One of the most cited limitations of capillary and microchip electrophoresis is the poor sensitivity. This review continues to update this series of biannual reviews, first published in Electrophoresis in 2007, on developments in the field of online/in-line concentration methods in capillaries and microchips, covering the period July 2016-June 2018. It includes developments in the field of stacking, covering all methods from field-amplified sample stacking and large-volume sample stacking, through to isotachophoresis, dynamic pH junction, and sweeping. Attention is also given to online or in-line extraction methods that have been used for electrophoresis.
Adsorption is one of the most efficient ways to remove heavy metal from wastewater. In this study, the adsorptive removal of hexavalent chromium, Cr (VI) from aqueous solution was investigated using natural zeolite, clinoptilolite, in the form of hollow fibre ceramic membrane (HFCM). The HFCM sample was prepared using phase inversion-based extrusion technique and followed by sintering process at different sintering temperatures in the range of 900-1050 °C. The fabricated HFCM was characterised using scanning electron microscopy (SEM), contact angle, water permeability, and mechanical strength for all HFCMs sintered at different temperatures. The adsorption and filtration test of Cr (VI) were performed using an in-house water permeation set up with a dead-end cross-flow permeation test. An asymmetric structure with sponge- and finger-like structures across the cross-section of HFCM was observed using SEM. Based on the characterisation data, 1050 °C was chosen to be the best sintering temperature as the water permeability and mechanical strength of this HFCM were 29.14 L/m2∙h and 50.92 MPa, respectively. The performance of the HFCM in adsorption/filtration was 44% of Cr (VI) removal at the Cr (VI) concentration of 40 mg/L and pH 4. In addition, the mathematical model was also performed in simulating the experimental data obtained from this study. All in all, the natural zeolite-based HFCM has a potential as a single-step Cr (VI) removal by membrane adsorption for the wastewater treatment.
Intensive land expansion of commercial oil palm agricultural lands results in reducing the size of peat swamp forests, particularly in Southeast Asia. The effect of this land conversion on macrofungal biodiversity is, however, understudied. We quantified macrofungal biodiversity by identifying mushroom sporocarps throughout four different habitats; logged peat swamp forest, large-scale oil palm plantation, monoculture, and polyculture smallholdings. We recorded a total of 757 clusters of macrofungi belonging to 127 morphospecies and found that substrates for growing macrofungi were abundant in peat swamp forest; hence, morphospecies richness and macrofungal clusters were significantly greater in logged peat swamp forest than converted oil palm agriculture lands. Environmental factors that influence macrofungi in logged peat swamp forests such as air temperature, humidity, wind speed, soil pH, and soil moisture were different from those in oil palm plantations and smallholdings. We conclude that peat swamp forests are irreplaceable with respect to macrofungal biodiversity. They host much greater macrofungal biodiversity than any of the oil palm agricultural lands. It is imperative that further expansion of oil palm plantation into remaining peat swamp forests should be prohibited in palm oil producing countries. These results imply that macrofungal distribution reflects changes in microclimate between habitats and reduced macrofungal biodiversity may adversely affect decomposition in human-modified landscapes.
The aim of this study was ultrasound assisted removal of Ceftriaxone sodium (CS) based on CCD model. Using sonochemical synthesized Bi2WO6 implanted on graphitic carbon nitride/Multiwall carbon nanotube (g-C3N4/MWCNT/Bi2WO6). For this purpose g-C3N4/MWCNT/Bi2WO6 was synthesized and characterized using diverse approaches including XRD, FE-SEM, XPS, EDS, HRTEM, FT-IR. Then, the contribution of conventional variables including pH, CS concentration, adsorbent dosage and ultrasound contact time were studied by central composite design (CCD) under response surface methodology (RSM). ANOVA was employed to the variable factors, and the most desirable operational conditions mass provided. Drug adsorption yield of 98.85% obtained under these defined conditions. Through conducting five experiments, the proper prediction of the optimum point were examined. The respective results showed that RSD% was lower than 5% while the t-test confirmed the high quality of fitting. Langmuir isotherm equation fits the experimental data best and the removal followed pseudo-second order kinetics. The estimation of the experimentally obtained maximum adsorption capacities was 19.57 mg.g- of g-C3N4/MWCNT/Bi2WO6 for CS. Boundary layer diffusion explained the mechanism of removal via intraparticle diffusion.
The effect of pre-treatment of dewatered sludge using different nitrite concentrations and pH for microbial fuel cell (MFC) application was investigated. The results show that the addition of nitrite was feasible to increase the solubilization rate of the sludge and may reduce mass transfer limitation at the anode. This helped the MFC to reach higher voltage and to generate more power. The higher free nitrous acid (FNA) concentration under the acidic condition helped to increase sludge solubilization. However, under an alkaline condition, during which the FNA concentration was relatively low, the solubilization of the sludge was higher. The highest voltage and power density produced was 390 mV and 153 mW/m2, respectively, with the addition of nitrite at 100 mg-N/L and pH 9. Furthermore, it was found that elevated levels of FNA could inhibit electrogenic bacteria thus reducing power generation.
