ABSTRACT
Inspired by the iron porphyrin structure of natural horseradish peroxidase (HRP), an efficient carbon-based nanozyme was fabricated using nitrogen-doped graphene quantum dots (NGQDs) and iron ion (Fe3+) nanocomposite, enabling selective distinguishment of hydroquinone (HQ) from its isomers. NGQDs with good dispersibility and uniform size were synthesized via a one-step hydrothermal process. NGQDs lacked peroxidase-like activity but the formed nanocomposite (Fe3+-NGQDs) upon Fe3+ addition possessed high peroxidase-like activity. Fe3+-NGQDs nanocomposite exhibited shuttle-shaped structure (â¼30 nm), the lattice structure of NGQDs and electron transfer between Fe3+ and NGQDs. The Fe3+-NGQDs nanocomposite can catalyze the production of superoxide radicals (â¢O2-) from H2O2. The Michaelis constant (Km) of Fe3+-NGQDs (0.115 mM) was lower than that of natural HRP (0.434 mM) with 3,3',5,5'-tetramethylbenzidine (TMB) as the substrate and the maximum initial reaction rate (Vmax, 16.47 × 10-8 M/s) was nearly 4 times higher than that of HRP using H2O2 substrate. HQ, unlike its isomers catechol (CC) and resorcinol (RE), could consume â¢O2- generated from the decomposition of H2O2 catalyzed by Fe3+-NGQDs nanocomposite, reducing the oxidation of TMB. This principle enabled selective colorimetric determination of HQ ranged from 1 µM to 70 µM and a limit of detection (LOD) of 0.2 µM. Successful determination of HQ in pond water was also realized.
ABSTRACT
Graphene quantum dots (GQDs) commonly suffer from the fluorescence problem of aggregation-caused quenching under high-concentration loading or in the solid state, which seriously hinders the application. Here we report a type of GQDs with red aggregation-induced enhanced emission (AIEE). It is confirmed that the aggregation state of the AIEE GQDs is a J-aggregate. The GQDs/poly(methyl methacrylate) film presented a photoluminescence quantum yield as high as 60.81%, and the record-high performance of luminescent solar concentrators (LSCs) was achieved. The power conversion efficiency (ηPCE) is up to 8.35% and the external optical efficiency (ηext) is â¼8.99% for the GQD-based LSCs (45 mW/cm2). Even under one sun illumination (100 mW/cm2), the corresponding ηPCE and ηext values are 3.12% and 4.52%, respectively. The internal photon efficiency (ηint) of an LSC device is about 5.02%. The synthesis of AIEE GQDs bridges the research gap in the emission mechanism of AIEE in GQDs.
ABSTRACT
Graphene quantum dots (GQDs) are an evolving class of carbon-based nanomaterial, seizing tremendous attention owing to their intense optical property, engineered shapes and structures, and good photostability. Being a zero-dimensional form of carbon structure, GQDs have superior photoluminescent behavior, tunable emission and absorption, excellent biocompatibility, low cytotoxicity, hydrophilic nature, modifying surface states. Their water dispersibility and functionalized surface structure, involving heteroatoms and various functional groups onto the surface of GQDs, make them particularly suitable for biological applications. Based on their absolute luminescence properties, GQDs emit blue, green, yellow, and red light under ultraviolet irradiation. Amongst the three colors, red luminescence can achieve deeper penetration of light into tissues, good cellular distribution, bio-sensing property, cell imaging, drug delivery, and serves as a better candidate for photodynamic therapy. The overall objective of this review is to provide a comprehensive overview of the synthesis methods for red fluorescence graphene quantum dots (RF-GQDs), critical comparative analyses of spectral techniques used for their characterization, the tunable photoluminescence mechanisms underpinning red emission, and the significance of chemically functionalizing GQDs' surface edges in achieving red fluorescence are discussed in depth. This review also discusses the effective biological applications and critical challenges associated with RF-GQDs are examined, providing insights into their future potential in clinical and industrial applications.
