A portable electrochemical sensor was developed to determine xylazine in spiked beverages by adsorptive stripping voltammetry (AdSV). The sensor was based on a graphene nanoplatelets-modified screen-printed carbon electrode (GNPs/SPCE). The electrochemical behavior of xylazine at the GNPs/SPCE was an adsorption-controlled irreversible oxidation reaction. The loading of graphene nanoplatelets (GNPs) on the modified SPCE, electrolyte pH, and AdSV accumulation potential and time were optimized. Under optimal conditions, the GNPs/SPCE provided high sensitivity, linear ranges of 0.4-6.0 mg L-1 (r = 0.997) and 6.0-80.0 mg L-1 (r = 0.998) with a detection limit of 0.1 mg L-1 and a quantitation limit of 0.4 mg L-1. Repeatability was good. The accuracy of the proposed sensor was investigated by spiking six beverage samples at 1.0, 5.0, and 10.0 mg L-1. The recoveries from this method ranged from 80.8 ± 0.2-108.1 ± 0.3 %, indicating the good accuracy of the developed sensor. This portable electrochemical sensor can be used to screen for xylazine in beverage samples as evidence in cases of sexual assault or robbery.
The treatment of cancer through chemotherapy is limited by its toxicity to healthy tissues and organs, and its inability to target the cancer site. In this study, we have designed an anticancer nanocomposite delivery system for protocatechuic acid (PCA) using graphene oxide⁻polyethylene glycol as the nanocarrier, and coated with folic acid (GO⁻PEG⁻PCA⁻FA) for targeting the cancer cells. The designed anticancer delivery system was found to show much better anticancer activity than the free drug PCA against liver cancer HEP-G2 cells and human colon cancer HT-29 cells; at same time, it was found to be less toxic to normal fibroblast 3T3 cells. The folate-coated anticancer delivery system was found to show better activity then the free drug and the uncoated anticancer delivery system. The in vitro release of the PCA was found to be sustained in human physiological pHs, i.e., blood pH 7.4 and intracellular lysosomal pH 4.8. These in vitro findings are highly encouraging for further in vivo evaluation studies.
Tuberculosis (TB) is a dreadful bacterial disease, infecting millions of human and cattle every year worldwide. More than 50 years after its discovery, ethambutol continues to be an effective part of the World Health Organization's recommended frontline chemotherapy against TB. However, the lengthy treatment regimens consisting of a cocktail of antibiotics affect patient compliance. There is an urgent need to improve the current therapy so as to reduce treatment duration and dosing frequency. In this study, we have designed a novel anti-TB multifunctional formulation by fabricating graphene oxide with iron oxide magnetite nanoparticles serving as a nano-carrier on to which ethambutol was successfully loaded. The designed nanoformulation was characterised using various analytical techniques. The release of ethambutol from anti-TB multifunctional nanoparticles formulation was found to be sustained over a significantly longer period of time in phosphate buffer saline solution at two physiological pH (7.4 and 4.8). Furthermore, the nano-formulation showed potent anti-tubercular activity while remaining non-toxic to the eukaryotic cells tested. The results of this in vitro evaluation of the newly designed nano-formulation endorse its further development in vivo.
Tuberculosis (TB) is a bacterial disease responsible for millions of infections and preventable deaths each year. Its treatment is complicated by patients' noncompliance due to dosing frequency, lengthy treatment, and adverse side effects associated with current chemotherapy. However, no modifications to the half-a-century old standard chemotherapy have been made based on a nanoformulation strategy to improve pharmacokinetic efficacy. In this study, we have designed a new nanodelivery formulation, using graphene oxide as the nanocarrier, loaded with the anti-TB antibiotic, ethambutol. The designed formulation was characterized using a number of molecular analytical techniques. It was found that sustained release of the drug resulted in better bioavailability. In addition, the designed formulation demonstrated high biocompatibility with mouse fibroblast cells. The anti-TB activity of the nanodelivery formulation was determined using whole-cell resazurin microtiter plate assay, modified-spot culture growth inhibition assay, and biofilm inhibition assay. The nanodelivery formulation showed good anti-mycobacterial activity. The anti-mycobacterial activity of Ethambutol was unaffected by the drug loading and release process. The results of this study demonstrated the potential of this new nanodelivery formulation strategy to be considered for modifying existing chemotherapy to yield more efficacious antibiotic treatment against TB.
