Graphene quantum dot-crafted nanocomposites: shaping the future landscape of biomedical advances.

Graphene quantum dots (GQDs) are a newly developed class of material, known as zero-dimensional nanomaterials, with characteristics derived from both carbon dots (CDs) and graphene. GQDs exhibit several ideal properties, including the potential to absorb incident energy, high water solubility, tunable photoluminescence, good stability, high drug-loading capacity, and notable biocompatibility, which make them powerful tools for various applications in the field of biomedicine. Additionally, GQDs can be incorporated with additional materials to develop nanocomposites with exceptional qualities and enriched functionalities. Inspired by the intriguing scientific discoveries and substantial contributions of GQDs to the field of biomedicine, we present a broad overview of recent advancements in GQDs-based nanocomposites for biomedical applications. The review first outlines the latest synthesis and classification of GQDs nanocomposite and enables their use in advanced composite materials for biomedicine. Furthermore, the systematic study of the biomedical applications for GQDs-based nanocomposites of drug delivery, biosensing, photothermal, photodynamic and combination therapies are emphasized. Finally, possibilities, challenges, and paths are highlighted to encourage additional research, which will lead to new therapeutics and global healthcare improvements.

Photothermal therapy using graphene quantum dots.

The rapid development of powerful anti-oncology medicines have been possible because of advances in nanomedicine. Photothermal therapy (PTT) is a type of treatment wherein nanomaterials absorb the laser energy and convert it into localized heat, thereby causing apoptosis and tumor eradication. PTT is more precise, less hazardous, and easy-to-control in comparison to other interventions such as chemotherapy, photodynamic therapy, and radiation therapy. Over the past decade, various nanomaterials for PTT applications have been reviewed; however, a comprehensive study of graphene quantum dots (GQDs) has been scantly reported. GQDs have received huge attention in healthcare technologies owing to their various excellent properties, such as high water solubility, chemical stability, good biocompatibility, and low toxicity. Motivated by the fascinating scientific discoveries and promising contributions of GQDs to the field of biomedicine, we present a comprehensive overview of recent progress in GQDs for PTT. This review summarizes the properties and synthesis strategies of GQDs including top-down and bottom-up approaches followed by their applications in PTT (alone and in combination with other treatment modalities such as chemotherapy, photodynamic therapy, immunotherapy, and radiotherapy). Furthermore, we also focus on the systematic study of in vitro and in vivo toxicities of GQDs triggered by PTT. Moreover, an overview of PTT along with the synergetic application used with GQDs for tumor eradication are discussed in detail. Finally, directions, possibilities, and limitations are described to encourage more research, which will lead to new treatments and better health care and bring people closer to the peak of human well-being.

Facile synthesis of PEG-glycerol coated bimetallic FePt nanoparticle as highly efficient electrocatalyst for methanol oxidation.

Direct methanol fuel cell (DMFC) has shown excellent growth as an alternative candidate for energy sources to substitute fossil fuels. However, developing cost-effective and highly durable catalysts with a facile synthesis method is still challenging. In this prospect, a facile strategy is used for the preparation of hydrophilic Fe-Pt nanoparticle catalyst via a polyethylene glycol-glycerol route to utilize the advantages of nanostructured surfaces. The synthesized electrocatalysts are characterized by XRD, XPS, TEM, EDS and FTIR to confirm their structure, morphology, composition, and surface functionalization. The performance of the catalysts towards methanol oxidation reaction (MOR) was investigated by cyclic voltammetry and chronoamperometry in both acidic and alkaline media. The Fe-Pt bimetallic catalyst exhibits better current density of 36.36 mA cm-2 in acidic medium than in alkali medium (12.52 mA cm-2). However, the high If/Ib ratio of 1.9 in alkali medium signifies better surface cleaning/regenerating capability of catalyst. Moreover, the catalyst possessed superior cyclic stability of ~ 80% in the alkaline electrolyte which is 1.6 times higher than in the acidic one. The better stability and poison tolerance capacity of catalyst in alkaline media is attributed to the OH- ions provided by the electrolyte which interact with the metal species to form M-(OH)x and reversibly release OH- and regenerate metal surface for further oxidation reactions. But synergism provided by Fe and Pt gives better activity in acidic electrolyte as Pt is favourable catalyst for dehydrogenation of methanol in acidic medium. This study will be useful for designing anodic electrocatalysts for MOR.