ABSTRACT
Easy, economical, and swift detecting tools are very demanded for assaying various chemical species. The introduction of label-free paper-based read-out devices has significantly reached the demand of analytical science for target analytes assays. Herein, a facile, and disposable inexpensive paper-based sensing tool was fabricated for sensing As3+ ion using graphene quantum dots (GQDs) as a fluorescent reader. The CA-GQDs were synthesized using citric acid (CA) as a precursor via the pyrolysis method, further physisorbed on the cellulose substrate for sensing of As3+ via aggregation-based fluorescence "turn-off" mechanism. The linear range for quantitating As3+ ion is in the range of 0.05-50 µM with a detection limit of 10 nM. The practical application of the CA-GQDs-based analytical platform was verified by assaying As3+ ion in water samples. The CA-GQDs-embedded paper strip can be easily extended for assaying of As3+ ion, which meets the demand for monitoring of As3+ ion in real samples.
Subject(s)
Cellulose , Graphite , Paper , Quantum Dots , Graphite/chemistry , Quantum Dots/chemistry , Cellulose/chemistry , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Spectrometry, Fluorescence , Ions/analysis , Ions/chemistry , Limit of Detection , FluorescenceABSTRACT
Graphene Quantum Dots (GQDs) have shown the potential for antimicrobial photodynamic treatment, due to their particular physicochemical properties. Here, we investigated the activity of three differently functionalized GQDs-Blue Luminescent GQDs (L-GQDs), Aminated GQDs (NH2-GQDs), and Carboxylated GQDs (COOH-GQDs)-against E. coli. GQDs were administrated to bacterial suspensions that were treated with blue light. Antibacterial activity was evaluated by measuring colony forming units (CFUs) and metabolic activities, as well as reactive oxygen species stimulation (ROS). GQD cytotoxicity was then assessed on human colorectal adenocarcinoma cells (Caco-2), before setting in an in vitro infection model. Each GQD exhibits antibacterial activity inducing ROS and impairing bacterial metabolism without significantly affecting cell morphology. GQD activity was dependent on time of exposure to blue light. Finally, GQDs were able to reduce E. coli burden in infected Caco-2 cells, acting not only in the extracellular milieu but perturbating the eukaryotic cell membrane, enhancing antibiotic internalization. Our findings demonstrate that GQDs combined with blue light stimulation, due to photodynamic properties, have a promising antibacterial activity against E. coli. Nevertheless, we explored their action mechanism and toxicity on epithelial cells, fixing and standardizing these infection models.
Subject(s)
Anti-Bacterial Agents , Blue Light , Escherichia coli , Graphite , Quantum Dots , Reactive Oxygen Species , Humans , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Caco-2 Cells , Escherichia coli/drug effects , Graphite/chemistry , Graphite/pharmacology , Photochemotherapy/methods , Quantum Dots/chemistry , Reactive Oxygen Species/metabolismABSTRACT
Herein, we report a single step synthesis of highly fluorescent Graphene Quantum Dots (GQDs) using tryptophan and glycerol as precursors via pyrolysis. The morphological and functional characterization of the prepared GQDs was performed using PXRD, FTIR, TEM, XPS and zeta potential measurements. The prepared GQDs found their practical application in ultrasensitive detection of an emerging potential cancer biomarker, H2O2, by exploiting the fluorescence quenching behaviour of H2O2. To evaluate the detection sensitivity, a series of various concentrations of H2O2 was spiked to biomatrices like, serum and MCF-7 (human breast cancer cell line) cell lysate medium. A remarkably low limit of detection (LOD) was found in serum medium (139.5 pM) which further improved in MCF-7 cell lysate medium (LOD 61.43 pM). Moreover, the sensing capacity of the GQDs was further validated in presence of various physiological variables such as glucose, cholesterol, insulin and nitrite. Sensing assay was also carried out in HaCaT (human keratinocyte cell line) cell lysate medium to compare the performance of our prepared sensor but the non-linearity of the F0/F versus H2O2 concentration plot pointed towards the conduciveness of the MCF-7 cell lysate medium for sensitive detection of H2O2.The mechanism behind the sensing was also explored using spectroscopic methods.
