Pharmaceutical residues are emerging pollutants in the aquatic environment and their removal by conventional wastewater treatment methods has proven to be ineffective. This research aimed to develop a three-dimensional reduced graphene oxide aerogel (rGOA) for the removal of diclofenac in aqueous solution. The preparation of rGOA involved facile self-assembly of graphene oxide under a reductive environment of L-ascorbic acid. Characterisation of rGOA was performed by Fourier transform infrared, scanning electron microscope, transmission electron microscopy, nitrogen adsorption-desorption, Raman spectroscopy and X-ray diffraction. The developed rGOA had a measured density of 20.39 ± 5.28 mg/cm3, specific surface area of 132.19 m2/g, cumulative pore volume of 0.5388 cm3/g and point of zero charge of 6.3. A study on the simultaneous interactions of independent factors by response surface methodology suggested dosage and initial concentration as the dominant parameters influencing the adsorption of diclofenac. The highest diclofenac adsorption capacity (596.71 mg/g) was achieved at the optimum conditions of 0.25 g/L dosage, 325 mg/L initial concentration, 200 rpm shaking speed and 30 °C temperature. The adsorption equilibrium data were best fitted to the Freundlich model with correlation coefficient (R2) varying from 0.9500 to 0.9802. The adsorption kinetic data were best correlated to the pseudo-first-order model with R2 ranging from 0.8467 to 0.9621. Thermodynamic analysis showed that the process was spontaneous (∆G = - 7.19 to - 0.48 kJ/mol) and exothermic (∆H = - 12.82 to - 2.17 kJ/mol). This research concluded that rGOA is a very promising adsorbent for the remediation of water polluted by diclofenac.
Graphene oxide/chitosan aerogel (GOCA) was prepared by a facile ice-templating technique without using any cross-linking reagent for metanil yellow dye sequestration. The adsorption performance of GOCA was investigated by varying the adsorbent mass, shaking speed, initial pH, contact time, concentration and temperature. The combined effects of adsorption parameters and the optimum conditions for dye removal were determined by response surface methodology. GOCA exhibited large removal efficiencies (91.5-96.4%) over a wide pH range (3-8) and a high adsorption capacity of 430.99 mg/g at 8 mg adsorbent mass, 400 mg/L concentration, 35.19 min contact time and 175 rpm shaking speed. The adsorption equilibrium was best represented by the Langmuir model. GOCA could be easily separated after adsorption and regenerated for re-use in 5 adsorption-desorption cycles thereby maintaining 80% of its adsorption capability. The relatively high adsorption and regeneration capabilities of GOCA render it an attractive adsorbent for treatment of azo dye-polluted water.
Deoxynivalenol (DON), a cosmopolitan mycotoxin found in agricultural commodities causes serious health maladies to human and animals when accidently consumed even at a low quantity. It necessitates selective and sensitive devices to analyse DON as the conventional methods are complex and time-consuming. This study is focused on developing a selective biosensing system using iron nanoflorets graphene nickel (INFGN) as the transducer and a specific aptamer as the biorecognition element. 3D-graphene is incorporated using a low-pressure chemical vapour deposition followed by the decoration of iron nanoflorets using electrochemical deposition. INFGN enables a feasible bio-capturing due to its large surface area. The X-ray photoelectron spectroscopy analysis confirms the presence of the hydroxyl groups on the INFGN surface, which acts as the linker. Clear Fourier-transform infrared peak shifts affirm the changes with surface chemical modification and biomolecular assembly. The limit of detection attained is 2.11 pg mL-1 and displays high stability whereby it retains 30.65% of activity after 48 h. The designed INFGN demonstrates remarkable discrimination of DON against similar mycotoxins (zearalenone and ochratoxin A). Overall, the high-performance biosensor shown here is an excellent, simple and cost-effective alternative for detecting DON in food and feed samples.
