The immobilization of photocatalyst nanoparticles on a solid substrate is an important aspect for improved post-treatment separation and photocatalyst reactor design. In this study, we report the simple preparation of reduced graphene oxide (rGO)-hybridized zinc oxide (ZnO) thin films using a one-step electrochemical deposition, and investigated the effect of rGO-hybridization on the photoinactivation efficiency of ZnO thin films towards Staphylococcus aureus (S. aureus) and Salmonella enterica serovar Typhi (S. Typhi) as target bacterial pathogens. Field-emission scanning electron microscopy (FESEM) revealed the formation of geometric, hexagonal flakes of ZnO on the ITO glass substrate, as well as the incorporation of rGO with ZnO in the rGO/ZnO thin film. Raman spectroscopy indicated the successful incorporation of rGO with ZnO during the electrodeposition process. Photoluminescence (PL) spectroscopy indicates that rGO hybridization with ZnO increases the amount of oxygen vacancies, evidenced by the shift of visible PL peak at 650 to 500nm. The photoinactivation experiments showed that the thin films were able to reduce the bacterial cell density of Staph. aureus and S. Typhi from an initial concentration of approximately 10(8) to 10(3)CFU/mL within 15min. The rGO/ZnO thin film increased the photoinactivation rate for S. aureus (log[N/No]) from -5.1 (ZnO) to -5.9. In contrast, the application of rGO/ZnO thin film towards the photoinactivation of S. Typhi did not improve its photoinactivation rate, compared to the ZnO thin film. We may summarise that (1) rGO/ZnO was effective to accelerate the photoinactivation of S. aureus but showed no difference to improve the photoinactivation of S. Typhi, in comparison to the performance of ZnO thin films, and (2) the photoinactivation in the presence of ZnO and rGO/ZnO was by ROS damage to the extracellular wall.
Hydroxyapatite (Ca10(PO4)6(OH)2) is widely investigated as an implantable material for hard tissue restoration due to its osteoconductive properties. However, hydroxyapatite in bulk form is limited as its mechanical properties are insufficient for load-bearing orthopedic applications. Attempts have been made to improve the mechanical properties of hydroxyapatite, by incorporating ceramic fillers, but the resultant composite materials require high sintering temperatures to facilitate densification, leading to the decomposition of hydroxyapatite into tricalcium phosphate, tetra-calcium phosphate and CaO phases. One method of improving the properties of hydroxyapatite is to incorporate bioactive glass particles as a second phase. These typically have lower softening points which could possibly facilitate sintering at lower temperatures. In this work, a bioactive glass (SiO2-CaO-ZnO-Na2O-TiO2) is incorporated (10, 20 and 30 wt%) into hydroxyapatite as a reinforcing phase. X-ray diffraction confirmed that no additional phases (other than hydroxyapatite) were formed at a sintering temperature of 560 ℃ with up to 30 wt% glass addition. The addition of the glass phase increased the % crystallinity and the relative density of the composites. The biaxial flexural strength increased to 36 MPa with glass addition, and there was no significant change in hardness as a function of maturation. The pH of the incubation media increased to pH 10 or 11 through glass addition, and ion release profiles determined that Si, Na and P were released from the composites. Calcium phosphate precipitation was encouraged in simulated body fluid with the incorporation of the bioactive glass phase, and cell culture testing in MC-3T3 osteoblasts determined that the composite materials did not significantly reduce cell viability.
Rice straw/magnetic nanocomposites (RS/Fe3O4-NCs) were prepared via co-precipitation method for removal of Pb(II) and Cu(II) from aqueous solutions. Response surface methodology (RSM) was utilized to find the optimum conditions for removal of ions. The effects of three independent variables including initial ion concentration, removal time, and adsorbent dosage were investigated on the maximum adsorption of Pb (II) and Cu (II). The optimum conditions for the adsorption of Pb(II) and Cu(II) were obtained (100 and 60 mg/L) of initial ion concentration, (41.96 and 59.35 s) of removal time and 0.13 g of adsorbent for both ions, respectively. The maximum removal efficiencies of Pb(II) and Cu(II) were obtained 96.25% and 75.54%, respectively. In the equilibrium isotherm study, the adsorption data fitted well with the Langmuir isotherm model. The adsorption kinetics was best depicted by the pseudo-second order model. Desorption experiments showed adsorbent can be reused successfully for three adsorption-desorption cycles.