Subject(s)
Graphite , Hydrogen Peroxide , Limit of Detection , Quantum Dots , Spectrometry, Fluorescence , Tryptophan , Graphite/chemistry , Quantum Dots/chemistry , Humans , Hydrogen Peroxide/analysis , Hydrogen Peroxide/chemistry , Tryptophan/analysis , Tryptophan/chemistry , MCF-7 Cells , Spectrometry, Fluorescence/methods , Fluorescent Dyes/chemistryABSTRACT
Due to high tissue penetration depth and low autofluorescence backgrounds, near-infrared (NIR) fluorescence imaging has recently become an advantageous diagnostic technique used in a variety of fields. However, most of the NIR fluorophores do not have therapeutic delivery capabilities, exhibit low photostabilities, and raise toxicity concerns. To address these issues, we developed and tested five types of biocompatible graphene quantum dots (GQDs) exhibiting spectrally-separated fluorescence in the NIR range of 928-1053 nm with NIR excitation. Their optical properties in the NIR are attributed to either rare-earth metal dopants (Ho-NGQDs, Yb-NGQDs, Nd-NGQDs) or defect-states (nitrogen doped GQDS (NGQDs), reduced graphene oxides) as verified by Hartree-Fock calculations. Moderate up to 1.34% quantum yields of these GQDs are well-compensated by their remarkable >4 h photostability. At the biocompatible concentrations of up to 0.5-2 mg ml-1 GQDs successfully internalize into HEK-293 cells and enable in vitro imaging in the visible and NIR. Tested all together in HEK-293 cells five GQD types enable simultaneous multiplex imaging in the NIR-I and NIR-II shown for the first time in this work for GQD platforms. Substantial photostability, spectrally-separated NIR emission, and high biocompatibility of five GQD types developed here suggest their promising potential in multianalyte testing and multiwavelength bioimaging of combination therapies.
ABSTRACT
Graphene quantum dots (GQDs) are used in diverse fields from chemistry-related materials to biomedicines, thus causing their substantial release into the environment. Appropriate visual function is crucial for facilitating the decision-making process within the nervous system. Given the direct interaction of eyes with the environment and even nanoparticles, herein, GQDs, sulfonic acid-doped GQDs (S-GQDs), and amino-functionalized GQDs (A-GQDs) were employed to understand the potential optic neurotoxicity disruption mechanism by GQDs. The negatively charged GQDs and S-GQDs disturbed the response to light stimulation and impaired the structure of the retinal nuclear layer of zebrafish larvae, causing vision disorder and retinal degeneration. Albeit with sublethal concentrations, a considerably reduced expression of the retinal vascular sprouting factor sirt1 through increased DNA methylation damaged the blood-retina barrier. Importantly, the regulatory effect on vision function was influenced by negatively charged GQDs and S-GQDs but not positively charged A-GQDs. Moreover, cluster analysis and computational simulation studies indicated that binding affinities between GQDs and the DNMT1-ligand binding might be the dominant determinant of the vision function response. The previously unknown pathway of blood-retinal barrier interference offers opportunities to investigate the biological consequences of GQD-based nanomaterials, guiding innovation in the industry toward environmental sustainability.