The remediation of wastewater requires treatment technologies which are robust, efficient, simple to operate and affordable such as adsorption. Lately, three-dimensional (3D) graphene based materials have attracted significant attention as effective adsorbents for wastewater treatment. The intrinsic properties of 3D graphene structure such as large surface area and interconnected porous structure can facilitate the transport of pollutants into the 3D network and provide abundant active sites for trapping the pollutants. For the synthesis of 3D graphene structure, ice-templating is commonly practiced due to its facile steps, cost effectiveness and high scalability potential. This review covers the ice-templating fabrication technique for 3D graphene based materials and their application as adsorbents in eliminating dyes and heavy metals from aqueous media. The assembly mechanisms of the ice-templating fsynthesis are comprehensively discussed. Further discussion on the fundamental principles, critical process parameters and characteristics of ice-templated 3D graphene structures is also included. A thorough review on the mechanisms for batch adsorption of dyes and heavy metals is presented based on the structures and properties of the 3D graphene materials. The review further evaluates the dynamic adsorption in packed columns and the regeneration of 3D graphene based materials.
As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and "earth-abundant" nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The construction and characteristics of each classification of the heterojunction system will be critically reviewed, namely metal-g-C3N4, semiconductor-g-C3N4, isotype g-C3N4/g-C3N4, graphitic carbon-g-C3N4, conducting polymer-g-C3N4, sensitizer-g-C3N4, and multicomponent heterojunctions. The band structures, electronic properties, optical absorption, and interfacial charge transfer of g-C3N4-based heterostructured nanohybrids will also be theoretically discussed based on the first-principles density functional theory (DFT) calculations to provide insightful outlooks on the charge carrier dynamics. Apart from that, the advancement of the versatile photoredox applications toward artificial photosynthesis (water splitting and photofixation of CO2), environmental decontamination, and bacteria disinfection will be presented in detail. Last but not least, this comprehensive review will conclude with a summary and some invigorating perspectives on the challenges and future directions at the forefront of this research platform. It is anticipated that this review can stimulate a new research doorway to facilitate the next generation of g-C3N4-based photocatalysts with ameliorated performances by harnessing the outstanding structural, electronic, and optical properties for the development of a sustainable future without environmental detriment.
In this work, a sunlight-sensitive photocatalyst of nanocubic-like titanium dioxide (TiO2) and N-doped graphene quantum dots (N-GQDs) is developed through a simple hydrothermal and physical mixing method. The successful amalgamation composite photocatalyst characteristics were comprehensively scrutinized through various physical and chemical analyses. A complete removal of bisphenol A (BPA) is attained by a synthesized composite after 30 min of sunlight irradiation as compared to pure TiO2. This clearly proved the unique contribution of N-GQDs that enhanced the ability of light harvesting especially under visible light and near-infrared region. This superior characteristic enables it to maximize the absorbance in the entire solar spectrum. However, the increase of N-GQDs weight percentage has created massive oxygen vacancies that suppress the generation of active radicals. This resulted in a longer duration for a complete removal of BPA as compared to lower weight percentage of N-GQDs. Hence, this finding can offer a new insight in developing effective sunlight-sensitive photocatalysts for various complex organic pollutants degradation.
Generally, in a waveguide-based humidity sensors, increasing the relative humidity (RH) causes the cladding refractive index (RI) to increase due to cladding water absorption. However, if graphene oxide (GO) is used, a reverse phenomenon is seen due to a gap increase in graphene layers. In this paper, this interesting property is applied in order to fabricate differential humidity sensor using the difference between RI of reduced GO (rGO) and nano-anatase TiO2 in a chip. First, a new approach is proposed to prepare high quality nano-anatase TiO2 in solution form making the fabrication process simple and straightforward. Then, the resulted solutions (TiO2 and GO) are effortlessly drop casted and reduced on SU8 two channels waveguide and extensively examined against several humid conditions. Investigating the sensitivity and performance (response time) of the device, reveals a great linearity in a wide range of RH (35% to 98%) and a variation of more than 30 dB in transmitted optical power with a response time of only ~0.7 sec. The effect of coating concentration and UV treatment are studied on the performance and repeatability of the sensor and the attributed mechanisms explained. In addition, we report that using the current approach, devices with high sensitivity and very low response time of only 0.3 sec can be fabricated. Also, the proposed device was comprehensively compared with other state of the art proposed sensors in the literature and the results were promising. Since high sensitivity ~0.47dB/%RH and high dynamic performances were demonstrated, this sensor is a proper choice for biomedical applications.