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%.
We demonstrate the preparation of nanostructures cobalt oxide/reduced graphene oxide (Co3O4/rGO) nanocomposites by a simple one-step cost-effective hydrothermal technique for possible electrode materials in supercapacitor application. The X-ray diffraction patterns were employed to confirm the nanocomposite crystal system of Co3O4/rGO by demonstrating the existence of normal cubic spinel structure of Co3O4 in the matrix of Co3O4/rGO nanocomposite. FTIR and FT-Raman studies manifested the structural behaviour and quality of prepared Co3O4/rGO nanocomposite. The optical properties of the nanocomposite Co3O4/rGO have been investigated by UV absorption spectra. The SEM/TEM images showed that the Co3O4 nanoparticles in the Co3O4/rGO nanocomposites were covered over the surface of the rGO sheets. The electrical properties were analyzed in terms of real and imaginary permittivity, dielectric loss and AC conductivity. The electrocatalytic activities of synthesized Co3O4/rGO nanocomposites were determined by cyclic voltammetry and charge-discharge cycle to evaluate the supercapacitive performance. The specific capacitance of 754 Fg-1 was recorded for Co3O4/rGO nanocomposite based electrode in three electrode cell system. The electrode material exhibited an acceptable capability and excellent long-term cyclic stability by maintaining 96% after 1000 continuous cycles. These results showed that the prepared sample could be an ideal candidate for high-energy application as electrode materials. The synthesized Co3O4/rGO nanocomposite is a versatile material and can be used in various application such as fuel cells, electrochemical sensors, gas sensors, solar cells, and photocatalysis.
A cost-effective, facile hydrothermal approach was made for the synthesis of SnO2/graphene (Gr) nano-composites. XRD diffraction spectra clearly confirmed the presence of tetragonal crystal system of SnO2 which was maintaining its structure in both pure and composite materials' matrix. The stretching and bending vibrations of the functional groups were analyzed using FTIR analysis. FESEM images illustrated the surface morphology and the texture of the synthesized sample. HRTEM images confirmed the deposition of SnO2 nanoparticles over the surface of graphene nano-sheets. Raman Spectroscopic analysis was carried out to confirm the in-plane blending of SnO2 and graphene inside the composite matrix. The photocatalytic performance of the synthesized sample under UV irradiation using methylene blue dye was observed. Incorporation of grapheme into the SnO2 sample had increased the photocatalytic activity compared with the pure SnO2 sample. The electrochemical property of the synthesized sample was evaluated.
Platinum nanoparticles were synthesized in graphene oxide aqueous solution using a laser ablation technique to investigate the effect of optical linear, nonlinear and thermal properties of platinum-graphene oxide nanocomposite solution. The samples were prepared with different ablation times. The platinum nanoparticles that formed a spherical shape on the surface of graphene oxide solution were authenticated using UV-visible spectrum and transmission electron microscopy patterns. The particle size decreased with increasing ablation time, and the concentration and volume fraction of samples were increased. To obtain the optical linear, nonlinear and thermal properties of platinum-graphene oxide nanocomposite solution, UV-visible spectroscopy, Z-scan, thermal lens and photoacoustic techniques were used. Consequently, the linear and nonlinear refractive indices increased with an increase in the volume fraction of platinum nanoparticles. It was observed from the spatial self-phase modulation patterns that, the optical nonlinear property of the graphene oxide was enhanced in the presence of platinum nanoparticles, and the nonlinearity increased with an increase in the volume fraction of platinum nanoparticles inside the graphene oxide solution. The thermal diffusivity and thermal effusivity of platinum nanoparticles graphene oxide were measured using a thermal lens and photoacoustic methods, respectively. The thermal diffusivity and thermal effusivity of samples were in the range of 0.0341 × 10-5 m2/s to 0.1223 × 10-5 m2/s and 0.163 W s1/2 cm-2 K-1 to 0.3192 W s1/2 cm-2 K-1, respectively. Consequently, the platinum enhanced the optical and thermal properties of graphene oxide.