Subject(s)
DNA Methylation , Graphite , Quantum Dots , Quantum Dots/chemistry , Quantum Dots/toxicity , Graphite/chemistry , Animals , Retinal Degeneration , Blood-Retinal Barrier/metabolism , ZebrafishABSTRACT
Many people lose their lives to cancer each year. The prevalence of illnesses, metabolic disorders, high-risk infections, and other conditions has been greatly slowed down by expanding scientific research. Chemotherapy and radiation are still the initial lines of treatment for cancer patients, along with surgical removal of tumors. Modifications have been made in chemotherapy since medicines frequently have substantial systemic toxicity and poor pharmacokinetics and still do not reach the tumor site at effective concentrations. Chemotherapy may now be administered more safely and effectively thanks to nanotechnology. Nanotechnology-based graphene quantum dots (GQDs) are very applicable in breast cancer detection, as a drug delivery system, and in the treatment of breast cancer because of their physical and chemical properties, lower toxicity, small size, fluorescence, and effective drug delivery. This paper analyzes the GQDs as cutting-edge platforms for biotechnology and nanomedicine also its application in drug delivery in cancer. It shows that GQDs can be effectively conjugated with hyaluronic acid (HA) to achieve efficient and target-specific delivery.
ABSTRACT
E6 and E7 oncogenes are pivotal in the carcinogenic transformation in HPV infections and efficient diagnostic methods can ensure the detection and differentiation of HPV genotype. This study describes the development and validation of an electrochemical, label-free genosensor coupled with a microfluidic system for detecting the E6 and E7 oncogenes in cervical scraping samples. The nanostructuring employed was based on a cysteine and graphene quantum dots layer that provides functional groups, surface area, and interesting electrochemical properties. Biorecognition tests with cervical scraping samples showed differentiation in the voltammetric response. Low-risk HPV exhibited a lower biorecognition response, reflected in ΔI% values of 82.33 % ± 0.29 for HPV06 and 80.65 % ± 0.68 for HPV11 at a dilution of 1:100. Meanwhile, high-risk, HPV16 and HPV18, demonstrated ΔI% values of 96.65 % ± 1.27 and 93 % ± 0.026, respectively, at the same dilution. Therefore, the biorecognition intensity followed the order: HPV16 >HPV18 >HPV06 >HPV11. The limit of detection and the limit of quantification of E6E7 microfluidic LOC-Genosensor was 26 fM, and 79.6 fM. Consequently, the E6E7 biosensor is a valuable alternative for clinical HPV diagnosis, capable of detecting the potential for oncogenic progression even in the early stages of infection.
ABSTRACT
BACKGROUND AND PURPOSE: Metal-based therapeutic agents are limited by the required concentration of metal-based agents. Hereby, we determined if combination with 17ß-oestradiol (E2) could reduce such levels and the therapy still be effective in type 2 diabetes mellitus (T2DM). EXPERIMENTAL APPROACH: The metal-based agent (vanadyl acetylacetonate [VAC])- 17ß-oestradiol (E2) combination is administered using the membrane-permeable graphene quantum dots (GQD), the vehicle, to form the active GQD-E2-VAC complexes, which was characterized by fluorescence spectra, infrared spectra and X-ray photoelectron spectroscopy. In db/db type 2 diabetic mice, the anti-diabetic effects of GQD-E2-VAC complexes were evaluated using blood glucose levels, oral glucose tolerance test (OGTT), serum insulin levels, homeostasis model assessment (homeostasis model assessment of insulin resistance [HOMA-IR] and homeostasis model assessment of ß-cell function [HOMA-ß]), histochemical assays and western blot. KEY RESULTS: In diabetic mice, GQD-E2-VAC complex had comprehensive anti-diabetic effects, including control of hyperglycaemia, improved insulin sensitivity, correction of hyperinsulinaemia and prevention of ß-cell loss. Co-regulation of thioredoxin interacting protein (TXNIP) activation by the combination of metal complex and 17ß-oestradiol contributed to the enhanced anti-diabetic effects. Furthermore, a potent mitochondrial protective antioxidant, coniferaldehyde, significantly potentiates the protective effects of GQD-E2-VAC complexes. CONCLUSION AND IMPLICATIONS: A metal complex-E2 combinatorial approach achieved simultaneously the protection of ß cells and insulin enhancement at an unprecedented low dose, similar to the daily intake of dietary metals in vitamin supplements. This study demonstrates the positive effects of combination and multi-modal therapies towards type 2 diabetes treatment.