A new supramolecular electrochemical sensor for highly sensitive detection of dopamine (DA) was fabricated based on supramolecular assemblies of mixed two surfactants, tetra-butylammonium bromide (TBABr) and sodium dodecyl sulphate (SDS), on the electrodeposition of gold nanoparticles on graphene oxide modified on glassy carbon electrode (AuNPs/GO/GCE). Self-assembled mixed surfactants (TBABr/SDS) were added into the solution to increase the sensitivity for the detection of DA. All electrodes were characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The supramolecular electrochemical sensor (TBABr/SDS⋅⋅⋅AuNPs/GO/GCE) showed excellent electrocatalytic activity toward the oxidation of DA. Under the optimum conditions, the concentration of DA was obtained in the range from 0.02 µM to 1.00 µM, with a detection limit of 0.01 µM (3s/b). The results displayed that TBABr/SDS⋅⋅⋅AuNPs/GO/GCE exhibited excellent performance, good sensitivity, and reproducibility. In addition, the proposed supramolecular electrochemical sensor was successfully applied to determine DA in human serum samples with satisfactory recoveries (97.26% to 104.21%).
This paper attempts to evaluate the mineralogical and chemical composition of sedimentary limestone mine waste alongside its mineral carbonation potential. The limestone mine wastes were recovered as the waste materials after mining and crushing processes and were analyzed for mineral, major and trace metal elements. The major mineral composition discovered was calcite (CaCO3) and dolomite [CaMg(CO3)2], alongside other minerals such as bustamite [(Ca,Mn)SiO3] and akermanite (Ca2MgSi2O7). Calcium oxide constituted the greatest composition of major oxide components of between 72 and 82%. The presence of CaO facilitated the transformation of carbon dioxide into carbonate form, suggesting potential mineral carbonation of the mine waste material. Geochemical assessment indicated that mean metal(loid) concentrations were found in the order of Al > Fe > Sr > Pb > Mn > Zn > As > Cd > Cu > Ni > Cr > Co in which Cd, Pb and As exceeded some regulatory guideline values. Ecological risk assessment demonstrated that the mine wastes were majorly influenced by Cd as being classified having moderate risk. Geochemical indices depicted that Cd was moderately accumulated and highly enriched in some of the mine waste deposited areas. In conclusion, the limestone mine waste material has the potential for sequestering CO2; however, the presence of some trace metals could be another important aspect that needs to be considered. Therefore, it has been shown that limestone mine waste can be regarded as a valuable feedstock for mineral carbonation process. Despite this, the presence of metal(loid) elements should be of another concern to minimize potential ecological implication due to recovery of this waste material.
We synthesized a dextrin (DEX)-conjugated graphene oxide (GO) nanocarrier (GO100-DEX) as a potential drug delivery system to respond to a tumor-associated stimulus, α-amylase, that has high permeability through the fenestrated endothelial barrier to the tumor site. At acidic pH and in the presence of α-amylase to simulate tumor conditions, GO100-DEX released a 1.5-fold higher amount of doxorubicin (DOX) than of GO100. Under the same conditions, the cytotoxic effects of GO100-DEX/DOX were 2-fold greater than those of free DOX and 2.9-fold greater than those of GO100/DOX. Employing an in vitro biomimetic microfluidic blood vessel model lined with human umbilical vein endothelial cells, we evaluated the tumor vasculature endothelial permeation of GO100-DEX and GO100 using dextrans of 10 and 70kDa for comparison and as standards to validate the microfluidic blood vessel model. The results showed that the permeabilities of GO100-DEX and GO100 were 4.3- and 4.9-fold greater than that of 70kDa dextran and 2.7- and 3.1-fold higher than that of 10kDa dextran, thus demonstrating the good permeability of the GO-based nanocarrier through the fenestrated endothelial barrier.
