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8-Anilino-1-naphthalenesulfonate-Conjugated Carbon-Coated Ferrite Nanodots for Fluoromagnetic Imaging, Smart Drug Delivery, and Biomolecular Sensing

Thirumalai, Anbazhagan, Girigoswami, Koyeli, Prabhu, Alex Daniel, Durgadevi, Pazhani, Kiran, Venkatakrishnan, Girigoswami, Agnishwar·2024·Pharmaceutics
DOI 10.3390/pharmaceutics16111378PMC PMC11597131
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Abstract

Background: Superparamagnetic properties and excitation independence have been incorporated into carbon-decorated manganese ferrite nanodots (MnFe@C) to introduce an economical and safer multimodal agent for use in both T1-T2 MRI and fluorescence-based imaging to replace the conventional highly toxic heavy metal contrast agents. Methods: The surface conjugation of 8-anilino-1-naphthalenesulfonate (ANS) to MnFe@C nanodots (ANS-MnFe@C) enhances both longitudinal and transverse MRI relaxation, improves fluorescence for optical imaging, and increases protein detection sensitivity, showing higher multimodal efficacy in terms of molar relaxivity, radiant efficiencies, and fluorescence sensitivity compared to MnFe@C. Results: The band gap energy was determined using Tauc’s equation to be 3.32 eV, while a 72% quantum yield demonstrated that ANS-MnFe@C was highly fluorescent, with the linear range and association constant calculated using the Stern–Volmer relation. The synthesized ANS-MnFe@C demonstrated excellent selectivity and sensitivity for bovine serum albumin (BSA), with a nanomolar detection limit of 367.09 nM and a broad linear range from 0.015 to 0.225 mM. Conclusions: In conclusion, ANS-MnFe@C holds ease of fabrication, good biocompatibility, as assessed in A375 cells, and an effective pH-sensitive doxorubicin release profile to establish anticancer activity in lung cancer cell line (A549), highlighting its potential as an affordable therapeutic agent for multimodal imaging, drug delivery, and protein sensing.

