A highly efficient electrochemical sensor for the analysis of anticancer drug 5-fluorouracil (5-FU), is fabricated based on silver nanoparticles-polyaniline nanotube (AgNPs@PANINTs). AgNPs@PANINTs nanocomposite has been synthesized by a simple one-step method. Synthesized AgNPs@PANINTs nanocomposite was studied by Fourier transform infrared spectrometry, Scanning Electron Microscopy and Energy Dispersive X-ray. The fabricated PANINTs@AgNPs PGE was applied to the electrochemical sensing of 5-FU. Cyclic voltammetry and differential pulse voltammetry experiments illustrated high electro activity for the AgNPs@PANINTs nanocomposite. The study was explored using the Taguchi experimental design method. Electrochemical measurements using differential pulse voltammetry showed a wide linear relationship between 5-FU concentration and peak height within the range 1.0-300.0 μM with a low detection limit (0.06 μM). Also, the fabricated sensor showed excellent selectivity in the presence of two anticancer drugs and a number of other interfering compounds. The as-prepared sensor showed to be a promising device for a simple, rapid, and direct analysis of 5-FU.
Discovery of a novel anticancer drug delivery agent is important to replace conventional cancer therapies which are often accompanied by undesired side effects. This study demonstrated the synthesis of superparamagnetic magnetite nanocomposites (Fe3O4-NCs) using a green method. Montmorillonite (MMT) was used as matrix support, while Fe3O4 nanoparticles (NPs) and carrageenan (CR) were used as filler and stabilizer, respectively. The combination of these materials resulted in a novel nanocomposite (MMT/CR/Fe3O4-NCs). A series of characterization experiments was conducted. The purity of MMT/CR/Fe3O4-NCs was confirmed by X-ray diffraction (XRD) analysis. High resolution transmission electron microscopy (HRTEM) analysis revealed the uniform and spherical shape of Fe3O4 NPs with an average particle size of 9.3 ± 1.2 nm. Vibrating sample magnetometer (VSM) analysis showed an Ms value of 2.16 emu/g with negligible coercivity which confirmed the superparamagnetic properties. Protocatechuic acid (PCA) was loaded onto the MMT/CR/Fe3O4-NCs and a drug release study showed that 15% and 92% of PCA was released at pH 7.4 and 4.8, respectively. Cytotoxicity assays showed that both MMT/CR/Fe3O4-NCs and MMT/CR/Fe3O4-PCA effectively killed HCT116 which is a colorectal cancer cell line. Dose-dependent inhibition was seen and the killing was enhanced two-fold by the PCA-loaded NCs (IC50-0.734 mg/mL) compared to the unloaded NCs (IC50-1.5 mg/mL). This study highlights the potential use of MMT/CR/Fe3O4-NCs as a biologically active pH-responsive drug delivery agent. Further investigations are warranted to delineate the mechanism of cell entry and cancer cell killing as well as to improve the therapeutic potential of MMT/CR/Fe3O4-NCs.
Superparamagnetic magnetite nanocomposites (Fe3O4-NCs) were successfully synthesized, which comprised of montmorillonite (MMT) as matrix support, Kappaphycus alvarezii (SW) as bio-stabilizer and Fe3O4 as filler in the composites to form MMT/SW/Fe3O4-NCs. Nanocomposite with 0.5 g Fe3O4 (MMT/SW/0.5Fe3O4) was selected for anticancer activity study because it revealed high crystallinity, particle size of 7.2 ± 1.7 nm with majority of spherical shape, and Ms = 5.85 emu/g with negligible coercivity. Drug loading and release studies were carried out using protocatechuic acid (PCA) as the model for anticancer drug, which showed 19% and 87% of PCA release in pH 7.4 and 4.8, respectively. Monolayer anticancer assay showed that PCA-loaded MMT/SW/Fe3O4 (MMT/SW/Fe3O4-PCA) had selectivity towards HCT116 (colorectal cancer cell line). Although MMT/SW/Fe3O4-PCA (0.64 mg/mL) showed higher IC50 than PCA (0.148 mg/mL) and MMT/SW/Fe3O4 (0.306 mg/mL, MMT/SW/Fe3O4-PCA showed more effective killing towards tumour spheroid model generated from HCT116. The IC50 for MMT/SW/Fe3O4-PCA, MMT/SW/Fe3O4 and PCA were 0.132, 0.23 and 0.55 mg/mL, respectively. This suggests the improved penetration efficiency and drug release of MMT/SW/Fe3O4-PCA towards HCT116 spheroids. Moreover, concentration that lower than 2 mg/mL MMT/SW/Fe3O4-PCA did not result any hemolysis in human blood, which suggests them to be ideal for intravenous injection. This study highlights the potential of MMT/SW/Fe3O4-NCs as drug delivery agent.