Bera Lake is the largest natural fresh water reservoir in Malaysia. It has vital environmental and ecological importance for human and wild life. Nevertheless, water quality of this lake has been degraded during the last few decades due to land development projects at catchment area. Therefore, a comprehensive water quality assessment of Bera Lake was implemented in order to compare current water quality with the implementation of land development projects. In situ water quality surveying was implemented using calibrated full option Hydrolab DS 5. Eleven parameters viz., temperature, depth of sampling, salinity, Turbidity, total dried solid, pH, NH4(+), N03(-), Cl(-), saturation percentage of dissolved oxygen, specific conductivity were recorded in fifty one stations at 0.2h, 0.5h, and 0.8h depth. National Water Quality Standards for Malaysia (NWQS) and Water Quality were used to evaluate Bera Lake quality based on previous and resultant data. Vertical water quality analysis revealed a clear stratification in Bera Lake water profile in terms of temperature, dissolved oxygen, chloride (Cl(-)), nitrate (NO(3)), pH and specific conductivity (EC) parameters. Results clearly demonstrate the important role of land use changes since 1972 in the physico-chemical condition of water quality at Bera Lake. Classifications of water quality before and after land development project were calculated as class II and class V, respectively. A long-term and comprehensive monitoring of water quality assessment is recommended in order to reach plan of sustainable water resources use with conservation approach.
In this study, a new magnetic adsorbent based on magnetite-sporopollenin/graphene oxide (Fe3O4-SP/GO) was successfully developed. The adsorbent was applied for magnetic solid phase extraction (MSPE) of three selected polar organophosphorus pesticides (OPPs), namely, dimethoate, phenthoate, and phosphamidon, prior to gas chromatography analysis with electron capture detection (GC-μECD). The Fe3O4-SP/GO adsorbent combines the advantages of superior adsorption capability of the modified sporopollenin (SP) with graphene oxide (GO) and magnetite (Fe3O4) for easy isolation from sample solution. Several MSPE parameters were optimized. Under optimized conditions, excellent linearity (R2 ≥ 0.9994) was achieved using matrix match calibration in the range of 0.1 to 500 ng mL-1. The limit of detection (LOD) method (S/N = 3) was from 0.02 to 0.05 ng mL-1. The developed Fe3O4-SP/GO MSPE method was successfully applied for the determination of these three polar OPPs in cucumber, long beans, bell pepper, and tomato samples. Good recoveries (81.0-120.0%) and good relative standard deviation (RSD) (1.4-7.8%, n = 3) were obtained for the spiked OPPs (1 ng mL-1) from real samples. This study is beneficial for adsorptive removal of toxic pesticide compounds from vegetable samples.
In this study, a disposable and simple electrochemical immunosensor was fabricated for the detection of carcinoembryonic antigen. In this method, silver nanoparticles (AgNPs) were mixed with reduced graphene oxide (rGO) to modify the surface of screen-printed carbon electrode (SPE). Initially, AgNPs-rGO modified-SPEs were fabricated by using simple electrochemical deposition method. Then the carcinoembryonic antigen (CEA) was immobilized between the primary antibody and horseradish peroxidase (HRP)-conjugated secondary antibody onto AgNPs-rGO modified-SPEs to fabricate a sandwich-type electrochemical immunosensor. The proposed method could detect the CEA with a linear range of 0.05-0.50µgmL-1 and a detection limit down to 0.035µgmL-1 as compared to its non-sandwich counterpart, which yielded a linear range of 0.05-0.40µgmL-1, with a detection limit of 0.042µgmL-1. The immunosensor showed good performance in the detection of carcinoembryonic antigen, exhibiting a simple, rapid and low-cost. The immunosensor showed a higher sensitivity than an enzymeless sensor.
