The granulation process in palm oil mill effluent using calcium oxide-cement kiln dust (CaO-CKD) provides an attractive and cost effective treatment option. In this study the efficiency of CaO-CKD at doses of 1.5-20 g/l was tested in batch experiments and found that 10 g of CaO/l caused the greatest degradation of VFA, butyrate and acetate. An upflow anaerobic sludge blanket (UASB) reactor was operated continuously at 35°C for 150 days to investigate the effect of CaO-CKD on sludge granulation and methanogenesis during start-up. The treatment of POME emphasized the influence of varying organic loading rates (OLR). Up to 94.9% of COD was removed when the reactor was fed with the 15.5-65.5 g-CODg/l at an OLR of 4.5-12.5 kg-COD/m(3)d, suggesting the feasibility of using CaO in an UASB process to treat POME. The ratio of volatile solids/total solids (VS/TS) and volatile fatty acids in the anaerobic sludge in the UASB reactor decreased significantly after long-term operation due to the precipitation of calcium carbonate in the granules. Granulation and methanogenesis decreased with an increase in the influent CaO-CKD concentration.
Thermodynamic and kinetic parameters of catalytic pyrolysis of rice hull (RH) pyrolysis using two different types of renewable catalysts namely natural limestone (LS) and eggshells (ES) using thermogravimetric analysis (TG) approach at different heating rates of 10-100 K min-1 in temperature range of 323-1173 K are investigated. Catalytic pyrolysis mechanism of both catalysts had shown significant effect on the degradation of RH. Model free kinetic of iso-conversional method (Flynn-Wall-Ozawa) and multi-step reaction model (Distributed Activation Energy Model) were employed into present study. The average activation energy was found in the range of 175.4-177.7 kJ mol-1 (RH), 123.3-132.5 kJ mol-1 (RH-LS), and 96.1-100.4 kJ mol-1 (RH-ES) respectively. The syngas composition had increased from 60.05 wt% to 63.1 wt% (RH-LS) and 63.4 wt% (RH-ES). However, the CO2 content had decreased from 24.1 wt% (RH) to 20.8 wt% (RH-LS) and 19.9 wt% (RH-ES).
We have synthesized a graphene oxide (GO)-based theranostic nanodelivery system (GOTS) for magnetic resonance imaging (MRI) using naturally occurring protocatechuic acid (PA) as an anticancer agent and gadolinium (III) nitrate hexahydrate (Gd) as the starting material for a contrast agent,. Gold nanoparticles (AuNPs) were subsequently used as second diagnostic agent. The GO nanosheets were first prepared from graphite via the improved Hummer's protocol. The conjugation of the GO and the PA was done via hydrogen bonding and π-π stacking interactions, followed by surface adsorption of the AuNPs through electrostatic interactions. GAGPA is the name given to the nanocomposite obtained from Gd and PA conjugation. However, after coating with AuNPs, the name was modified to GAGPAu. The physicochemical properties of the GAGPA and GAGPAu nanohybrids were studied using various characterization techniques. The results from the analyses confirmed the formation of the GOTS. The powder X-ray diffraction (PXRD) results showed the diffractive patterns for pure GO nanolayers, which changed after subsequent conjugation of the Gd and PA. The AuNPs patterns were also recorded after surface adsorption. Cytotoxicity and magnetic resonance imaging (MRI) contrast tests were also carried out on the developed GOTS. The GAGPAu was significantly cytotoxic to the human liver hepatocellular carcinoma cell line (HepG2) but nontoxic to the standard fibroblast cell line (3T3). The GAGPAu also appeared to possess higher T1 contrast compared to the pure Gd and water reference. The GOTS has good prospects of serving as future theranostic platform for cancer chemotherapy and diagnosis.