Fabrication of Multifunctional Drug Loaded Magnetic Phase Supported Calcium Phosphate Nanoparticle for Local Hyperthermia Combined Drug Delivery and Antibacterial Activity.

Magnetic calcium phosphate nanoparticles are biocompatible and have attracted much attention as biomaterials for bone tissue engineering and theranostic applications. In this study, we report the fabrication of a biocompatible magnetic nickel ferrite supported fluorapatite nanoparticle as a bone substitute material with hyperthermia potential using a facile wet precipitation approach. The composition and magnetic properties of the sample were analyzed using X-ray diffraction (XRD) and a vibrating sample magnetometer (VSM). The presence of both magnetic (NiFe2O4 and γ-Fe2O3) and fluorapatite phases was identified, and the sample exhibited ferromagnetic behavior with saturation magnetization and coercivity of 3.08 emu/g and 109 Oe, respectively. The fabricated sample achieved the hyperthermia temperature of ∼43 °C under tumor mimic conditions (neglecting Brownian relaxation) in 2.67 min, and the specific loss power (SLP) was estimated to be 898 W/g(Ni+Fe) which is sufficient to prompt irreversible cell apoptosis. Biocompatibility of the synthesized nanoparticle was assessed using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide tetrazolium (MTT) assay with fibroblast NIH 3T3 and L929 cells. An in vitro drug release experiment was conducted at pH 5 (tumor mimic) and 7.4 (physiological), which revealed a release of 49.8% in the former and 11.6% in the latter pH for 11 days. The prepared sample showed antibacterial activity against S. aureus.

Functionalization and Haemolytic analysis of pure superparamagnetic magnetite nanoparticle for hyperthermia application.

Superparamagnetic iron oxide nanoparticles (SPIONPs) are widely used in clinical research. The single domain nanoparticles are used in magnetic fluid hyperthermia (MFH) to treat cancer. When nanoparticles are exposed to an external magnetic field, it generates heat destroying tumour cells. SPIONPs have a large surface area, so the particles tend to aggregate, which leads to the destabilization of the colloidal system. To enhance the stability and biocompatibility of the nanomaterials, it is necessary to coat the surface with biocompatible material. Magnetite (Fe3O4) is a superparamagnetic nanoparticle (SPNPs) that was functionalized with oleic acid (OA) by sol-gel process using ethanol as the solvent. The oleic acid-coated magnetite (OA-Fe3O4) was characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), UV-Visible diffuse reflectance spectroscopy (UV-DRS) and vibrating sample magnetometer (VSM). The haemolysis test has been used to investigate the haemocompatibility properties of nanomaterials. Hyperthermia study shows a high SAR value for the concentration of 1 mg/ml at the field of 600 Oe and frequency of 316 kHz. The OA coating enhanced the haemocompatibility of synthesized magnetite nanoparticles which can be used for magnetic fluid hyperthermia applications.

Degradation of mixed cationic dye pollutant by metal free melem derivatives and graphitic carbon nitride.

Graphitic carbon nitride (GCN), a polymeric metal free catalyst is widely used to degrade the toxic organic dye from the aqueous pollution. However, its catalytic efficiency and effective simultaneous reduction of mixed dye is still a challenge. Here, we have tuned the physiochemical properties of the GCN and melem derivatives by facilely tuning the degree of polycondensation and examined their catalytic activity towards the removal of cationic dye individually and together in solution. Catalysts were synthesized by thermal treatment of low-cost melamine and characterized by XRD, FTIR, RAMAN, FE-SEM, EDX, UV-DRS, and FL spectroscopy to confirm materials' structure, phase, morphology and optical properties. A suitable phase of the catalyst (M-450) exhibited superior removal capacity with a high-rate constant compared to others. The results demonstrate that M-450 has a maximum loading efficacy of 2.13 and 1.12 mg g-1 for methylene blue (MB) and Rhodamine B (RhB) dyes respectively in a single dye system. Attractively, when MB and RhB co-exist in the solution, the efficacy increased by 14% (2.44 mg g-1) and 27% (1.43 mg g-1) for MB and RhB respectively. The adsorption kinetics, stability, effect of pH and reusability of M-450 catalyst was testified. Further, radical scavenger experiments and terephthalic acid tests were carried out to explain the reaction mechanism involved in the degradation of textile dyes. Moreover, electron paramagnetic resonance (EPR) analysis validated the availability of hydroxyl radicals in the photocatalytic reaction. Excellent stability and reusability were attained even after five successive cycles, demonstrating a suitable photocatalyst for the efficient degradation of mixed dye.