Tungsten trioxide (WO₃) possesses a small band gap energy of 2.4-2.8 eV and is responsive to both ultraviolet and visible light irradiation including strong absorption of the solar spectrum and stable physicochemical properties. Thus, controlled growth of one-dimensional (1D) WO₃ nanotubular structures with desired length, diameter, and wall thickness has gained significant interest. In the present study, 1D WO₃ nanotubes were successfully synthesized via electrochemical anodization of tungsten (W) foil in an electrolyte composed of 1 M of sodium sulphate (Na₂SO₄) and ammonium fluoride (NH₄F). The influence of NH₄F content on the formation mechanism of anodic WO₃ nanotubular structure was investigated in detail. An optimization of fluoride ions played a critical role in controlling the chemical dissolution reaction in the interface of W/WO₃. Based on the results obtained, a minimum of 0.7 wt% of NH₄F content was required for completing transformation from W foil to WO₃ nanotubular structure with an average diameter of 85 nm and length of 250 nm within 15 min of anodization time. In this case, high aspect ratio of WO₃ nanotubular structure is preferred because larger active surface area will be provided for better photocatalytic and photoelectrochemical (PEC) reactions.
The addition of a photocatalyst to ordinary building materials such as concrete creates environmentally friendly materials by which air pollution or pollution of the surface can be diminished. The use of LiNbO3 photocatalyst in concrete material would be more beneficial since it can produce artificial photosynthesis in concrete. In these research photoassisted solid-gas phases reduction of carbon dioxide (artificial photosynthesis) was performed using a photocatalyst, LiNbO3, coated on concrete surface under illumination of UV-visible or sunlight and showed that LiNbO3 achieved high conversion of CO2 into products despite the low levels of band-gap light available. The high reaction efficiency of LiNbO3 is explained by its strong remnant polarization (70 µC/cm(2)), allowing a longer lifetime of photoinduced carriers as well as an alternative reaction pathway. Due to the ease of usage and good photocatalytic efficiency, the research work done showed its potential application in pollution prevention.
We present results from the OP3 campaign in Sabah during 2008 that allow us to study the impact of local emission changes over Borneo on atmospheric composition at the regional and wider scale. OP3 constituent data provide an important constraint on model performance. Treatment of boundary layer processes is highlighted as an important area of model uncertainty. Model studies of land-use change confirm earlier work, indicating that further changes to intensive oil palm agriculture in South East Asia, and the tropics in general, could have important impacts on air quality, with the biggest factor being the concomitant changes in NO(x) emissions. With the model scenarios used here, local increases in ozone of around 50 per cent could occur. We also report measurements of short-lived brominated compounds around Sabah suggesting that oceanic (and, especially, coastal) emission sources dominate locally. The concentration of bromine in short-lived halocarbons measured at the surface during OP3 amounted to about 7 ppt, setting an upper limit on the amount of these species that can reach the lower stratosphere.
This paper reports measurements of land-atmosphere fluxes of sensible and latent heat, momentum, CO(2), volatile organic compounds (VOCs), NO, NO(2), N(2)O and O(3) over a 30 m high rainforest canopy and a 12 m high oil palm plantation in the same region of Sabah in Borneo between April and July 2008. The daytime maximum CO(2) flux to the two canopies differs by approximately a factor of 2, 1200 mg C m(-2) h(-1) for the oil palm and 700 mg C m(-2) h(-1) for the rainforest, with the oil palm plantation showing a substantially greater quantum efficiency. Total VOC emissions are also larger over the oil palm than over the rainforest by a factor of 3. Emissions of isoprene from the oil palm canopy represented 80 per cent of the VOC emissions and exceeded those over the rainforest in similar light and temperature conditions by on average a factor of 5. Substantial emissions of estragole (1-allyl-4-methoxybenzene) from the oil palm plantation were detected and no trace of this VOC was detected in or above the rainforest. Deposition velocities for O(3) to the rainforest were a factor of 2 larger than over oil palm. Emissions of nitrous oxide were larger from the soils of the oil palm plantation than from the soils of the rainforest by approximately 25 per cent. It is clear from the measurements that the large change in the species composition generated by replacing rainforest with oil palm leads to profound changes in the net exchange of most of the trace gases measured, and thus on the chemical composition of the boundary layer over these surfaces.