This paper presents the fabrication of a highly sensitive and selective glucose sensor based on cuprous oxide/graphene nanocomposites-modified glassy carbon electrode (Cu2O/graphene/GCE). The Cu2O/graphene nanocomposites were synthesized based on a simple and straightforward chemical reduction process in alkaline aqueous solution using sodium carbonate as reductant. The size and shape of Cu2O nanoparticles on graphene sheets can be controlled by changing the amount of graphene oxide added during reaction. The electrochemical properties of Cu2O/graphene/GCE in 0.1M phosphate buffer solution were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. It was found that the pH, concentration of supporting electrolyte, and scan rate had very crucial effect on the sensitivity of prepared sensor towards glucose oxidation. At an applied potential of +0.50V, the Cu2O/graphene/GCE presented a high sensitivity of 1330.05μAmM(-1)cm(-2) and fast response (within 3s). The amperometric non-enzymatic glucose sensor developed had a linear relationship from 0.01mM to 3.0mM glucose and detection limit of 0.36μM. In the presence of ascorbic acid, uric acid, dopamine, chloride and citrate ion and other carbohydrates, the interferences were negligible. The proposed sensor was successfully applied for the determination of glucose concentration in real human blood samples.
Oily wastewater, especially water-oil emulsion has become serious environmental issue and received global attention. Chemical demulsifiers are widely used to treat oil-water emulsion, but the toxicity, non-recyclable and non-environmental friendly characteristic of chemical demulsifiers had limited their practical application in oil-water separation. Therefore, it is imperative to develop an efficient, simple, eco-friendly and recyclable demulsifiers for breaking up the emulsions from the oily wastewater. In this study, a magnetic demulsifier, magnetite-reduced graphene oxide (M-rGO) nanocomposites were proposed as a recyclable demulsifier to break up the surfactant stabilized crude oil-in-water (O/W) emulsion. M-rGO nanocomposites were prepared via in situ chemical synthesis by using only one type Fe salt and GO solid as precursor at room temperature. The prepared composites were fully characterized by various techniques. The effect of demulsifier dosage and pH of emulsion on demulsification efficiency (ED) has been studied in detailed. The demulsification mechanism was also proposed in this study. Results showed that M-rGO nanocomposites were able to demulsify crude O/W emulsion. The ED reaches 99.48% when 0.050 wt.% of M-rGO nanocomposites were added to crude O/W emulsion (pH = 4). Besides, M-rGO nanocomposites can be recycled up to 7 cycles without showing a significant change in terms of ED. Thus, M-rGO nanocomposite is a promising demulsifier for surfactant stabilized crude O/W emulsion.
In this study, Li3V2(PO4)3 (LVP) powders are prepared by a solution synthesis method. The effects of two reducing agents on crystal structure and morphology and electrochemical properties are investigated. Preliminary studies on reducing agents such as oxalic acid and citric acid, are used to reduce the vanadium (V) precursor. The oxalic acid-assisted synthesis induces smaller particles (30 nm) compared with the citric acid-assisted synthesis (70 nm). The LVP powders obtained by the oxalic acid exhibit a higher specific capacity (124 mAh g-1 at 1C) and better cycling performance (122 mAh g-1 following 50 cycles at 1C rate) than those for the citric acid. This is due to their higher electronic conductivity caused by carbon coating and downsizing the particles. The charge-discharge plateaus obtained from cyclic voltammetry are in good agreement with galvanostatic cycling profiles.