Carboxylated PEG-Functionalized MnFe2O4 Nanocubes Synthesized in a Mixed Solvent: Morphology, Magnetic Properties, and Biomedical Applications.

Ferrites are one of the most studied materials around the globe due to their distinctive biological and magnetic properties. In the same line, anisotropic MnFe2O4 nanoparticles have been explored as a potential candidate possessing excellent magnetic properties, biocompatibility, and strong magnetic resonance imaging (MRI) properties such as r2 relaxivity for magnetic field-guided biomedical applications. The current work reports the synthesis and morphological evolution of MnFe2O4 nanocubes (MNCs) in a hydrothermal process using different volume ratios of water and ethanol. The synthesis protocol was designed to influence the properties of the ferrite nanocubes, for example, the variation in surface tension, dielectric properties, and the ionic character of the solvent, and this has been achieved by adding ethanol into water during the synthesis. Pristine MnFe2O4 is formed with well-defined cubic to irregular cubic shapes with the addition of ethanol, as evidenced from XRD, field emission scanning electron microscopy, and porosity measurements. MNCs have been investigated for magnetic hyperthermia and MRI applications. Well-defined cubic-shaped MNCs with uniform size distribution possessed a high saturation magnetization of 63 emu g-1 and a transverse relaxivity (r2) of 216 mM-1 s-1 (Mn + Fe). Furthermore, the colloidal nanocubes showed concentration-dependent hyperthermic response under an alternating magnetic field. The MNCs are biocompatible but advantageously show anticancer activities on breast cancer MCF 7 and MDA-MB-231 cells.

Assessing magnetic and inductive thermal properties of various surfactants functionalised Fe3O4 nanoparticles for hyperthermia.

This work reports the fabrication of magnetite (Fe3O4) nanoparticles (NPs) coated with various biocompatible surfactants such as glutamic acid (GA), citric acid (CA), polyethylene glycol (PEG), polyvinylpyrrolidine (PVP), ethylene diamine (EDA) and cetyl-trimethyl ammonium bromide (CTAB) via co-precipitation method and their comparative inductive heating ability for hyperthermia (HT) applications. X-ray and electron diffraction analyses validated the formation of well crystallined inverse spinel structured Fe3O4 NPs (crystallite size of ~ 8-10 nm). Magnetic studies confirmed the superparamagnetic (SPM) behaviour for all the NPs with substantial magnetisation (63-68 emu/g) and enhanced magnetic susceptibility is attributed to the greater number of occupations of Fe2+ ions in the lattice as revealed by X-ray photoelectron spectroscopy (XPS). Moreover, distinctive heating response (specific absorption rate, SAR from 130 to 44 W/g) of NPs with similar size and magnetisation is observed. The present study was successful in establishing a direct correlation between relaxation time (~ 9.42-15.92 ns) and heating efficiency of each surface functionalised NPs. Moreover, heat dissipated in different surface grafted NPs is found to be dependent on magnetic susceptibility, magnetic anisotropy and magnetic relaxation time. These results open very promising avenues to design surface functionalised magnetite NPs for effective HT applications.

Synthesis of manganese doped ß-FeOOH and MnFe2O4 nanorods for enhanced drug delivery and hyperthermia application.