We have synthesized a bimodal theranostic nanodelivery system (BIT) that is based on graphene oxide (GO) and composed of a natural chemotherapeutic agent, chlorogenic acid (CA) used as the anticancer agent, while gadolinium (Gd) and gold nanoparticles (AuNPs) were used as contrast agents for magnetic resonance imaging (MRI) modality. The CA and Gd guest agents were simultaneously loaded on the GO nanolayers using chemical interactions, such as hydrogen bonding and π-π non-covalent interactions to form GOGCA nanocomposite. Subsequently, the AuNPs were doped on the surface of the GOGCA by means of electrostatic interactions, which resulted in the BIT. The physico-chemical studies of the BIT affirmed its successful development. The X-ray diffractograms (XRD) collected of the various stages of BIT synthesis showed the successive development of the hybrid system, while 90% of the chlorogenic acid was released in phosphate buffer solution (PBS) at pH 4.8. This was further reaffirmed by the in vitro evaluations, which showed stunted HepG2 cancer cells growth against the above 90% cell growth in the control cells. A reverse case was recorded for the 3T3 normal cells. Further, the acquired T1-weighted image of the BIT doped samples obtained from the MRI indicated contrast enhancement in comparison with the plain Gd and water references. The abovementioned results portray our BIT as a promising future chemotherapeutic for anticancer treatment with diagnostic modalities.
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.
The present study examines the synthesis of Co3O4 ultra-nanosheets (Co3O4 UNSs) and Co3O4 ultra-nanosheet-Ni(OH)2 (Co3O4 UNS-Ni(OH)2) via solvothermal process and their application as non-enzymatic electrochemical sensors for glucose detection. X-ray diffraction and transmission electron microscopy results confirmed the Co3O4 UNS deposition on Ni(OH)2 surface. The presence of Co3O4 UNSs on Ni (OH) 2 surface improved the sensitivity of glucose detection, from the increase of glucose oxidation peak current at the Co3O4 UNS-Ni(OH)2/glassy carbon electrode (current density: 2000μA·cm(-2)), compared to the Co3O4 UNSs. These results confirmed that Ni(OH)2 on glassy carbon electrode is a sensitive material for glucose detection, moreover the Co3O4 UNSs can increase the interaction and detection of glucose due to their high surface area. The estimated limit of detection (S/N=3) and limit of quantification (S/N=10) of the linear segment (5-40μM) are 1.08μM and 3.60μM respectively. The reproducibility experiments confirmed the feasibility of Co3O4 UNS-Ni(OH)2 for the quantitative detection of certain concentration ranges of glucose.
Chitosan/PVA/Na-titanate/TiO2 composite was synthesized by solution casting method. The composite was analyzed via Fourier Transform Infrared Spectroscopy, X-ray diffraction, Field Emission Scanning Electron Microscopy, Thermal gravimetric analysis and water stability test. Incorporation of Na-titanate shown decrease of crystallinity for chitosan but increase water stability. However, the composite structure was deteriorated with considerable weight loss in acidic medium. Two anionic dyes, methyl orange and congo red were used for the adsorption test. The adsorption behavior of the composites were described by pseudo-second-order kinetic model and Lagergren-first-order model for methyl orange and congo red, respectively. For methyl orange, adsorption was started with a promising decolorization rate. 99.9% of methyl orange dye was removed by the composite having higher weightage of chitosan and crystalline TiO2 phase. On the other hand, for the congo red the composite having higher chitosan and Na-titanate showed an efficient removal capacity of 95.76%. UV-vis results showed that the molecular backbone of methyl orange and congo red was almost destroyed when equilibrium was obtained, and the decolorization rate was reaching 100%. Kinetic study results showed that the photocatalytic degradation of methyl orange and congo red could be explained by Langmuir-Hinshelwood model. Thus, chitosan/PVA/Na-titanate/TiO2 possesses efficient adsorptivity and photocatalytic property for dye degradation.
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.
A rapid growth in the development of power generation and transportation sectors would result in an increase in the carbon dioxide (CO2) concentration in the atmosphere. As it will continue to play a vital role in meeting current and future needs, significant efforts have been made to address this problem. Over the past few years, extensive studies on the development of heterogeneous catalysts for CO2 methanation have been investigated and reported in the literatures. In this paper, a comprehensive overview of methanation research studies over lanthanide oxide catalysts has been reviewed. The utilisation of lanthanide oxides as CO2 methanation catalysts performed an outstanding result of CO2 conversion and improvised the conversion of acidity from CO2 gas to CH4 gas. The innovations of catalysts towards the reaction were discussed in details including the influence of preparation methods, the structure-activity relationships as well as the mechanism with the purpose of outlining the pathways for future development of the methanation process.
