views
1
Downloads
0
CSCD
Publicity Resources
Related Articles
Related Author
Related Institution
京公网安备11010802024621