Preparation of manganese ferrite (MnFe2O4) nanorods by the reduction of akaganeite seeds in the presence of oleylamine is reported. The Mn-doped ß-FeOOH akaganeite seeds have been processed by the hydrolysis of metal-chloride salts in the presence of polyethylenimine (PEI) surfactant. The hydrophobic oleylamine capped nanorods are made hydrophilic using trisodium citrate as a phase transferring agent. The nanorods form with an aspect ratio of 5.47 and possess a high magnetisation value of 69 emu/g at an applied magnetic field of 1.5 T. The colloidal water dispersion of nanorods exhibits superior heating efficiency by the application of alternating magnetic field (AMF). A specific absorption rate value of 798 W/g is achieved at an applied AMF of field strength 500 Oe and frequency 316 kHz. Further, the citrate functionalised nanorods are capable of attaching with doxorubicin (DOX) electrostatically with a loading efficiency of 97% and the drug release is pH responsive. The DOX loaded nanorods show a promising effect on the apoptosis of MCF-7 as experimented in vitro.

Synthesis of ZnO/Fe3O4/rGO nanocomposites and evaluation of antibacterial activities towards E. coli and S. aureus.

Antibacterial activity of nanoparticles (NPs) and nanocomposites (NCs) has received wide spread attention in biomedical applications. In this direction, the authors prepared zinc oxide (ZnO), iron oxide (Fe3O4), and their composite including reduced graphene oxide (rGO) by hydrothermal method. The structural and microstructural properties of the synthesised NPs and NCs were investigated by XRD, FT-IR, UV-Vis, TGA, and TEM analysis. PEG-coated ZnO and Fe3O4 form in hexagonal wurtzite and inverse spinel structures, respectively. ZnO forms in rod-shaped (aspect ratio of ∼3) morphology, whereas well-dispersed spherical-shaped morphology of ∼10 nm is observed in Fe3O4 NPs. The ZnO/Fe3O4 composite possesses a homogeneous distribution of above two phases and shows a very good colloidal stability in aqueous solvent. These synthesised particles exhibited varying antibacterial activity against gram-positive strain Staphylococcus aureus (S. aureus) and gram-negative strain Escherichia coli (E. coli). The nanocomposite exhibits a better cidal effect on E. coli when compared to S. aureus when treated with 1 mg/ml concentration. Further, the addition of rGO has intensified the anti-bacterial effect to a much higher extent due to synergistic influence of individual components.

Management of chronic central serous chorioretinopathy.

New treatment modalities for the management of central serous chorioretinopathy (CSC) now exist. While acute CSC generally resolves without the requirement for intervention, chronic CSC has been associated with persistent disruption in visual function. Current treatment approaches include photodynamic therapy, oral aldosterone antagonism and subthreshold multifocal laser. There has also been further investigation into a number of new treatments including antivascular endothelial growth factor treatment. Further investigation using developing optical coherence tomography imaging is helping to determine biomarkers of CSC activity, potential indicators of treatment response and indications of chronicity of disease activity. Further comparative study is required to determine the effectiveness of different forms of treatment in a range of patients with varied demographics, aetiology and chronicity of disease.

PEGylated FePt-Fe3O4 composite nanoassemblies (CNAs): in vitro hyperthermia, drug delivery and generation of reactive oxygen species (ROS).

Chemothermal therapy is widely used in clinical applications for the treatment of tumors. However, the major challenge is the use of a multifunctional nano platform for significant regression of the tumor. In this study, a simple synthesis of highly aqueous stable, carboxyl enriched, PEGylated mesoporous iron platinum-iron(ii,iii) oxide (FePt-Fe3O4) composite nanoassemblies (CNAs) by a simple hydrothermal approach is reported. CNAs exhibit a high loading capacity ∼90 wt% of the anticancer therapeutic drug, doxorubicin (DOX) because of its porous nature and the availability of abundant negatively charged carboxylic groups on its surface. DOX loaded CNAs (CNAs + DOX) showed a pH responsive drug release in a cell-mimicking environment. Furthermore, the release was enhanced by the application of a alternating current magnetic field. CNAs show no appreciable cytotoxicity in mouse fibroblast (L929) cells but show toxic effects in cervical cancer (HeLa) cells at a concentration of ∼1 mg mL(-1). A suitable composition of CNAs with a concentration of 2 mg mL(-1) can generate a hyperthermic temperature of ∼43 °C. Also, CNAs, because of their Fe and Pt contents, have an ability to generate reactive oxygen species (ROS) in the presence of hydrogen peroxide inside the cancer cells which helps to enhance its therapeutic effects. The synergistic combination of chemotherapy and ROS is very efficient for killing cancer cells.