The use of deoxyribonucleic acid (DNA) hybridization to detect disease-related gene expression is a valuable diagnostic tool. An ion-sensitive field-effect transistor (ISFET) with a graphene layer has been utilized for detecting DNA hybridization. Silicene is a two-dimensional silicon allotrope with structural properties similar to graphene. Thus, it has recently experienced intensive scientific research interest due to its unique electrical, mechanical, and sensing characteristics. In this paper, we proposed an ISFET structure with silicene and electrolyte layers for the label-free detection of DNA hybridization. When DNA hybridization occurs, it changes the ion concentration in the surface layer of the silicene and the pH level of the electrolyte solution. The process also changes the quantum capacitance of the silicene layer and the electrical properties of the ISFET device. The quantum capacitance and the corresponding resonant frequency readout of the silicene and graphene are compared. The performance evaluation found that the changes in quantum capacitance, resonant frequency, and tuning ratio indicate that the sensitivity of silicene is much more effective than graphene.
Tissue engineering embraces the potential of recreating and replacing defective body parts by advancements in the medical field. Being a biocompatible nanomaterial with outstanding physical, chemical, optical, and biological properties, graphene-based materials were successfully employed in creating the perfect scaffold for a range of organs, starting from the skin through to the brain. Investigations on 2D and 3D tissue culture scaffolds incorporated with graphene or its derivatives have revealed the capability of this carbon material in mimicking in vivo environment. The porous morphology, great surface area, selective permeability of gases, excellent mechanical strength, good thermal and electrical conductivity, good optical properties, and biodegradability enable graphene materials to be the best component for scaffold engineering. Along with the apt microenvironment, this material was found to be efficient in differentiating stem cells into specific cell types. Furthermore, the scope of graphene nanomaterials in liver tissue engineering as a promising biomaterial is also discussed. This review critically looks into the unlimited potential of graphene-based nanomaterials in future tissue engineering and regenerative therapy.
We present a biogenic method for the synthesis of palladium nanoparticle (PdNP)-modified by reducing graphene oxide sheets (rGO) in a one-pot strategy using Ficus carica fruit juice as the reducing agent. The synthesized material was well characterized by morphological and structural analyses, including, Ultraviolet-Visible spectroscopy (UV-Vis), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and Transmission Electron Microscopy (TEM) and Raman spectroscopy. The results revealed that the PdNP modified GO are spherical in shape and estimated to be a dimension of ~0.16 nm. The PdNP/graphene exhibits a great catalytic activity in Suzuki cross-coupling reactions for the synthesis of biaryl compounds with various substrates under both aqueous and aerobic conditions. The catalyst can be recovered easily and is suitable for repeated use because it retains its original catalytic activity. The PdNP/rGO catalyst synthesized by an eco-friendly protocol was used for the Suzuki coupling reactions. The method offers a mild and effective substitute to the existing methods and may significantly contribute to green chemistry.
In this paper, Response Surface Methodology with central composite design (RSM/CCD) was used to optimize a modified electrode for improved electron transfer rate and electrochemical performance. The modification was done on a screen-printed carbon electrode (SPCE) with reduced graphene oxide (ERGO)/calix [4] arene (ERGOC4-SPCE). The properties of the modified electrodes were analyzed via cyclic voltammetry, Raman spectroscopy, and Fourier-Transform Infrared (FT-IR) spectroscopy. Then, different variables were optimized, namely, the concentration of graphene oxide, GO (A), the number of scan cycles of graphene oxide (B), and the deposition time (C). The effect of the optimized variables on the reduction-oxidation peak current response of the potassium ferricyanide redox system was analyzed. By using statistical analysis, it shows a significant effect of the concentration of GO, the deposition time, and the number of scans cycles on the peak current response. The coefficient of determination (R2) value of 0.9987 produced indicated a good fit of the model with experimental finding.