ABSTRACT
Contrary to the initial belief that myofibroblasts are terminally differentiated cells, myofibroblasts have now been widely recognized as an activation state that is reversible. Therefore, strategies targeting myofibroblast to be a quiescent state may be an effective way for antihypertrophic scar therapy. Graphene quantum dots (GQDs), a novel zero-dimensional and carbon-based nanomaterial, have recently garnered significant interest in nanobiomedicine, owing to their excellent biocompatibility, tunable photoluminescence, and superior physiological stability. Although multiple nanoparticles have been used to alleviate hypertrophic scars, a GQD-based therapy has not been reported. Our in vivo studies showed that GQDs exhibited significant antiscar efficacy, with scar appearance improvement, collagen reduction and rearrangement, and inhibition of myofibroblast overproliferation. Further in vitro experiments revealed that GQDs inhibited α-SMA expression, collagen synthesis, and cell proliferation and migration, inducing myofibroblasts to become quiescent fibroblasts. Mechanistic studies have demonstrated that the effect of GQDs on myofibroblast proliferation blocked cell cycle progression by disrupting the cyclin-CDK-E2F axis. This study suggests that GQDs, which promote myofibroblast-to-fibroblast transition, could be a novel antiscar nanomedicine for the treatment of hypertrophic scars and other types of pathological fibrosis.
Subject(s)
Cell Proliferation , Cicatrix, Hypertrophic , Graphite , Myofibroblasts , Quantum Dots , Quantum Dots/chemistry , Myofibroblasts/drug effects , Myofibroblasts/pathology , Myofibroblasts/metabolism , Graphite/chemistry , Graphite/pharmacology , Cicatrix, Hypertrophic/drug therapy , Cicatrix, Hypertrophic/pathology , Cell Proliferation/drug effects , Animals , Humans , Mice , Collagen/chemistry , Cell Movement/drug effectsABSTRACT
Excessive reactive oxygen species (ROS) in cellular environments leads to oxidative stress, which underlies numerous diseases, including inflammatory diseases, neurodegenerative diseases, cardiovascular diseases, and cancer. Oxidative stress can be particularly damaging to biological membranes such as those found in mitochondria, which are abundant with polyunsaturated fatty acids (PUFAs). Oxidation of these biological membranes results in concomitant disruption of membrane structure and function, which ultimately leads to cellular dysfunction. Graphene quantum dots (GQDs) have garnered significant interest as a therapeutic agent for numerous diseases that are linked to oxidative stress. Specifically, GQDs have demonstrated an ability to protect mitochondrial structure and function under oxidative stress conditions. However, the fundamental mechanisms by which GQDs interact with membranes in oxidative environments are poorly understood. Here, we used C11-BODIPY, a fluorescent lipid oxidation probe, to develop quantitative fluorescence assays that determine both the extent and rate of oxidation that occurs to PUFAs in biological membranes. Based on kinetics principles, we have developed a generalizable model that can be used to assess the potency of antioxidants that scavenge ROS in the presence of biological membranes. By augmenting our fluorescence assays with 1H NMR spectroscopy, the results demonstrate that GQDs scavenge nascent hydroxyl and peroxyl ROS that interact with membranes and that GQDs are potent inhibitors of ROS-induced lipid oxidation in PUFA-containing biological membranes. The antioxidant potency of GQDs is comparable to or even greater than established antioxidant molecules, such as ascorbic acid and Trolox. This work provides mechanistic insights into the mitoprotective properties of GQDs under oxidative stress conditions, as well as a quantitative framework for assessing antioxidant interactions in biological membrane systems.