In this study, we synthesized covalently functionalized graphene nanoplatelet (GNP) aqueous suspensions that are highly stable and environmentally friendly for use as coolants in heat transfer systems. We evaluated the heat transfer and hydrodynamic properties of these nano-coolants flowing through a horizontal stainless steel tube subjected to a uniform heat flux at its outer surface. The GNPs functionalized with clove buds using the one-pot technique. We characterized the clove-treated GNPs (CGNPs) using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). We then dispersed the CGNPs in distilled water at three particle concentrations (0.025, 0.075 and 0.1wt%) in order to prepare the CGNP-water nanofluids (nano-coolants). We used ultraviolet-visible (UV-vis) spectroscopy to examine the stability and solubility of the CGNPs in the distilled water. There is significant enhancement in thermo-physical properties of CGNPs nanofluids relative those for distilled water. We validated our experimental set-up by comparing the friction factor and Nusselt number for distilled water obtained from experiments with those determined from empirical correlations, indeed, our experimental set-up is reliable and produces results with reasonable accuracy. We conducted heat transfer experiments for the CGNP-water nano-coolants flowing through the horizontal heated tube in fully developed turbulent condition. Our results are indeed promising since there is a significant enhancement in the Nusselt number and convective heat transfer coefficient for the CGNP-water nanofluids, with only a negligible increase in the friction factor and pumping power. More importantly, we found that there is a significant increase in the performance index, which is a positive indicator that our nanofluids have potential to substitute conventional coolants in heat transfer systems because of their overall thermal performance and energy savings benefits.
The spread of graphene in low-density polyethylene (LDPE) improves LDPE/graphene nanocompounds' thermal/mechanical/electrical characteristics. The images of scanning electron microscopy (SEM) verify full graphene exfoliation at 1000 °C. Inclusion graphene develops crystallinity; increases the local order of lattice and thermal stability of LDPE/graphene nanocompounds. The consistent distributions and further inclusion of graphene caused the great heat breakdown strength, increasing heat breakdown activation energy and a superior melting point (Tm) for LDPE nanocompounds. Percolation occurs with the graphene incorporation of 0.5 wt%. The complex viscosity test showed Newtonian behavior for LDPE at a very low frequency. But, graphene inclusion to LDPE changed the viscosity performance from liquid-like to solid-like which caused a decrease in the melt flow rate (MFR) values for all LDPE/graphene nanocompounds.
The objective of this research was to determine the durability of an engineered cementitious composite (ECC) incorporating crumb rubber (CR) and graphene oxide (GO) with respect to resistance to acid and sulphate attacks. To obtain the mix designs used for this study, response surface methodology (RSM) was utilized, which yielded the composition of 13 mixes containing two variables (crumb rubber and graphene oxide). The crumb rubber had a percentage range of 0-10%, whereas the graphene oxide was tested in the range of 0.01-0.05% by volume. Three types of laboratory tests were used in this study, namely a compressive test, an acid attack test to study its durability against an acidic environment, and a sulphate attack test to examine the length change while exposed to a sulphate solution. Response surface methodology helped develop predictive responsive models and multiple objectives that aided in the optimization of results obtained from the experiments. Furthermore, a rubberized engineered cementitious composite incorporating graphene oxide yielded better chemical attack results compared to those of a normal rubberized engineered cementitious composite. In conclusion, nano-graphene in the form of graphene oxide has the ability to enhance the properties and overcome the limitations of crumb rubber incorporated into an engineered cementitious composite. The optimal mix was attained with 10% crumb rubber and 0.01 graphene oxide that achieved 43.6 MPa compressive strength, 29.4% weight loss, and 2.19% expansion. The addition of GO enhances the performance of rubberized ECC, contributing to less weight loss due to the deterioration of acidic media on the ECC. It also contributes to better resistance to changes in the length of the rubberized ECC samples.