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Figures

Figure 1 XRD spectral images of MnFe@C (A) and ANS-MnFe@C (B).
Figure 1 XRD spectral images of MnFe@C (A) and ANS-MnFe@C (B).CC BY · PubMed Central
Figure 2 (A) XPS analysis of MnFe@C. (B–D) Deconvoluted XPS spectra of C 1s, N 1s, and O 1s, respectively. (E) FTIR spectra of ANS, MnFe@C, and ANS-MnFe@C. (F) Room temperature magnetic hysteresis loop of ANS-MnFe@C.
Figure 2 (A) XPS analysis of MnFe@C. (B–D) Deconvoluted XPS spectra of C 1s, N 1s, and O 1s, respectively. (E) FTIR spectra of ANS, MnFe@C, and ANS-MnFe@C. (F) Room temperature magnetic hysteresis loop of ANS-MnFe@C.CC BY · PubMed Central
Figure 3 (A) Absorption spectra of MnFe@C, ANS, and ANS-MnFe@C. (B) Fluorescence spectra [emission (λex = 515 nm)/excitation (λem = 550 nm)] of MnFe@C and ANS-MnFe@C. (C) Emission spectra of ANS-MnFe@C containing increasing ANS concentrations.
Figure 3 (A) Absorption spectra of MnFe@C, ANS, and ANS-MnFe@C. (B) Fluorescence spectra [emission (λex = 515 nm)/excitation (λem = 550 nm)] of MnFe@C and ANS-MnFe@C. (C) Emission spectra of ANS-MnFe@C containing increasing ANS concentrations.CC BY · PubMed Central
Figure 4 Band gap energy estimations using the Tauc plot. Direct bandgaps of (A) MnFe@C and (B) ANS-MnFe@C, and indirect bandgaps of (C) MnFe@C and (D) ANS-MnFe@C.
Figure 4 Band gap energy estimations using the Tauc plot. Direct bandgaps of (A) MnFe@C and (B) ANS-MnFe@C, and indirect bandgaps of (C) MnFe@C and (D) ANS-MnFe@C.CC BY · PubMed Central
Figure 5 (A) SEM and (B) TEM images of ANS-MnFe@C; (C) DLS and (D) seta potential studies of MnFe@C and ANS-MnFe@C.
Figure 5 (A) SEM and (B) TEM images of ANS-MnFe@C; (C) DLS and (D) seta potential studies of MnFe@C and ANS-MnFe@C.CC BY · PubMed Central
Figure 6 Stability of the MnFe@C and ANS-MnFe@C are different storage temperatures using (A) the emission intensity, (B) hydrodynamic diameter, and (C) zeta potential.
Figure 6 Stability of the MnFe@C and ANS-MnFe@C are different storage temperatures using (A) the emission intensity, (B) hydrodynamic diameter, and (C) zeta potential.CC BY · PubMed Central
Figure 7 (A) T1-weighted and (B) T2-weighted phantom images of MnFe@C and ANS-MnFe@C with increasing concentrations. (C) The calculated relaxivity was plotted against the concentration and compared with commercially available Gd-DOTA.
Figure 7 (A) T1-weighted and (B) T2-weighted phantom images of MnFe@C and ANS-MnFe@C with increasing concentrations. (C) The calculated relaxivity was plotted against the concentration and compared with commercially available Gd-DOTA.CC BY · PubMed Central
Figure 8 (A) Phantom optical images of MnFe@C and ANS-MnFe@C with different concentrations. (B) The molar radiant efficiencies were determined by plotting fluorescence image intensities against the concentration.
Figure 8 (A) Phantom optical images of MnFe@C and ANS-MnFe@C with different concentrations. (B) The molar radiant efficiencies were determined by plotting fluorescence image intensities against the concentration.CC BY · PubMed Central
Figure 9 Fluorescence emission spectra of ANS-MnFe@C show the increasing intensity upon the addition of an increasing amount of the BSA protein. (A) λex = 365 nm and λem = 411 nm, (B) λex = 515 nm and λem = 550 nm. (C,D) The fluorescence intensity was plotted against the concentration for λem = 411 nm and λem = 550 nm, respectively.
Figure 9 Fluorescence emission spectra of ANS-MnFe@C show the increasing intensity upon the addition of an increasing amount of the BSA protein. (A) λex = 365 nm and λem = 411 nm, (B) λex = 515 nm and λem = 550 nm. (C,D) The fluorescence intensity was plotted against the concentration for λem = 411 nm and λem = 550 nm, respectively.CC BY · PubMed Central
Figure 10 (A,B) Scatchard plots for ANS-MnFe@C and BSA binding monitored at λem = 411 and 550 nm, respectively. (C,D) Benesi–Hildebrand (BH) plots of ANS-MnFe@C in the presence of BSA monitored at λem = 411 and 550 nm, respectively.
Figure 10 (A,B) Scatchard plots for ANS-MnFe@C and BSA binding monitored at λem = 411 and 550 nm, respectively. (C,D) Benesi–Hildebrand (BH) plots of ANS-MnFe@C in the presence of BSA monitored at λem = 411 and 550 nm, respectively.CC BY · PubMed Central
Figure 11 (A) Viability of A375 cells treated with different concentrations (0.31, 0.5, 1.1, 2.2, and 2.5 mM) of ANS-conjugated and unconjugated MnFe@C; fluorescence images of AO/EtBr-stained (10× magnification) A375 cells: (B) control; (C) MnFe@C; and (D) ANS-MnFe@C.
Figure 11 (A) Viability of A375 cells treated with different concentrations (0.31, 0.5, 1.1, 2.2, and 2.5 mM) of ANS-conjugated and unconjugated MnFe@C; fluorescence images of AO/EtBr-stained (10× magnification) A375 cells: (B) control; (C) MnFe@C; and (D) ANS-MnFe@C.CC BY · PubMed Central
Figure 12 (A) Drug release profile for-Dox loaded ANS-MnFe@C in different release media (pH 4.5, 7.5, and 9.2). (B) The Korsmeyer–Peppas model was used to profile Dox release from ANS-MnFe@C. (C) Percentage of A549 cells killed after treatment with Dox and ANS-MnFe@C-Dox.
Figure 12 (A) Drug release profile for-Dox loaded ANS-MnFe@C in different release media (pH 4.5, 7.5, and 9.2). (B) The Korsmeyer–Peppas model was used to profile Dox release from ANS-MnFe@C. (C) Percentage of A549 cells killed after treatment with Dox and ANS-MnFe@C-Dox.CC BY · PubMed Central

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Metadata

Authors
Thirumalai, A., Girigoswami, K., Prabhu, A. D., Durgadevi, P., Kiran, V., & Girigoswami, A.
Venue
Pharmaceutics
Publisher
MDPI AG
Published
2024-10-26
Volume
16
Issue
11
Pages
1378
ISSN
1999-4923
DOI
10.3390/pharmaceutics16111378
PMC
PMC11597131
Cited by
40
References
1
Language
en
Licence
creativecommons.org/licenses/by/4.0/ (vor)

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