TY - JOUR
T1 - Methylammonium Tin Tribromide Quantum Dots for Heavy Metal Ion Detection and Cellular Imaging
AU - Shellaiah, Muthaiah
AU - Awasthi, Kamlesh
AU - Chandran, Sarala
AU - Aazaad, Basheer
AU - Sun, Kien Wen
AU - Ohta, Nobuhiro
AU - Wu, Shu Pao
AU - Lin, Ming Chang
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/2/25
Y1 - 2022/2/25
N2 - Development of luminescent and nontoxic Pb-free perovskite quantum dots (PQDs) for quantification of toxic/nontoxic heavy metal ions has attracted much attention recently. In this paper, blue emissive Pb-free bare and poly(ethylenimine), oleic acid stabilized methylammonium tin tribromide quantum dots (MASnBr3QDs and PEI-OA-MASnBr3QDs) are developed via modified synthetic routes with fluorescent quantum yields of (φf) of 8.7 and 14.6%, respectively. The particle size, structures, diffraction patterns, and surface potential of PQDs are investigated using a high-resolution transmission electron microscope (HR-TEM), powder X-ray diffraction (PXRD), dynamic light scattering (DLS), and zeta potential techniques. Photoluminescence (PL) investigations demonstrate agglomeration-mediated energy transfer at various precursor concentrations and water sensitivity of PQDs. At 20 μL precursor concentration in DMSO, both QDs exhibit diverse fluorescent quenching to Fe3+and Cr6+with linear regression between 1-500 μM and nanomolar detection limits (LODs). Estimated Stern-Volmer quenching constant values are on the order of 103-104M-1higher than those of other ions. PL and time-resolved PL studies confirm involvement of dynamic and static quenching in quantification of Fe3+/Cr6+for MASnBr3QDs and PEI-OA-MASnBr3QDs, respectively. Agglomeration of PQDs, Sn2+/MA+cationic displacement by Fe3+/Cr6+, and the existence of metal-oxide/hydroxide layer above the surface of QDs are confirmed by HR-TEM, DLS, zeta potential, X-ray photoelectron spectroscopy, and energy-dispersive spectroscopy investigations and supported by the density functional theory optimization. Biocompatibility of PQDs is authenticated by the methyl thiazolyl tetrazolium assay and IC50interrogations with supporting results from time-dependent cellular imaging of Fe3+and Cr6+ions. Individual titrations of PQDs with Fe3+and Cr6+in tap, lake, and seawater samples display linear behavior with micro/nanomolar LODs. Fe3+and Cr6+in spiked real water sample experiments show exceptional PL recoveries (>100%), which agree with the inductively coupled plasma-mass analysis.
AB - Development of luminescent and nontoxic Pb-free perovskite quantum dots (PQDs) for quantification of toxic/nontoxic heavy metal ions has attracted much attention recently. In this paper, blue emissive Pb-free bare and poly(ethylenimine), oleic acid stabilized methylammonium tin tribromide quantum dots (MASnBr3QDs and PEI-OA-MASnBr3QDs) are developed via modified synthetic routes with fluorescent quantum yields of (φf) of 8.7 and 14.6%, respectively. The particle size, structures, diffraction patterns, and surface potential of PQDs are investigated using a high-resolution transmission electron microscope (HR-TEM), powder X-ray diffraction (PXRD), dynamic light scattering (DLS), and zeta potential techniques. Photoluminescence (PL) investigations demonstrate agglomeration-mediated energy transfer at various precursor concentrations and water sensitivity of PQDs. At 20 μL precursor concentration in DMSO, both QDs exhibit diverse fluorescent quenching to Fe3+and Cr6+with linear regression between 1-500 μM and nanomolar detection limits (LODs). Estimated Stern-Volmer quenching constant values are on the order of 103-104M-1higher than those of other ions. PL and time-resolved PL studies confirm involvement of dynamic and static quenching in quantification of Fe3+/Cr6+for MASnBr3QDs and PEI-OA-MASnBr3QDs, respectively. Agglomeration of PQDs, Sn2+/MA+cationic displacement by Fe3+/Cr6+, and the existence of metal-oxide/hydroxide layer above the surface of QDs are confirmed by HR-TEM, DLS, zeta potential, X-ray photoelectron spectroscopy, and energy-dispersive spectroscopy investigations and supported by the density functional theory optimization. Biocompatibility of PQDs is authenticated by the methyl thiazolyl tetrazolium assay and IC50interrogations with supporting results from time-dependent cellular imaging of Fe3+and Cr6+ions. Individual titrations of PQDs with Fe3+and Cr6+in tap, lake, and seawater samples display linear behavior with micro/nanomolar LODs. Fe3+and Cr6+in spiked real water sample experiments show exceptional PL recoveries (>100%), which agree with the inductively coupled plasma-mass analysis.
KW - bioimaging
KW - heavy metals detection
KW - polymer capping
KW - real analysis
KW - surface tuned recognition
KW - tin-halide perovskite
UR - http://www.scopus.com/inward/record.url?scp=85125076464&partnerID=8YFLogxK
U2 - 10.1021/acsanm.2c00028
DO - 10.1021/acsanm.2c00028
M3 - Article
AN - SCOPUS:85125076464
SN - 2574-0970
VL - 5
SP - 2859
EP - 2874
JO - ACS Applied Nano Materials
JF - ACS Applied Nano Materials
IS - 2
ER -