A fluorometric assay is described for highly sensitive quantification of Escherichia coli O157:H7. Reporter oligos were immobilized on graphene quantum dots (GQDs), and quencher oligos were immobilized on gold nanoparticles (AuNPs). Target DNA was co-hybridized with reporter oligos on the GQDs and quencher oligos on AuNPs. This triggers quenching of fluorescence (with excitation/emission peaks at 400 nm/530 nm). On introducing target into the system, fluorescence is quenched by up to 95% by 100 nM concentrations of target oligos having 20 bp. The response to the fliC gene of E. coli O157:H7 increases with the logarithm of the concentration in the range from 0.1 nM to 150 nM. The limit of detection is 1.1 ± 0.6 nM for n = 3. The selectivity and specificity of the assay was confirmed by evaluating the various oligos sequences and PCR product (fliC gene) amplified from genomic DNA of the food samples spiked with E. coli O157:H7. Graphical abstractSchematic representation of fluorometric assay for highly sensitive quantification of Escherichia coli O157:H7 based on fluorescence quenching gene assay for fliC gene of E. coli O157:H7.
Control synthesis of high quality large-area graphene on transition metals (TMs) by chemical vapor deposition (CVD) is the most fascinating approach for practical device applications. Interaction of carbon atoms and TMs is quite critical to obtain graphene with precise layer number, crystal size and structure. Here, we reveal a solid phase reaction process to achieve Cu assisted graphene growth in nanoscale by in-situ transmission electron microscope (TEM). Significant structural transformation of amorphous carbon nanofiber (CNF) coated with Cu is observed with an applied potential in a two probe system. The coated Cu particle recrystallize and agglomerate toward the cathode with applied potential due to joule heating and large thermal gradient. Consequently, the amorphous carbon start crystallizing and forming sp(2) hybridized carbon to form graphene sheet from the tip of Cu surface. We observed structural deformation and breaking of the graphene nanoribbon with a higher applied potential, attributing to saturated current flow and induced Joule heating. The observed graphene formation in nanoscale by the in-situ TEM process can be significant to understand carbon atoms and Cu interaction.
We propose a surface plasmon resonance (SPR) sensor based on photonic crystal fiber (PCF) with selectively filled analyte channels. Silver is used as the plasmonic material to accurately detect the analytes and is coated with a thin graphene layer to prevent oxidation. The liquid-filled cores are placed near to the metallic channel for easy excitation of free electrons to produce surface plasmon waves (SPWs). Surface plasmons along the metal surface are excited with a leaky Gaussian-like core guided mode. Numerical investigations of the fiber's properties and sensing performance are performed using the finite element method (FEM). The proposed sensor shows maximum amplitude sensitivity of 418 Refractive Index Units (RIU-1) with resolution as high as 2.4 × 10(-5) RIU. Using the wavelength interrogation method, a maximum refractive index (RI) sensitivity of 3000 nm/RIU in the sensing range of 1.46-1.49 is achieved. The proposed sensor is suitable for detecting various high RI chemicals, biochemical and organic chemical analytes. Additionally, the effects of fiber structural parameters on the properties of plasmonic excitation are investigated and optimized for sensing performance as well as reducing the sensor's footprint.