Graphene and its hybrids are being employed as potential materials in light-sensing devices due to their high optical and electronic properties. However, the absence of a bandgap in graphene limits the realization of devices with high performance. In this work, a boron-doped reduced graphene oxide (B-rGO) is proposed to overcome the above problems. Boron doping enhances the conductivity of graphene oxide and creates several defect sites during the reduction process, which can play a vital role in achieving high-sensing performance of light-sensing devices. Initially, the B-rGO is synthesized using a modified microwave-assisted hydrothermal method and later analyzed using standard FESEM, FTIR, XPS, Raman, and XRD techniques. The content of boron in doped rGO was found to be 6.51 at.%. The B-rGO showed a tunable optical bandgap from 2.91 to 3.05 eV in the visible spectrum with an electrical conductivity of 0.816 S/cm. The optical constants obtained from UV-Vis absorption spectra suggested an enhanced surface plasmon resonance (SPR) response for B-rGO in the theoretical study, which was further verified by experimental investigations. The B-rGO with tunable bandgap and enhanced SPR could open up the solution for future high-performance optoelectronic and sensing applications.
Graphene is an allotrope of carbon with two-dimensional (2D) monolayer honeycombs. A larger detection area and higher sensitivity can be provided by graphene-based nanosenor because of its 2D structure. In addition, owing to its special characteristics, including electrical, optical and physical properties, graphene is known as a more suitable candidate compared to other materials used in the sensor application. A novel model employing a field-effect transistor structure using graphene is proposed and the current-voltage (I-V) characteristics of graphene are employed to model the sensing mechanism. This biosensor can detect Escherichia coli (E. coli) bacteria, providing high levels of sensitivity. It is observed that the graphene device experiences a drastic increase in conductance when exposed to E. coli bacteria at 0-10(5) cfu/ml concentration. The simple, fast response and high sensitivity of this nanoelectronic biosensor make it a suitable device in screening and functional studies of antibacterial drugs and an ideal high-throughput platform which can detect any pathogenic bacteria. Artificial neural network and support vector regression algorithms have also been used to provide other models for the I-V characteristic. A satisfactory agreement has been presented by comparison between the proposed models with the experimental data.
In this study, the authors investigated the effects of a single layer graphene as a coating layer on top of metal thin films such as silver, gold, aluminum and copper using finite-difference time domain method. To enhance the resolution of surface plasmon resonance (SPR) sensor, it is necessary to increase the SPR reflectivity and decrease the full-width-half maximum (FWHM) of the SPR curve so that there is minimum uncertainty in the determination of the resonance dip. Numerical data was verified with analytical and experimental data where all the data were in good agreement with resonance angle differing in <10% due to noise present in components such as humidity and temperature. In further analysis, reflectivity and FWHM were compared among four types of metal with various thin film thicknesses where graphene was applied on top of the metal layers, and data was compared against pure conventional metal thin films. A 60 nm-thick Au thin film results in higher performance with reflectivity of 92.4% and FWHM of 0.88° whereas single layer graphene-on-60 nm-thick Au gave reflectivity of 91.7% and FWHM of 1.32°. However, a graphene-on-40 nm-thick Ag also gave good performance with narrower FWHM of 0.88° and reflection spectra of 89.2%.
The chemical route of producing geranyl propionate involves the use of toxic chemicals, liberation of unwanted by-products as well as problematic separation process. In view of such problems, the use of Rhizomucor miehei lipase (RML) covalently bound onto activated chitosan-graphene oxide (RML-CS/GO) support is suggested. Following analyses using Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, and thermogravimetry, properties of the RML-CS/GO were characterized. A response surface methodological approach using a 3-level-four-factor (incubation time, temperature, substrate molar ratio, and stirring rate) Box-Behnken design was used to optimize the experimental conditions to maximize the yield of geranyl propionate. Results revealed that 76 ± 0.02% of recovered protein had yielded 7.2 ± 0.04 mg g(-1) and 211 ± 0.3% U g(-1) of the maximum protein loading and esterification activity, respectively. The actual yield of geranyl propionate (49.46%) closely agreed with the predicted value (49.97%) under optimum reaction conditions (temperature: 37.67°C, incubation time: 10.20 hr, molar ratio (propionic acid:geraniol): 1:3.28, and stirring rate: 100.70 rpm) and hence, verifying the suitability of this approach. Since the method is performed under mild conditions, the RML-CS/GO biocatalyst may prove to be an environmentally benign alternative for producing satisfactory yield of geranyl propionate.
