Photophysical Study of Heteroatom-Doped Carbon Dots-MnO2-Based Nanosensor: Selective Detection of Glutathione in the Nanomolar Level.

Heteroatom doping on carbon dots (Cdots) has been developed as an efficient approach to modify its optical and electronic properties. The four different types of heteroatom-doped Cdots (undoped Cdots (u-Cdots, nitrogen-doped Cdots (N-Cdots), sulfur-doped Cdots (Cdots), nitrogen, sulfur codoped Cdots (N, S-Cdots)) have been synthesized through a simple heat treatment of 5 min. Among four different heteroatoms doped nanosensors, N, S-Cdots with MnO2 nanospheres (Mn NS) showed one of the best fluorescents "on-off-on" nanosensors for selective sensing of glutathione (GSH) and cell imaging. N, S-Cdots showed a high fluorescence quantum yield, good photostability, ionic strength, and pH stability. N, S-Cdots with Mn NS demonstrated extremely high fluorescence quenching efficiency and the maximum fluorescence recovery rate after adding GSH to the produced solution. The photophysical study of N, S-Cdots-Mn NS used as a sensor confirms the inner filter effect (IFE) quenching mechanism between them. The developed sensor has an 80 nM limit of detection (LOD) for GSH. The heteroatom-doped framework of Cdots plays a significant role in the sensitive detection of GSH. N, S-Cdots-Mn NS have good permeability, biocompatibility, and low toxicity, due to which it was used in the intracellular imaging of GSH in living cells. The prepared sensor is rapid, economical, less toxic, and highly applicable in diagnosing diseases.

Morphology Effect of One-Dimensional MnO2 Nanostructures on Heteroatom-Doped Carbon Dot-Based Biosensors for Selective Detection of Glutathione.

Structural versatility of MnO2 nanostructures plays a significant role in biosensing applications. So, we have prepared simple and selective "turn-off-on" sensing probes for the detection of glutathione (GSH), based on nitrogen, sulfur codoped carbon dots (N, S-Cdots) and different morphologies of one-dimensional (1-D) MnO2 nanostructures. N, S-Cdots with a high fluorescence quantum yield (73.42%) were prepared by a green approach through high-temperature pyrolysis in just 5 min. The different morphologies of 1-D MnO2 nanostructures (nanowires with varying aspect ratios and nanorods) were synthesized through a hydrothermal method by varying the reaction period (8, 10, and 12 h). MnO2 nanowires prepared at 8 h showed a high specific surface area (34 m2 g-1) with a large aspect ratio. They showed significant fluorescence quenching, Stern-Volmer constants, and binding constants in the presence of N, S-Cdots. Further, ultraviolet-visible absorption, zeta potential, and time decay studies showed that the quenching mechanism of the developed sensing system was the inner filter effect, which was further confirmed by using the Parker equation. The N, S-Cdots-MnO2 nanowire (with a high aspect ratio) sensing system showed the best limit of detection, i.e., 28.5 µM for GSH. This fast, simple, eco-friendly, and cost-effective sensing system can be further used for real-time biosensing and bioimaging application.

Recent advances in heteroatom-doped graphene quantum dots for sensing applications.

Graphene quantum dots (GQDs) are carbon-based fluorescent nanomaterials having various applications due to attractive properties. But the low photoluminescence (PL) yield and monochromatic PL behavior of GQDs put limitations on their real-time applications. Therefore, heteroatom doping of GQDs is recognized as the best approach to modify the optical as well as electronic properties of GQDs by modifying their chemical composition and electronic structure. In this review, the new strategies for preparing the heteroatom (N, B, S, P) doped GQDs by using different precursors and methods are discussed in detail. The particle size, emission wavelength, PL emissive color, and quantum yield of recently developed heteroatom doped GQDs are reported in this article. The investigation of structure, crystalline nature, and composition of heteroatom doped GQDs by various characterization techniques such as high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) are also described. The recent progress on the impact of mono or co-doping of heteroatoms on PL behavior, and optical, electrochemiluminescence (ECL), and electrochemical properties of GQDs is also surveyed. Further, heteroatom doped GQDs with attractive properties used in sensing of various metal ions, biomolecules, small organic molecules, etc. by using various techniques with different limits of detection are also summarized. This review provides progressive trends in the development of heteroatom doped GQDs and their various applications.