We report measurements of atmospheric composition over a tropical rainforest and over a nearby oil palm plantation in Sabah, Borneo. The primary vegetation in each of the two landscapes emits very different amounts and kinds of volatile organic compounds (VOCs), resulting in distinctive VOC fingerprints in the atmospheric boundary layer for both landscapes. VOCs over the Borneo rainforest are dominated by isoprene and its oxidation products, with a significant additional contribution from monoterpenes. Rather than consuming the main atmospheric oxidant, OH, these high concentrations of VOCs appear to maintain OH, as has been observed previously over Amazonia. The boundary-layer characteristics and mixing ratios of VOCs observed over the Borneo rainforest are different to those measured previously over Amazonia. Compared with the Bornean rainforest, air over the oil palm plantation contains much more isoprene, monoterpenes are relatively less important, and the flower scent, estragole, is prominent. Concentrations of nitrogen oxides are greater above the agro-industrial oil palm landscape than over the rainforest, and this leads to changes in some secondary pollutant mixing ratios (but not, currently, differences in ozone). Secondary organic aerosol over both landscapes shows a significant contribution from isoprene. Primary biological aerosol dominates the super-micrometre aerosol over the rainforest and is likely to be sensitive to land-use change, since the fungal source of the bioaerosol is closely linked to above-ground biodiversity.
Anodizing could be used for bio-functionalization of the surfaces of titanium alloys. In this study, we use anodizing for creating nanotubes on the surface of porous titanium alloy bone substitutes manufactured using selective laser melting. Different sets of anodizing parameters (voltage: 10 or 20V anodizing time: 30min to 3h) are used for anodizing porous titanium structures that were later heat treated at 500°C. The nanotopographical features are examined using electron microscopy while the bioactivity of anodized surfaces is measured using immersion tests in the simulated body fluid (SBF). Moreover, the effects of anodizing and heat treatment on the performance of one representative anodized porous titanium structures are evaluated using in vitro cell culture assays using human periosteum-derived cells (hPDCs). It has been shown that while anodizing with different anodizing parameters results in very different nanotopographical features, i.e. nanotubes in the range of 20 to 55nm, anodized surfaces have limited apatite-forming ability regardless of the applied anodizing parameters. The results of in vitro cell culture show that both anodizing, and thus generation of regular nanotopographical feature, and heat treatment improve the cell culture response of porous titanium. In particular, cell proliferation measured using metabolic activity and DNA content was improved for anodized and heat treated as well as for anodized but not heat-treated specimens. Heat treatment additionally improved the cell attachment of porous titanium surfaces and upregulated expression of osteogenic markers. Anodized but not heat-treated specimens showed some limited signs of upregulated expression of osteogenic markers. In conclusion, while varying the anodizing parameters creates different nanotube structure, it does not improve apatite-forming ability of porous titanium. However, both anodizing and heat treatment at 500°C improve the cell culture response of porous titanium.