Subject(s)
Graphite , Lipid Peroxidation , Quantum Dots , Quantum Dots/chemistry , Graphite/chemistry , Graphite/pharmacology , Lipid Peroxidation/drug effects , Cell Membrane/metabolism , Cell Membrane/drug effects , Reactive Oxygen Species/metabolism , Biocompatible Materials/chemistry , Biocompatible Materials/pharmacology , Antioxidants/pharmacology , Antioxidants/chemistry , Materials Testing , Boron Compounds/chemistry , Boron Compounds/pharmacology , Oxidative Stress/drug effects , Particle Size , Humans , Fluorescent Dyes/chemistry , Fatty Acids, Unsaturated/chemistry , Fatty Acids, Unsaturated/pharmacology , Fatty Acids, Unsaturated/metabolism , Molecular StructureABSTRACT
This research explores the fluorescence properties and photostability of boron nitrogen co-doped graphene quantum dots (BN-GQDs), evaluating their effectiveness as sensors for rutin (RU). BN-GQDs are biocompatible and exhibit notable absorbance and fluorescence characteristics, making them suitable for sensing applications. The study utilized various analytical techniques to investigate the chemical composition, structure, morphology, optical attributes, elemental composition, and particle size of BN-GQDs. Techniques included X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The average particle size of the BN-GQDs was determined to be approximately 3.5 ± 0.3 nm. A clear correlation between the emission intensity ratio and RU concentration was identified across the range of 0.42 to 4.1 µM, featuring an impressively low detection limit (LOD) of 1.23 nM. The application of BN-GQDs as fluorescent probes has facilitated the development of a highly sensitive and selective RU detection method based on Förster resonance energy transfer (FRET) principles. This technique leverages emission at 465 nm. Density Functional Theory (DFT) analyses confirm that FRET is the primary mechanism behind fluorescence quenching, as indicated by the energy levels of the lowest unoccupied molecular orbitals (LUMOs) of BN-GQDs and RU. The method's effectiveness has been validated by measuring RU concentrations in human serum samples, showing a recovery range between 97.8% and 103.31%. Additionally, a smartphone-based detection method utilizing BN-GQDs has been successfully implemented, achieving a detection limit (LOD) of 49 nM.
ABSTRACT
An electrochemical immunoassay system was developed to detect CA-125 using a glassy carbon electrode (GCE) modified with MXene, graphene quantum dots (GQDs), and gold nanoparticles (AuNPs). The combined MXene-GQD/AuNPs modification displayed advantageous electrochemical properties due to the synergistic effects of MXene, GQDs, and AuNPs. The MXene-GQD composite in the modified layer provided strong mechanical properties and a large specific surface area. Furthermore, the presence of AuNPs significantly improved conductivity and facilitated the binding of anti-CA-125 on the modified GCE, thereby enhancing sensitivity. Various analytical techniques such as FE-SEM and EDS were utilized to investigate the structural and morphological characteristics as well as the elemental composition. The performance of the developed immunosensor was assessed using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), square wave voltammetry (SWV), and differential pulse voltammetry (DPV). Under optimized conditions in a working potential range of -0.2 to 0.6 V (vs. Ag/AgCl), the sensitivity, linear range (LR), limit of detection (LOD), and correlation coefficient (R2) were determined to be 315.250 µA pU.mL-1/cm2, 0.1 to 1 nU/mL, 0.075 nU/mL, and 0.9855, respectively. The detection of CA-125 in real samples was investigated using the developed immunoassay platform, demonstrating satisfactory results including excellent selectivity and reproducibility.