Ce³âº sensitized GdPO4:Tb³âº with iron oxide nanoparticles: a potential biphasic system for cancer theranostics.

We report a biphasic system (BPS) consisting of PEGylated Tb(3+)-doped GdPO4 nanorice sensitized with Ce(3+) (PEG-NRs) and glutamic acid coated iron oxide nanoparticles (IONPs) with multifunctional capabilities. The mesoporous PEG-NRs exhibit green light luminescence properties and a high degree of aqueous stability. Their drug loading and release capacities were investigated for anti-cancer chemo doxorubicin (DOX). Their mesoporous nature and availability of plenty of negatively charged functional groups (-COO(-)) on the surface of PEG-NRs facilitate approximately 94 wt% DOX loading. In vitro studies carried out for PEG-NRs and their biphasic integrated system with iron oxide using HeLa and MCF-7 cell lines demonstrated their cell killing efficacy. The green luminescence observed under confocal laser scanning microscopy (CLSM) confirms the cellular uptake of PEG-NRs by HeLa cell lines and their accumulation in the cytoplasm. Approximately 50-55% of HeLa and MCF-7 cell death was observed after 24 h of incubation with DOX loaded BPS (2 mg IONPs and 0.25 mg PEG-NRs + DOX), which further increased to about 90% when exposed to an AC magnetic field (ACMF) for 25 min. Our findings demonstrate that the therapeutic efficacy of BPS loaded with DOX could be a powerful multimodal system for imaging and synergistic chemo-thermal cancer therapy.

Role of different platinum precursors on the formation and reaction mechanism of FePt nanoparticles and their electrocatalytic performance towards methanol oxidation.

We report the formation mechanism of FePt nanoparticles (NPs) by a high temperature polyol method using an equimolar ratio of Fe and Pt-precursor with different Pt-precursors. Pt(acac)2, PtCl2, PtCl4 and H2PtCl6·H2O were used as Pt-precursors and Fe(acac)3 as the only Fe-precursor. Different stoichiometric compositions along with variation in size were obtained by using different precursors of Pt. Nearly, equiatomic FePt having a size ~2 nm was formed with Pt(acac)2. However, Pt rich phases were formed using all other precursors with a size ranging between 3.6 to 6.4 nm. It was found that the atomic percentage (at%) of Fe in the FePt NPs depends on the reaction parameters. The decomposition behaviour of Fe and Pt-precursors were examined by vibrating sample magnetometer and thermogravimetric measurements. A possible reaction mechanism for Fe depleted FePt formation is proposed which suggests that the reduction potential and decomposition behaviour of the organic and inorganic salts of Pt significantly modify the nucleation behaviour. The electrocatalytic properties of all the four nanomaterials towards methanol oxidation have been investigated by cyclic voltammetry. It is found that Fe19Pt81 with an average size of 6.2 nm shows the highest catalytic response.

In vitro evaluation of PEGylated mesoporous MgFe2O4 magnetic nanoassemblies (MMNs) for chemo-thermal therapy.

A size tunable synthesis of mesoporous MgFe2O4 magnetic nanoassemblies (MMNs) through a PEG-diacid mediated polyol method is reported. The PEG-diacid coated MMNs exhibit a significant specific surface area of 92 m2 g-1 and saturation magnetization of 57 emu g-1. These MMNs exhibit a very good colloidal stability in PBS (pH 7.4) with nonappreciable cytotoxicity in mouse fibroblast (L929) and cervical cancer (HeLa) cells. We demonstrate the potential of MMNs as an integrated nanosystem for drug delivery and magnetic hyperthermia (MHT) through in vitro studies. 80% loading efficiency of doxorubicin (DOX) has been achieved due to the highly negative surface charge and mesoporous nature of MMNs. It is observed that 65-70% of HeLa cells undergo apoptosis through DNA fragmentation after 24 h of incubation with DOX loaded MMNs. MHT alone induces the death of 40-45% of cells, whereas the synergistic effect of a combination of DOX and MHT leads to the death of about 90% of cells. Our results show that MHT significantly increases the therapeutic efficacy of DOX to induce more apoptosis in cancer cells. Hence, a combination of MHT with chemotherapy makes MMNs a powerful multimodal system for synergistic chemo-thermal cancer therapy.