The sol-gel/ultrasonically rout produced the novel MnS2-SiO2 nano-hetero-photocatalysts with the various ratio of MnS2. Prepared nano-catalyst were investigated in the photo-degradation of methylene blue under UV light illumination. Structural and optical attributes of as-prepared nano-catalysts were evaluated by X-ray diffraction and photoelectron spectroscopy. The morphological were studied by scanning electron microscopy-EDS, and dynamic light scattering. The diffuse reflectance spectroscopy was applied to examine the band gap energy. The Eg values of SiO2, MnS2-SiO2-0, MnS2-SiO2-1, and MnS2-SiO2-2 nanocomposites are 6.51, 3.85, 3.17, and 2.67 eV, respectively. The particle size of the SiO2 and MnS2-SiO2-1 nanocomposites were 100.0, and 65.0 nm, respectively. The crystallite size values of MnS2-SiO2-1 were 52.21 nm, and 2.9 eV, respectively. MnS2-SiO2 nano-photocatalyst was recognized as the optimum sample by degrading 96.1% of methylene blue from water. Moreover, the influence of pH of the solution, and contact time as decisive factors on the photo-degradation activity were investigated in this project. The optimum data for pH and time were found 9 and 60 min, respectively. The photo-degradation capacity of MnS2-SiO2-2 is improved (96.1%) due to the low band gap was found from UV-vis DRS. The antimicrobial data of MnS2-SiO2 were studied and demonstrated that the MnS2-SiO2 has fungicidal and bactericidal attributes.
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.
Hepatitis B virus core antigen (HBcAg) is the major structural protein of hepatitis B virus (HBV). The presence of anti-HBcAg antibody in a blood serum indicates that a person has been exposed to HBV. This study demonstrated that the immobilization of HBcAg onto the gold nanoparticles-decorated reduced graphene oxide (rGO-en-AuNPs) nanocomposite could be used as an antigen-functionalized surface to sense the presence of anti-HBcAg. The modified rGO-en-AuNPs/HBcAg was then allowed to undergo impedimetric detection of anti-HBcAg with anti-estradiol antibody and bovine serum albumin as the interferences. Upon successful detection of anti-HBcAg in spiked buffer samples, impedimetric detection of the antibody was then further carried out in spiked human serum samples. The electrochemical response showed a linear relationship between electron transfer resistance and the concentration of anti-HBcAg ranging from 3.91ngmL-1 to 125.00ngmL-1 with lowest limit of detection (LOD) of 3.80ngmL-1 at 3σm-1. This established method exhibits potential as a fast and convenient way to detect anti-HBcAg.
In this study, nanohybrid materials consisting of graphene oxide (GO), β‑cyclodextrin (CD) and poly(amido amine) dendrimer (DEN) were successfully prepared by covalent bonding. GO-CD and GO-CD-DEN were found to be potential nanocarriers for anticancer drugs including chemotherapeutics (doxorubicin (DOX), camptothecin (CPT)) and photosensitizer (protoporphyrin IX (PpIX)). GO-CD possessed 1.2 times higher DOX-loading capacity than GO due to inclusion of additional DOX to the CD. The drug loading on GO-CD-DEN increased in the order: DOX
We have synthesized graphene oxide using improved Hummer's method in order to explore the potential use of the resulting graphene oxide as a nanocarrier for an active anticancer agent, chlorogenic acid (CA). The synthesized graphene oxide and chlorogenic acid-graphene oxide nanocomposite (CAGO) were characterized using Fourier transform infrared (FTIR) spectroscopy, thermogravimetry and differential thermogravimetry analysis, Raman spectroscopy, powder X-ray diffraction (PXRD), UV-vis spectroscopy and high resolution transmission electron microscopy (HRTEM) techniques. The successful conjugation of chlorogenic acid onto graphene oxide through hydrogen bonding and π-π interaction was confirmed by Raman spectroscopy, FTIR analysis and X-ray diffraction patterns. The loading of CA in the nanohybrid was estimated to be around 13.1% by UV-vis spectroscopy. The release profiles showed favourable, sustained and pH-dependent release of CA from CAGO nanocomposite and conformed well to the pseudo-second order kinetic model. Furthermore, the designed anticancer nanohybrid was thermally more stable than its counterpart. The in vitro cytotoxicity results revealed insignificant toxicity effect towards normal cell line, with a viability of >80% even at higher concentration of 50μg/mL. Contrarily, CAGO nanocomposite revealed enhanced toxic effect towards evaluated cancer cell lines (HepG2 human liver hepatocellular carcinoma cell line, A549 human lung adenocarcinoma epithelial cell line, and HeLa human cervical cancer cell line) compared to its free form.