In recent assassinations reported in London and Malaysia, nerve agents were used to cause death, by skin poisoning. Skin decontamination is the ultimate and most important defense against nerve agent poisoning, because no effective antidote currently exists. However, almost no existing material can achieve effective and rapid decontamination without irritating the skin. This study links proteins that exhibit no decontamination ability with polymers to form a nanocomposite. This creates a nanospace on the surface of the protein that attracts and traps organic molecules, effectively adsorbing the nerve agent Soman within several seconds, without irritating the skin. Analysis of the different components of proteins and polymers reveals that the decontamination efficiency is considerably affected by the thickness of the coated polymer. Moreover, the thickness of the layer is predominantly determined by the size and species of the core and the crosslinking method. Further in vivo experiments on rats poisoned with Soman verify the efficiency and safety of the nanocomposite. These results could be used to design and synthesize more multi-functional and effective decontamination materials.
Nanocellulose prepared from the natural material has a promising wide range of opportunities to obtain the superior material properties towards various end-products. In this research, commercially available natural cotton was treated with aqueous sodium hydroxide solution to eliminate the hemicellulose and lignin, then cellulose was collected. The collected cellulose was subjected to acid hydrolysis using sulfuric acid to obtain nanocellulose. The prepared nanocellulose was further characterized with the aid of Fourier transform infrared spectroscopy, X-ray diffraction and Scanning Electron Microscopy to elucidate the chemical structure, crystallinity and the morphology.
Graphene is a 2-dimensional nanomaterial with an atomic thickness has attracted a strong scientific interest owing to their remarkable optical, electronic, thermal, mechanical and electrochemical properties. Graphene-based materials particularly graphene oxide and reduced graphene oxide are widely utilized in various applications ranging from food industry, environmental monitoring and biomedical fields as well as in the development of various types of biosensing devices. The richness in oxygen functional groups in the materials serves as a catalysis for the development of biosensors/electrochemical biosensors which promotes for an attachment of biological recognition elements, surface functionalization and compatible with micro- and nano- bio-environment. In this review, the graphene-based materials application in electrochemical biosensors based on recent advancement (e.g; the surface modification and analytical performances) and the utilization of such biosensors to monitor the noncommunicable diseases are presented. The detection performances of the graphene-based electrochemical biosensors are in the range of ng/mL and have reached up to fg/mL in detecting the targets of NCDs with higher selectivity, sensitivity and stability with good reproducibility attributes. We have discussed the advances while addressing the very specific biomarkers for the NCDs detection. Challenges and possible future research directions for the NCDs detection based on graphene nanocomposite with other 2D nanomaterials are outlined.
This research work represents the first major step towards constructing an effective therapeutic silibinin (SB) in cancer treatment using oxidised multi-walled carbon nanotubes (MWCNT-COOH) functionalised with biocompatible polymers as the potential drug carrier. In an attempt to increase the solubility and dispersibility of SB-loaded nanotubes (MWSB), four water-soluble polymers were adopted in the preparation process, namely polysorbate 20 (T20), polysorbate 80 (T80), polyethylene glycol (PEG) and chitosan (CHI). From the geometry point of view, the hydrophobic regions of the nanotubes were loaded with water-insoluble SB while the hydrophilic polymers functionalised on the outer surfaces of the nanotubes serve as a protective shell to the external environment. The chemical interaction between MWSB nanocomposites and polymer molecules was confirmed by Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. Besides, high-resolution transmission electron microscopy (HR-TEM), field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA) and UV-visible spectrophotometry were also employed to characterise the synthesised nanocomposites. The morphological study indicated that the polymers were deposited on the external surfaces of MWSB and the nanocomposites were seen to preserve their tubular structures even after the coating process was applied. The TGA results revealed that the incorporation of biopolymers practically improved the overall thermal stability of the coated MWSB nanocomposites. Evaluation of the in vitro effect on drug release rate by the nanocomposites was found to follow a biphasic release manner, showing a fast release at an initial stage and then a sustained-release over 2500 min. Besides, the drug release mechanisms of the nanocomposites demonstrated that the amount of SB released in the simulated environment was governed by pseudo-second order in which, the rate-limiting step mainly depends on diffusion of drug through chemisorption reaction. Finally, MTT assay showed that the coated MWSB nanocomposites on 3T3 cells were very much biocompatible at a concentration up to 100 g/mL, which is an evidence of MWSB reduced cytotoxicity.