Motivated by the success and exhaustive research on carbon nanotubes (CNTs) based drug delivery, graphene, a two-dimensional; honey-comb crystal lattice has emerged as the rising star in recent years. Graphene is a flat monolayer of carbon atoms that holds many promising properties such as unparalleled thermal conductivity, remarkable electronic properties, and most intriguingly higher planar surface and superlative mechanical strength, which are attractive in biotechnological applications. Delivery of anti-cancer drugs using graphene and its derivatives has sparked major interest in this emerging field. The anti-cancer therapies often pose a limitation of insolubility, administration problems and cell penetration ability. In addition, systemic toxicity caused by lack of selective targeting towards cancer cells and inefficient distribution limits its clinical applications. Graphene nanocomposite is a promising tool to address these drawbacks. This review will focus on various synthesis and functionalization of graphene and graphene oxide for providing better solubility and targeted drug delivery at cancer cells. A more advanced and 'smart' graphene hybrid nanostructures that have several functionalities such as stimulus-response mediated delivery, imaging at release sites as well as transfection into cancer cells are also presented. A brief description on the challenges and perspectives for future research in this field is also discussed.
The effect of the recently developed graphene nanoflakes (GNFs) on the polymerase chain reaction (PCR) has been investigated in this paper. The rationale behind the use of GNFs is their unique physical and thermal properties. Experiments show that GNFs can enhance the thermal conductivity of base fluids and results also revealed that GNFs are a potential enhancer of PCR efficiency; moreover, the PCR enhancements are strongly dependent on GNF concentration. It was found that GNFs yield DNA product equivalent to positive control with up to 65% reduction in the PCR cycles. It was also observed that the PCR yield is dependent on the GNF size, wherein the surface area increases and augments thermal conductivity. Computational fluid dynamics (CFD) simulations were performed to analyze the heat transfer through the PCR tube model in the presence and absence of GNFs. The results suggest that the superior thermal conductivity effect of GNFs may be the main cause of the PCR enhancement.
A simple single-stage approach, based on the hydrothermal technique, has been introduced to synthesize reduced graphene oxide/titanium dioxide nanocomposites. The titanium dioxide nanoparticles are formed at the same time as the graphene oxide is reduced to graphene. The triethanolamine used in the process has two roles. It acts as a reducing agent for the graphene oxide as well as a capping agent, allowing the formation of titanium dioxide nanoparticles with a narrow size distribution (~20 nm). Transmission electron micrographs show that the nanoparticles are uniformly distributed on the reduced graphene oxide nanosheet. Thermogravimetric analysis shows the nanocomposites have an enhanced thermal stability over the original components. The potential applications for this technology were demonstrated by the use of a reduced graphene oxide/titanium dioxide nanocomposite-modified glassy carbon electrode, which enhanced the electrochemical performance compared to a conventional glassy carbon electrode when interacting with mercury(II) ions in potassium chloride electrolyte.
Graphene nanoplatelet (xGnP) was investigated as a novel reinforcement filler in mechanical properties for poly(lactic acid) (PLA)/epoxidized palm oil (EPO) blend. PLA/EPO/xGnP green nanocomposites were successfully prepared by melt blending method. PLA/EPO reinforced with xGnP resulted in an increase of up to 26.5% and 60.6% in the tensile strength and elongation at break of the nanocomposites respectively, compared to PLA/EPO blend. XRD pattern showed the presence of peak around 26.5° in PLA/EPO nanocomposites which corresponds to characteristic peak of graphene nanoplatelets. However, incorporation of xGnP has no effect on the flexural strength and modulus. Impact strength of PLA/5 wt% EPO improved by 73.6% with the presence of 0.5 wt% xGnP loading. Mechanical properties of PLA were greatly improved by the addition of a small amount of graphene nanoplatelets (<1 wt%).
We demonstrate mode locking of a thulium-bismuth codoped fiber laser (TBFL) operating at 1901.6 nm, using a graphene-based saturable absorber (SA). In this work, a single layer graphene is mechanically exfoliated using the scotch tape method and directly transferred onto the surface of a fiber pigtail to fabricate the SA. The obtained Raman spectrum characteristic indicates that the graphene on the core surface has a single layer. At 1552 nm pump power of 869 mW, the mode-locked TBFL self starts to generate an optical pulse train with a repetition rate of 16.7 MHz and pulse width of 0.37 ps. This is a simple, low-cost, stable, and convenient laser oscillator for applications where eye-safe and low-photon-energy light sources are required, such as sensing and biomedical diagnostics.