During the process and operation of the dyes, the wastes produced were commonly found to contain organic and inorganic impurities leading to risks in the ecosystem and biodiversity with the resultant impact on the environment. Improper effluent disposal in aqueous ecosystems leads to reduction of sunlight penetration which in turn diminishes photosynthetic activity, resulting in acute toxic effects on the aquatic flora/fauna and dissolved oxygen concentration. Recently, photodegradation of various synthetic dyes has been studied in terms of their absorbance and the reduction of oxygen content by changes in the concentration of the dye. The advantages that make photocatalytic techniques superior to traditional methods are the ability to remove contaminates in the range of ppb, no generation of polycyclic compounds, higher speed, and lower cost. Semiconductor metal oxides, typically TiO2, ZnO, SnO, NiO, Cu2O, Fe3O4, and also CdS have been utilized as photocatalyst for their nontoxic nature, high photosensitivity, wide band gap and high stability. Various process parameters like photocatalyst dose, pH and initial dye concentrations have been varied and highlighted. Research focused on surface modification of semiconductors and mixed oxide semiconductors by doping them with noble metals (Pt, Pd, Au, and Ag) and organic matter (C, N, Cl, and F) showed enhanced dye degradation compared to corresponding native semiconductors. This paper reviews recent advances in heterogeneous photocatalytic decolorization for the removal of synthetic dyes from water and wastewater. Thus, the main core highlighted in this paper is the critical selection of semiconductors for photocatalysis based on the chemical, physical, and selective nature of the poisoning dyes.
Magnetic field sensors are becoming an essential part of everyday life due to the improvements in their sensitivities and resolutions, while at the same time they have become compact, smaller in size and economical. In the work presented herein a Lorentz force based CMOS-MEMS magnetic field sensor is designed, fabricated and optically characterized. The sensor is fabricated by using CMOS thin layers and dry post micromachining is used to release the device structure and finally the sensor chip is packaged in DIP. The sensor consists of a shuttle which is designed to resonate in the lateral direction (first mode of resonance). In the presence of an external magnetic field, the Lorentz force actuates the shuttle in the lateral direction and the amplitude of resonance is measured using an optical method. The differential change in the amplitude of the resonating shuttle shows the strength of the external magnetic field. The resonance frequency of the shuttle is determined to be 8164 Hz experimentally and from the resonance curve, the quality factor and damping ratio are obtained. In an open environment, the quality factor and damping ratio are found to be 51.34 and 0.00973 respectively. The sensitivity of the sensor is determined in static mode to be 0.034 µm/mT when a current of 10 mA passes through the shuttle, while it is found to be higher at resonance with a value of 1.35 µm/mT at 8 mA current. Finally, the resolution of the sensor is found to be 370.37 µT.
The recent developments of nanostructured WO3 thin films synthesized through the electrochemical route of electrochemical anodization and cathodic electrodeposition for the application in photoelectrochemical (PEC) water splitting are reviewed. The key fundamental reaction mechanisms of electrochemical anodization and cathodic electrodeposition methods for synthesizing nanostructured WO3 thin films are explained. In addition, the effects of metal oxide precursors, electrode substrates, applied potentials and current densities, and annealing temperatures on size, composition, and thickness of the electrochemically synthesized nanostructured WO3 thin films are elucidated in detail. Finally, a summary is given for the general evaluation practices used to calculate the energy conversion efficiency of nanostructured WO3 thin films and a recommendation is provided to standardize the presentation of research results in the field to allow for easy comparison of reported PEC efficiencies in the near future.