Cellulose nanofibers (CNF) isolated from plant biomass have attracted considerable interests in polymer engineering. The limitations associated with CNF-based nanocomposites are often linked to the time-consuming preparation methods and lack of desired surface functionalities. Herein, we demonstrate the feasibility of preparing a multifunctional CNF-zinc oxide (CNF-ZnO) nanocomposite with dual antibacterial and reinforcing properties via a facile and efficient ultrasound route. We characterized and examined the antibacterial and mechanical reinforcement performances of our ultrasonically induced nanocomposite. Based on our electron microscopy analyses, the ZnO deposited onto the nanofibrous network had a flake-like morphology with particle sizes ranging between 21 to 34 nm. pH levels between 8-10 led to the formation of ultrafine ZnO particles with a uniform size distribution. The resultant CNF-ZnO composite showed improved thermal stability compared to pure CNF. The composite showed potent inhibitory activities against Gram-positive (methicillin-resistant Staphylococcus aureus (MRSA)) and Gram-negative Salmonella typhi (S. typhi) bacteria. A CNF-ZnO-reinforced natural rubber (NR/CNF-ZnO) composite film, which was produced via latex mixing and casting methods, exhibited up to 42% improvement in tensile strength compared with the neat NR. The findings of this study suggest that ultrasonically-synthesized palm CNF-ZnO nanocomposites could find potential applications in the biomedical field and in the development of high strength rubber composites.
Cellulose nanowhisker (NWC) was extracted by hydrolysing Pennisetum purpureum (PP) fibres with acid and alkali. They were subjected to different periods of acid hydrolysis; 30, 45, and 60 min. NWC morphology and physicochemical properties were characterised by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), particle size analyser, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and thermogravimetric analysis. NWC3, which underwent the longest hydrolysis time, showed the smallest width and length, under TEM. All samples presented a needle-like shape under TEM and AFM; uneven lengths and irregular shapes under FESEM; and a broad range of distribution, with the particle size analyser. All samples exhibited a good crystallinity index (CrI)-72.0 to 74.6%. The highest CrI% corresponded to 60 min of acid hydrolysis. Thermogravimetric analysis showed thermal stability between 310.72 °C and 336.28 °C. Thus, cellulose nanowhisker from PP fibres, have high potential as bio-nanocomposites.
The sol-gel method was carried out to synthesize nanosized Yttrium Iron Garnet (YIG). The nanomaterials with ferrite structure were heat-treated at different temperatures from 500 to 1000 °C. The phase identification, morphology and functional groups of the prepared samples were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR), respectively. The YIG ferrite nanopowder was composited with polyvinylidene fluoride (PVDF) by a solution casting method. The magnitudes of reflection and transmission coefficients of PVDF/YIG containing 6, 10 and 13% YIG, respectively, were measured using rectangular waveguide in conjunction with a microwave vector network analyzer (VNA) in X-band frequencies. The results indicate that the presence of YIG in polymer composites causes an increase in reflection coefficient and decrease in transmission coefficient of the polymer.