Subject(s)
CA-125 Antigen , Electrochemical Techniques , Gold , Graphite , Limit of Detection , Metal Nanoparticles , Ovarian Neoplasms , Quantum Dots , CA-125 Antigen/blood , CA-125 Antigen/analysis , Gold/chemistry , Metal Nanoparticles/chemistry , Humans , Ovarian Neoplasms/blood , Electrochemical Techniques/methods , Electrochemical Techniques/instrumentation , Immunoassay/methods , Female , Quantum Dots/chemistry , Graphite/chemistry , Antibodies, Immobilized/immunology , Biosensing Techniques/methods , Electrodes , Membrane ProteinsABSTRACT
Photodynamic therapy (PDT) is a non-invasive therapy that has made significant progress in treating different diseases, including cancer, by utilizing new nanotechnology products such as graphene and its derivatives. Graphene-based materials have large surface area and photothermal effects thereby making them suitable candidates for PDT or photo-active drug carriers. The remarkable photophysical properties of graphene derivates facilitate the efficient generation of reactive oxygen species (ROS) upon light irradiation, which destroys cancer cells. Surface functionalization of graphene and its materials can also enhance their biocompatibility and anticancer activity. The paper delves into the distinct roles played by graphene-based materials in PDT such as photosensitizers (PS) and drug carriers while at the same time considers how these materials could be used to circumvent cancer resistance. This will provide readers with an extensive discussion of various pathways contributing to PDT inefficiency. Consequently, this comprehensive review underscores the vital roles that graphene and its derivatives may play in emerging PDT strategies for cancer treatment and other medical purposes. With a better comprehension of the current state of research and the existing challenges, the integration of graphene-based materials in PDT holds great promise for developing targeted, effective, and personalized cancer treatments.
Subject(s)
Drug Resistance, Neoplasm , Graphite , Neoplasms , Photochemotherapy , Photosensitizing Agents , Reactive Oxygen Species , Graphite/chemistry , Graphite/pharmacology , Photochemotherapy/methods , Humans , Neoplasms/drug therapy , Photosensitizing Agents/chemistry , Photosensitizing Agents/pharmacology , Reactive Oxygen Species/metabolism , Drug Resistance, Neoplasm/drug effects , Drug Carriers/chemistry , AnimalsABSTRACT
CONTEXT: The development of efficient solar energy conversion technologies is crucial for addressing global energy challenges and reducing reliance on fossil fuels. Platinum(II) complexes are promising materials for photovoltaic applications due to their strong light absorption and long-lived excited states. However, their narrow absorption in the visible spectrum and stability issues limit their performance. Combining platinum(II) complexes with graphene quantum dots (GQDs) can enhance photovoltaic performance by leveraging the complementary light harvesting and charge transfer characteristics of the two components. This study utilizes density functional theory (DFT) calculations to explore their electronic structures, charge transfer dynamics, and photoelectric performance. Specifically, it investigates the effects of incorporating different substituents, either electron-donating or electron-withdrawing, onto the fluorene motif of the Pt(II) complex. The findings reveal that combining GQDs with Pt(II) complexes extends light absorption into the UV range, enabling comprehensive solar utilization. Upon photoexcitation, electrons migrate between the GQD conduction band and the Pt(II) complex, stabilizing charges and enhancing extraction. Substituents significantly influence charge transfer dynamics: electron-withdrawing groups promote transfer to the GQD, while electron-donating groups encourage charge separation and delocalization. Nanocomposites featuring electron-donating substituents achieve the highest energy conversion efficiencies, with GQD@Pt(II)-NPh2 reaching 24.6%. This is attributed to improved light harvesting, efficient charge injection, and reduced recombination. These insights guide the rational design of GQD-Pt(II) nanocomposites, optimizing charge separation and transfer processes for enhanced photovoltaic performance. The computational approach employed here provides a robust tool for developing advanced materials in renewable energy technologies. METHODS: The computational studies reported in this work were performed using the DFT approach, specifically employing the hybrid functional PBE0. The PBE0 functional's accuracy in describing electronic structures and excited-state properties is essential for understanding charge transfer processes, photoabsorption, and emission characteristics in metal-organic complexes. Geometry optimizations and time-dependent DFT (TD-DFT) calculations were carried out to investigate the properties of the nanocomposites. The effects of solvents were replicated using the conductor-like polarizable continuum model (CPCM). The charge transfer length (ΔL) and interfragment charge transfer (ΔQ) were calculated using the Multiwfn software package, and all calculations were performed using the BDF software package.