The application of magnetized graphene (G) layers synthesized on the carbon nanofibers (CNFs) (m-G/CNF) was investigated as novel adsorbent for the magnetic solid-phase extraction (MSPE) of polycyclic aromatic hydrocarbons (PAHs) in water samples followed by gas chromatography-flame ionization detector (GC-FID). Six important parameters, affecting the extraction efficiency of PAHs, including: amount of adsorbent, adsorption and desorption times, type and volume of the eluent solvent and salt content of the sample were evaluated. The optimum extraction conditions were obtained as: 5min for extraction time, 20mg for sorbent amount, dichloromethane as desorption solvent, 1mL for desorption solvent volume, 5min for desorption time and 15% (w/v) for NaCl concentration. Good performance data were obtained at the optimized conditions. The calibration curves were linear over the concentration ranges from 0.012 to 100ngmL(-1) with correlation coefficients (r) between 0.9950 and 0.9967 for all the analytes. The limits of detection (LODs, S/N=3) of the proposed method for the studied PAHs were 0.004-0.03ngmL(-1). The relative standard deviations (RSDs) for five replicates at two concentration levels (0.1 and 50ngmL(-1)) of PAHs were ranged from 3.4 to 5.7%. Appropriate relative recovery values, in the range of 95.5-99.9%, were also obtained for the real water sample analysis.
This study investigated the engine performance and emission characteristics of biodiesel blends with combined Graphene oxide nanoplatelets (GNPs) and 10% v/v dimethyl carbonate (DMC) as fuel additives as well as analysed the tribological characteristics of those blends. 10% by volume DMC was mixed with 30% palm oil biodiesel blends with diesel. Three different concentrations (40, 80 and 120 ppm) of GNPs were added to these blends via the ultrasonication process to prepare the nanofuels. Sodium dodecyl sulphate (SDS) surfactant was added to improve the stability of these blends. GNPs were characterised using Scanning Electron Microscope (SEM) and Fourier Transform Infrared (FTIR), while the viscosity of nanofuels was investigated by rheometer. UV-spectrometry was used to determine the stability of these nanoplatelets. A ratio of 1:4 GNP: SDS was found to produce maximum stability in biodiesel. Performance and emissions characteristics of these nanofuels have been investigated in a four-stroke compression ignition engine. The maximum reduction in BSFC of 5.05% and the maximum BTE of 22.80% was for B30GNP40DMC10 compared to all other tested blends. A reduction in HC (25%) and CO (4.41%) were observed for B30DMC10, while a reduction in NOx of 3.65% was observed for B30GNP40DMC10. The diesel-biodiesel fuel blends with the addition of GNP exhibited a promising reduction in the average coefficient of friction 15.05%, 8.68% and 3.61% for 120, 80 and 40 ppm concentrations compared to B30. Thus, combined GNP and DMC showed excellent potential for utilisation in diesel engine operation.
In this paper, we propose a metal-polydopamine (MPDA) framework with a specific molecular probe which appears to be the most promising approach to a strong fluorescence quencher. The MPDA framework quenching ability toward various organic fluorophore such as aminoethylcoumarin acetate, 6-carboxyfluorescein (FAM), carboxyteramethylrhodamine, and Cy5 are used to establish a fluorescent biosensor that can selectively recognize Hg2+ and Ag+ ions. The fluorescent quenching efficiency was sufficient to achieve more than 96%. The MPDA framework also exhibits different affinities with ssDNA and dsDNA. In addition, the FAM-labeled ssDNA was adsorbed onto the MPDA framework, based on their interaction with the complex formed between MPDA frameworks/ssDNA taken as a sensing platform. By taking advantage of this sensor, highly sensitive and selective determination of Hg2+ and Ag+ ions is achieved through exonuclease III signal amplification activity. The detection limits of Hg2+ and Ag+ achieved to be 1.3 and 34 pM, respectively, were compared to co-existing metal ions and graphene oxide-based sensors. Furthermore, the potential applications of this study establish the highly sensitive fluorescence detection targets in environmental and biological fields.