The utilization of renewable and functional group enriched nano-lignin as bio-additve in fabricating composite has become the focus of attention worldwide. Herein, lignin nanoparticles in the form of hollow spheres with the diameter of the order of 138 ± 39 nm were directly prepared from agro-industrial waste (palm kernel shell) using recyclable tetrahydrofuran in an acidified aqueous system without any chemical modification steps. We then fabricated a new chitosan/nano-lignin composite material as highly efficient sorbent, as demonstrated by efficient removal (~83%) of methylene blue (MB) dye under natural pH conditions. The adsorption process obeyed pseudo-second-order kinetics and adequate fitting of the adsorption data using Langmuir model suggested a monolayer adsorption with a maximum adsorption capacity of 74.07 mg g-1. Moreover, thermodynamic study of the system revealed spontaneous and endothermic nature of the sorption process. Further studies revealed that chitosan composite with nano-lignin showed better performance in dye decontamination compared to native chitosan and chitosan/bulk lignin composite. This could essentially be attributed to synergistic effects of size particularity (nano-effect) and incorporated functionalities due to lignin nanoparticles. Recyclability study performed in four repeated adsorption/regeneration cycles revealed recyclable nature of as-prepared composite, whilst adsorption experiments using spiked real water samples indicated recoveries as high as 89%. Based on this study, as-prepared bio-nanocomposite may thus be considered as an efficient and reusable adsorptive platform for the decontamination of water supplies.
Bionanocomposite films based on regenerated cellulose (RC) and incorporated with zeolite at different concentrations were fabricated by dissolving cellulose in 1-ethyl-3-methylimidazolium chloride (EMIMCl) ionic liquid using a simple green method. The interactions between the zeolite and the cellulose matrix were confirmed by Fourier transform infrared spectra. Mechanical properties of the nanocomposite films significantly improved as compared with the pure regenerated cellulose film, without the loss of extensibility. Zeolite incorporation enhanced the thermal stability and char yield of the nanocomposites. The scanning electron microscopy and transmission electron microscopy showed that zeolite was uniformly dispersed in the regenerated cellulose matrix. In vitro cytotoxicity test demonstrated that both RC and RC/zeolite nanocomposite films are cytocompatible. These results indicate that the prepared nanocomposites have potential applications in biodegradable packaging, membranes and biomedical areas.
In this study, novel nanocomposite films based on regenerated cellulose/halloysite nanotube (RC/HNT) have been prepared using an environmentally friendly ionic liquid 1-butyl-3-methylimidazolium chloride (BMIMCl) through a simple green method. The structural, morphological, thermal and mechanical properties of the RC/HNT nanocomposites were investigated using X-ray diffraction (XRD), Fourier transform infrared (FTIR), field emission scanning electron microscopy (FESEM), thermal analysis and tensile strength measurements. The results obtained revealed interactions between the halloysite nanotubes and regenerated cellulose matrix. The thermal stability and mechanical properties of the nanocomposite films, compared with pure regenerated cellulose film, were significantly improved When the halloysite nanotube (HNT) loading was only 2 wt.%, the 20% weight loss temperature (T20) increased 20°C. The Young's modulus increased from 1.8 to 4.1 GPa, while tensile strength increased from 35.30 to 60.50 MPa when 8 wt.% halloysite nanotube (HNT) was incorporated, interestingly without loss of ductility. The nanocomposite films exhibited improved oxygen barrier properties and water absorption resistance compared to regenerated cellulose.
Cotton linters were dissolved in aq. (8% LiOH+15% urea) that was pre-cooled to -12.5°C. Using this solution cellulose gel films were prepared by regeneration method with ethyl alcohol as a coagulant. These wet films were diffused with 10wt% Cassia alata leaf extract that acted as a reducing agent. The leaf extract diffused cellulose wet films were used as the matrix. The wet matrix films were dipped individually in lower concentrated 1-5mM aq.AgNO3 source solutions in the presence of sunlight and allowed the solutions to react with the diffused leaf extract reducing agent which in situ generated the silver nanoparticles (AgNPs) inside the films as well as in the source solution. The AgNPs formed in the source solution were observed by transmission electron microscope (TEM) and scanning electron microscope (SEM) while those formed in situ the films were observed by SEM and the particle size distribution was determined. The cellulose/AgNP composite films showed good antibacterial activity against Escherichia coli bacteria. These nanocomposite films were also characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA) and tensile tests. At temperatures below 300°C, the thermal stability of the nanocomposite films was lower than that of the matrix due to the catalytic effect of AgNPs. The nanocomposite films also possessed good tensile properties. The ecofriendly cellulose/AgNP composite films with good antibacterial activity and tensile properties can be considered for medical applications like dressing materials.