ABSTRACT
Benzene, as a common volatile organic compound, represents serious risk to human health and environment even at low level concentration. There is an urgent concern on visualized, sensitive and real time detection of benzene gases. Herein, by doping Fe3+ and graphene quantum dots (GQDs), a cellulose nanocrystal (CNC) chiral nematic film was designed with dual response of photonic colors and fluorescence to benzene gas. The chiral nematic CNC/Fe/GQDs film could respond to benzene gas changes by reversible motion. Moreover, chiral nematic film also displays reversible responsive to humidity changes. The resulting CNC/Fe/GQDs chiral nematic film showed excellent response performance at benzene gas concentrations of 0-250 mg/m3. The maximal reflection wavelength film red shifted from 576 to 625 nm. Furthermore, structural color of CNC/Fe/GQDs chiral nematic film change at 44 %, 54 %, 76 %, 87 %, and 99 % relative humidity. Interestingly, due to the stability of GQDs to water molecules, CNC/Fe/GQDs chiral nematic film exhibit fluorescence response to benzene gas even in high humidity (RH = 99 %) environment. Besides, we further developed a smartphone-based response network system for quantitively determinization and signal transformation. This work provides a promising routine to realize a new benzene gas response regime and promotes the development of real-time benzene gas detection.
Subject(s)
Benzene , Cellulose , Nanoparticles , Cellulose/chemistry , Benzene/chemistry , Benzene/analysis , Nanoparticles/chemistry , Quantum Dots/chemistry , Graphite/chemistry , Fluorescence , Gases/analysis , Gases/chemistry , Color , PhotonsABSTRACT
A TiO2/graphene quantum dots composite (TiO2/GQDs) obtained by in situ synthesis of GQDs, derived from coffee grounds, and peroxo titanium complexes was used as electrode modifier in the simultaneous electrochemical determination of uric acid and hypoxanthine. The TiO2/GQDs material was characterized by photoluminescence, X-ray diffraction, Raman spectroscopy, high-resolution transmission electron microscopy, and energy-dispersive X-ray mapping. The TiO2/GQDs-GCE exhibits better electrochemical activity for uric acid and hypoxanthine than GQDs/GCE or TiO2/GCE in differential pulse voltammetry (DPV) measurements. Under optimized conditions, the calibration plots were linear in the range from 1.00 to 15.26 µM for both uric acid and hypoxanthine. The limits of detection of this method were 0.58 and 0.68 µM for uric acid and hypoxanthine, respectively. The proposed DPV method was employed to determine uric acid and hypoxanthine in urine samples with acceptable recovery rates.
ABSTRACT
A new type of 0-dimensional carbon-based materials called graphene quantum dots (GQDs) is gaining significant attention as a non-toxic and eco-friendly nanomaterial. GQDs are nanomaterials composed of sp2hybridized carbon domains and functional groups, with their lateral size less than 10 nm. The unique and exceptional physical, chemical, and optical properties arising from the combination of graphene structure and quantum confinement effect due to their nano-size make GQDs more intriguing than other nanomaterials. Particularly, the low toxicity and high solubility derived from the carbon core and abundant edge functional groups offer significant advantages for the application of GQDs in the biomedical field. In this review, we summarize various synthetic methods for preparing GQDs and important factors influencing the physical, chemical, optical, and biological properties of GQDs. Furthermore, the recent application of GQDs in the biomedical field, including biosensor, bioimaging, drug delivery, and therapeutics are discussed. Through this, we provide a brief insight on the tremendous potential of GQDs in biomedical applications and the challenges that need to be overcome in the future.