A new graphene-based tetraethoxysilane-methyltrimethoxysilane sol-gel hybrid magnetic nanocomposite (Fe3O4@G-TEOS-MTMOS) was synthesised, characterized and successfully applied in magnetic solid-phase extraction (MSPE) for simultaneous analysis of polar and non-polar organophosphorus pesticides from several water samples. The Fe3O4@G-TEOS-MTMOS nanocomposite was characterized using Fourier transform-infrared spectroscopy, energy-dispersive X-ray spectroscopy, field emission scanning electron microscopy and X-ray diffraction. Separation, determination and quantification were achieved using gas chromatography coupled with micro electron capture detector. Adsorption capacity of the sorbent was calculated using Langmuir equation. MSPE was linear in the range 100-1000 pg mL(-1) for phosphamidon and dimethoate, and 10-100 pg mL(-1) for chlorpyrifos and diazinon, with limit of detection (S/N = 3) of 19.8, 23.7, 1.4 and 2.9 pg mL(-1) for phosphamidon, dimethoate, diazinon and chlorpyrifos, respectively. The LODs obtained is well below the maximum residual level (100 pg mL(-1)) as set by European Union for pesticides in drinking water. Acceptable precision (%RSD) was achieved for intra-day (1.3-8.7%, n = 3) and inter-day (7.6-17.8%, n = 15) analyses. Fe3O4@G-TEOS-MTMOS showed high adsorption capacity (54.4-76.3 mg g(-1)) for the selected OPPs. No pesticide residues were detected in the water samples analysed. Excellent extraction recoveries (83-105%) were obtained for the spiked OPPs from tap, river, lake and sea water samples. The newly synthesised Fe3O4@G-TEOS-MTMOS showed high potential as adsorbent for OPPs analysis.
Graphene (G) modified with magnetite (Fe3O4) and sol-gel hybrid tetraethoxysilane-methyltrimethoxysilane (TEOS-MTMOS) was used as a clean-up adsorbent in magnetic solid phase extraction (MSPE) for direct determination of acrylamide in various food samples prior to gas chromatography-mass spectrometry analysis. Good linearity (R2=0.9990) was achieved for all samples using matrix-matched calibration. The limit of detection (LOD=3×SD/m) obtained was 0.061-2.89µgkg-1 for the studied food samples. Native acrylamide was found to be highest in fried potato with bright-fleshed (900.81µgkg-1) and lowest in toasted bread (5.02µgkg-1). High acrylamide relative recovery (RR=82.7-105.2%) of acrylamide was obtained for spiked (5 and 50µgkg-1) food samples. The Fe3O4@G-TEOS-MTMOS is reusable up to 7 times as a clean-up adsorbent with good recovery (>85%). The presence of native acrylamide was confirmed by mass analysis at m/z=71 ([C3H5NO]+) and m/z=55 ([C3H3O]+).
New-generation adsorbent, Fe3O4@SiO2/GO, was developed by modification of graphene oxide (GO) with silica-coated (SiO2) magnetic nanoparticles (Fe3O4). The synthesized adsorbent was characterized using Fourier transform infrared spectroscopy, X-ray diffractometry, energy-dispersive X-ray spectroscopy, and field emission scanning electron microscopy. The developed adsorbent was used for the removal and simultaneous preconcentration of As(III) and As(V) from environmental waters prior to ICP-MS analysis. Fe3O4@SiO2/GO provided high adsorption capacities, i.e., 7.51 and 11.46 mg g(-1) for As(III) and As(V), respectively, at pH 4.0. Adsorption isotherm, kinetic, and thermodynamic were investigated for As(III) and As(V) adsorption. Preconcentration of As(III) and As(V) were studied using magnetic solid-phase extraction (MSPE) method at pH 9.0 as the adsorbent showed selective adsorption for As(III) only in pH range 7-10. MSPE using Fe3O4@SiO2/GO was developed with good linearities (0.05-2.0 ng mL(-1)) and high coefficient of determination (R (2) = 0.9992 and 0.9985) for As(III) and As(V), respectively. The limits of detection (LODs) (3× SD/m, n = 3) obtained were 7.9 pg mL(-1) for As(III) and 28.0 pg mL(-1) for As(V). The LOD obtained is 357-1265× lower than the WHO maximum permissible limit of 10.0 ng mL(-1). The developed MSPE method showed good relative recoveries (72.55-109.71 %) and good RSDs (0.1-4.3 %, n = 3) for spring water, lake, river, and tap water samples. The new-generation adsorbent can be used for the removal and simultaneous preconcentration of As(III) and As(V) from water samples successfully. The adsorbent removal for As(III) is better than As(V).