Exploring the new catalytic systems for the reduction of organic and inorganic pollutants from an indispensable process in chemical, petrochemical, pharmaceutical and food industries, etc. Hence, in the present work, authors motivated to synthesize bare reduced graphene oxide (rGO), polyaniline (PANI), three different ratios of rGO-PANI(80:20,50:50, 10:90) composites and rGO-PANI(80:20,50:50, 10:90) supported mono (Pd) & bimetallic [Pd: Au(1:1,1:2, 2:1)] nanocomposite by a facile chemical reduction method. Also, it investigated their catalytic performances for the reduction of organic/inorganic pollutants and antimicrobial activities. All the freshly prepared bare rGO, PANI, three different ratios of rGO-PANI(80:20, 50:50,10:90) composites and rGO-PANI(80:20, 50:50,10:90)/Pd & Pd: Au(1:1, 1:2,2:1) nanocomposite hybrid catalysts were characterized using UV-Vis, FT-IR, SEM, FE-SEM, EDAX, HR-TEM, XRD, XPS and Raman spectroscopy analysis. Among them, an optimized best composition of rGO-PANI(80:20)/Pd: Au(1:1) bimetallic nanocomposite hybrid catalyst exhibits better catalytic reduction and antimicrobial activities than other composites, as a result of strong electrostatic interactions between rGO, PANI and bimetal (Pd: Au) NPs through a synergistic effect. Hence, an optimized rGO-PANI(80:20)/Pd:Au(1:1) bimetallic nanocomposite catalyst would be considered as a suitable catalyst for the reduction of different nitroarenes, organic dyes, heavy metal ions and also significantly inhibit the growth of S. aureus, S. Typhi as well as Candida albicans and Candida kruesi in wastewater.
A microbial fuel cell is a sustainable and environmental-friendly device that combines electricity generation and wastewater treatment through metabolic activities of microorganisms. However, low power output from inadequate electron transfer to the anode electrode hampers its practical implementation. Nanocomposites of oxidized carbon nanotubes and medium-chain-length polyhydroxyalkanoates (mcl-PHA) grafted with methyl acrylate monomers enhance the electrochemical function of electrodes in microbial fuel cell. Extensive polymerization of methyl acrylate monomers within mcl-PHA matrix, and homogenous dispersion of carbon nanotubes within the graft matrix are responsible for the enhancement. Modified electrodes exhibit high conductivities, better redox peak and reduction of cell internal resistance up to 76%. A stable voltage output at almost 700 mV running for 225 H generates maximum power and current density of 351 mW/m2 and 765 mA/m2 , respectively. Superior biofilm growth on modified surface is responsible for improved electron transfer to the anode hence stable and elevated power output generation.
Graphene-based adsorbents have attracted wide interests as effective adsorbents for heavy metals removal from the environment. Due to their excellent electrical, mechanical, optical and transport properties, graphene and its derivatives such as graphene oxide (GO) have found various applications. However, in many applications, surface modification is necessary as pristine graphene/GO may be ineffective in some specific applications such as adsorption of heavy metal ions. Consequently, the modification of graphene/GO using various metals and non-metals is an ongoing research effort in the carbon-material realm. The use of organic materials represents an economical and environmentally friendly approach in modifying GO for environmental applications such as heavy metal adsorption. This review discusses the applications of organo-functionalized GO composites for the adsorption of heavy metals. The aspects reviewed include the commonly used organic materials for modifying GO, the performance of the modified composites in heavy metals adsorption, effects of operational parameters, adsorption mechanisms and kinetic, as well as the stability of the adsorbents. Despite the significant research efforts on GO modification, many aspects such as the interaction between the functional groups and the heavy metal ions, and the quantitative effect of the functional groups are yet to be fully understood. The review, therefore, offers some perspectives on the future research needs.