Heteroatom-doped
carbon dots (C-dots) have captured widespread
research interest owing to high fluorescence and biocompatibility
for multimodal bioimaging applications. Here, we exemplify a rapid,
facile synthesis of ethylenediamine (EDA)-functionalized transition
metal ion (Mn2+, Fe2+, Co2+, and
Ni2+)-doped C-dots via one-pot microwave (MW)-assisted
pyrolysis at 800 W within 6 min using Citrus limon (lemon) extract as a carbon source. During MW pyrolysis, the precursor
extract undergoes simultaneous carbonization and doping of metal ions
onto C-dot surfaces in the presence of EDA. The EDA-functionalized
transition metal ion-doped C-dots (i.e., Mn/C, Fe/C, Co/C, and Ni/C-dots)
are collectively termed as TMCDs. The water-soluble TMCDs exhibited
a size of 3.2 ± 0.485 nm and were enriched with amino and oxo
functionalities and corresponding metal-oxide traces on the surfaces,
as revealed from Fourier transfer infrared and X-ray photoelectron
spectroscopy analyses. Interestingly, TMCDs demonstrated excitation-wavelength-dependent
emission with brighter photoluminescence (PL) at 460 nm. Compared
to pristine C-dots with a PL quantum yield (QY) of 48.31% and a fluorescence
lifetime of 3.6 ns, the synthesized Mn/C, Fe/C, Co/C, and Ni/C-dots
exhibited PL QY values of 35.71, 41.72, 75.07, and 50.84% as well
as enhanced fluorescence lifetimes (τav) of 9.4,
8.6, 9.2, and 8.9 ns, respectively. The TMCDs significantly exhibited
enhanced biocompatibility in human colon cancer cells (SW480) for
fluorescence bioimaging and showed ferromagnetic and superparamagnetic
behavior with vibrant T
1-contrast ability.
Interestingly, the maximum longitudinal (r
1) relaxivity of 0.341 mM–1 s–1 was observed for Mn/C-dots in comparison to that of 3.1–3.5
mM–1 s–1 of clinically used Gd-DTPA
magnetic resonance (MR)-contrast agent in vitro (1.5 T). Similarly,
the maximum longitudinal relaxivity (r
1) of 0.356 mM–1 s–1 was observed
for Ni/C-dots (1.5 T) with respect to 4.16 ± 0.02 mM–1 s–1 attained for Gd-DTPA in vivo (8.45 T). Thus,
the rapid, energy-efficient MW-assisted pyrolysis presents lemon extract
derived, EDA-functionalized TMCDs with enhanced PL and efficient T
1 contrast as potential magneto-fluorescent
nanoprobes for dual-modality bioimaging applications.