Encapsulation and release of non-fluorescent crystal violet confined in bile-salt aggregates.

In this work, the entrapment of non-fluorescent dye Crystal Violet (CV) in presence of bio-mimetic confined bile-salt aggregates has been studied. The photophysical characteristic properties of CV have been carried out by changing different kinds of hydrophilic head groups and hydrophobic skeletons of bile-salt aggregates (NaC, NaDC, NaTC and NaTGC). The main aim of this work is to modulate the solubility behaviour, fluorescence properties and elucidation of different kinds of non-covalent interaction of CV confined in bile-salt aggregates. To interpret the result, steady state absorption and fluorescence emission techniques have been employed. In aqueous buffer, the CV molecule is non-fluorescent in nature. The value of fluorescence quantum yield (Φ) is ∼10-4. It has been observed that CV confined in bile-salt aggregates becomes highly fluorescent in nature. The enhancement of 'Φ' value of CV in bile-salt aggregates is ∼1000 fold compared to that of aqueous buffer medium. It has also been observed that in the presence of different bile-salt aggregates, CV exhibits remarkable enhancement of absorption and fluorescence emission spectral behaviour. The ground state and the excited state binding constant values of CV in the presence of different bile-salt aggregates have been determined. Moreover, the release of the dye molecule from the confined bile-salt aggregates to the aqueous medium has been executed. It has been found that addition of a very minute concentration of KCl salt (100 nm) to the bile-salt aggregates leads to extreme modification of their photophysical properties of CV. The absorption, fluorescence intensity, fluorescence quantum yield, ground state and excited state binding constant values, partition coefficient and aggregation number of CV molecules entrapped in bile-salt aggregates significantly reduces by addition of KCl. This result clearly confirms that CV releases from the confined system to the aqueous medium.

Morphology-Dependent Performance of MnO2 Nanostructure-Carbon Dot-Based Biosensors for the Detection of Glutathione.

Herein, we develop a facile, sensitive, and selective fluorescent nanosensor for the detection of glutathione (GSH). In this protocol, carbon dots (Cdots) with a fairly high quantum yield were synthesized by a microwave-assisted pyrolysis technique. Moreover, different shapes of the MnO2 nanostructure were also prepared by the hydrothermal technique. A comparative photophysical study of different morphology-dependent Cdots@MnO2 nanostructure-based biosensors was explored, which showed different results for the quenching values of ("turn-off") fluorescence intensity, quantum yields, electron transfer rate, and average lifetime. The structure, property, and performance of nanomaterials are interdependent. Therefore, the different shapes of MnO2, that is, nanoflowers (NFs), nanorods (NRs), and a mixture of NFs/NRs was prepared by the hydrothermal method owing to different specific surface areas (23-69 m2 g-1) which put the impact on their sensing activity. It was observed that the variation in the different photophysical parameters of fluorescent Cdots such as quantum yield (Φ), average lifetime values [τav (ns)], radiative (kr) rate constant, nonradiative (knr) rate constant, rate of electron transfer (kET), the efficiency of electron transfer (ΦEET), FRET efficiency (E), and Förster distance (R0) were dependent on the different shapes of the MnO2 nanostructure. These results indicate that the transfer of energy occurs between the Cdots and different shapes of MnO2 nanostructures based on fluorescence resonance energy transfer at different charge-transfer rates. The recovery rate ("turn-on") of fluorescence of Cdots with the addition of GSH was obtained best for the NF structure by conversion of MnO2 to Mn2+, and the limit of detection was obtained as ∼19 µM for GSH. The developed sensing probes were rapid, easy, cheap, and eco-friendly for the determination of GSH.