Double perovskite-type catalysts including La2CoMnO6 and La2CuMnO6 are first evaluated for the effectiveness in removing volatile organic compounds (VOCs), and single perovskites (LaCoO3, LaMnO3, and LaCuO3) are also tested for comparison. All perovskites are tested with the gas hourly space velocity (GHSV) of 30,000hr-1, and the temperature range of 100-600°C for C7H8 removal. Experimental results indicate that double perovskites have better activity if compared with single perovskites. Especially, toluene (C7H8) can be completely oxidized to CO2 at 300°C as La2CoMnO6 is applied. Characterization of catalysts indicates that double perovskites own unique surface properties and are of higher amounts of lattice oxygen, leading to higher activity. Additionally, apparent activation energy of 68kJ/mol is calculated using Mars-van Krevelen model for C7H8 oxidation with La2CoMnO6 as catalyst. For durability test, both La2CoMnO6 and La2CuMnO6 maintain high C7H8 removal efficiencies of 100% and 98%, respectively, at 300°C and 30,000hr-1, and they also show good resistance to CO2 (5%) and H2O(g) (5%) of the gas streams tested. For various VOCs including isopropyl alcohol (C3H8O), ethanal (C2H4O), and ethylene (C2H4) tested, as high as 100% efficiency could be achieved with double perovskite-type catalysts operated at 300-350°C, indicating that double perovskites are promising catalysts for VOCs removal.
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.
Cobalt oxide nanocubes incorporated with reduced graphene oxide (rGO-Co3O4) was prepared by using simple one-step hydrothermal route. Crystallinity and structural characteristics of the nanocomposite were analyzed and confirmed using X-ray diffraction (XRD) and Raman analysis, respectively. The cubical shape of the Co3O4 nanostructures and the distribution of Co3O4 nanocubes on the surface of rGO sheets were identified through field emission scanning electron microscopy (FESEM) and energy dispersive X-ray (EDX) mapping analysis, respectively. Raman spectra depicted the presence of D and G bands for GO and rGO with different ID/IG values and thus confirmed the reduction of GO into rGO. The electrochemical study reflects that the rGO-Co3O4 nanocomposite shows good electrocatalytic activity in oxidation of depression biomarker serotonin (5-HT) in phosphate buffer (pH 7.2). The detection of 5-HT was carried out by using rGO-Co3O4 nanocomposite modified glassy carbon electrode under dynamic condition using amperometry technique with a linear range of 1-10 μM. The limit of detection and limit of quantification were calculated and found to be 1.128 and 3.760 μM, respectively with a sensitivity value of 0.133 μΑ·μM-1. The sensor showed selectivity in the presence of different interferent species such as ascorbic acid, dopamine and uric acid.
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.
In this research work, carbon nanofibers (CNFs) were synthesized on honeycomb monolith substrates using injection chemical vapor deposition (ICVD) technique. The effect of various wash-coated materials and catalyst promoter on the growth rate of CNFs on monolith substrates were examined. The characteristics of the synthesized CNFs-coated monolith composites were examined using Raman spectroscopy, Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FE-SEM), and Transmission electron microscopy (TEM) techniques. According to the textural characterization study, the specific surface area and pore volume of CNFs-coated monolith composites were significantly improved as compared to bare monolith which might be attributed to the growth of highly pure and aligned CNFs over monolith substrate. Besides that, the synthesized CNFs-coated monolith possessed extremely well thermal stability up to the temperature of 550 °C which was corresponded to the strong attachment of highly graphitized CNFs over monolith substrates.
High performance sorbents for flue gas desulfurization can be synthesized by hydration of coal fly ash, calcium sulfate, and calcium oxide. In general, higher desulfurization activity correlates with higher sorbent surface area. Consequently, a major aim in sorbent synthesis is to maximize the sorbent surface area by optimizing the hydration conditions. This work presents an integrated modeling and optimization approach to sorbent synthesis based on statistical experimental design and two artificial intelligence techniques: neural network and genetic algorithm. In the first step of the approach, the main and interactive effects of three hydration variables on sorbent surface area were evaluated using a full factorial design. The hydration variables of interest to this study were hydration time, amount of coal fly ash, and amount of calcium sulfate and the levels investigated were 4-32 h, 5-15 g, and 0-12 g, respectively. In the second step, a neural network was used to model the relationship between the three hydration variables and the sorbent surface area. A genetic algorithm was used in the last step to optimize the input space of the resulting neural network model. According to this integrated modeling and optimization approach, an optimum sorbent surface area of 62.2m(2)g(-1) could be obtained by mixing 13.1g of coal fly ash and 5.5 g of calcium sulfate in a hydration process containing 100ml of water and 5 g of calcium oxide for a fixed hydration time of 10 h.
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.
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