Cephalexin (CFX) antibiotic, a potent pharmaceutical water pollutant, was efficiently removed by activated carbon (AC) derived from a single-step pyrolysis of phosphoric acid-activated chitin. Experimental conditions such as temperature, CFX initial concentration, and solution pH were screened in batch adsorption. Phosphoric acid activation of chitin and subsequent pyrolysis tailored the Brunauer-Emmett-Teller surface area, total pore volume, and average pore diameter to 1199.02 m2/g, 0.641 cm3/g, and 21.37 Å, respectively. The Langmuir isotherm adequately described the equilibrium data for CFX adsorption on chitin-AC, with an R2 of 0.99 and a monolayer capacity of 245.19 mg/g at 50 °C. Chitin-AC showed higher adsorption capacity compared with other ACs derived from industrial and agricultural precursors. When activated by phosphoric acid, chitin-AC featured functional multi-sites for vast antibiotic adsorption treatment. Overall, chitin-AC could be a promising adsorbent for removal of CFX.
Surface modified Multi-walled carbon nanotubes (MWCNTs) Buckypaper/Polyvinyl Alcohol (BP/PVA) composite membrane was synthesized and utilized as support material for immobilization of Jicama peroxidase (JP). JP was successfully immobilized on the BP/PVA membrane via covalent bonding by using glutaraldehyde. The immobilization efficiency was optimized using response surface methodology (RSM) with the face-centered central composite design (FCCCD) model. The optimum enzyme immobilization efficiency was achieved at pH 6, with initial enzyme loading of 0.13 U/mL and immobilization time of 130 min. The results of BP/PVA membrane showed excellent performance in immobilization of JP with high enzyme loading of 217 mg/g and immobilization efficiency of 81.74%. The immobilized system exhibited significantly improved operational stability under various parameters, such as pH, temperature, thermal and storage stabilities when compared with free enzyme. The effective binding of peroxidase on the surface of the BP/PVA membrane was evaluated and confirmed by Field emission scanning electron microscopy (FESEM) coupled with Energy Dispersive X-Ray Spectroscopy (EDX), Fourier transform infrared spectroscopy (FTIR) and Thermogravimetric Analysis (TGA). This work reports the characterization results and performances of the surface modified BP/PVA membrane for peroxidase immobilization. The superior properties of JP-immobilized BP/PVA membrane make it promising new-generation nanomaterials for industrial applications.
The data available in this repository were gathered from Balok, the only most productive spawning site for horseshoe crabs Tachypleus gigas and Carcinoscorpius rotundicauda in East Coast of Peninsular Malaysia. The mangrove horseshoe crab, C. rotundicauda population and spawning data are available in the first table. The horseshoe crabs were retrieved from Balok River using 11.43 cm mesh size gill nets installed at the river mouth, the confluence and last meander. The arthropods were inspected for damage, abnormality and growth before their release into Balok River, particularly at the site of capture. Sediment samples were retrieved at their spawning grounds to ascertain sediment composition and size classifications which were also processed using Logarithmic Method of Moments. Water parameters like temperature, pH and salinity were also investigated during year 2016. All these information are compiled into the second table and arranged according to the period of data availability. The horseshoe crab catch data of years 2012, 2013, 2014, 2015 and 2016 were made available by artisanal fisher and compiled in the third and fourth table for inter-species comparison.
Biocarriers are pivotal in enhancing the reusability of biocatalyst that would otherwise be less economical for industrial application. Ever since the induction of enzymatic technology, varied materials have been assessed for their biocompatibility with enzymes of distinct functionalities. Herein, cellulase was immobilized onto polymethacrylate particles (ICP) as the biocarrier grafted with ethylenediamine (EDA) and glutaraldehyde (GA). Carboxymethyl cellulose (CMC) was used as a model substrate for activity assay. Enzyme immobilization loading was determined by quantifying the dry weight differential of ICP (pre-& post-immobilization). Cellulase was successfully demonstrated to be anchored upon ICP and validated by FTIR spectra analysis. The optimal condition for cellulase immobilization was determined to be pH 6 at 20 °C. The maximum CMCase activity was achieved at pH 5 and 50 °C. Residual activity of ∼50% was retained after three iterations and dipped to ∼18% on following cycle. Also, ICP displayed superior pH adaptability as compared to free cellulase. The specific activity of ICP was 65.14 ± 1.11% relative to similar amount of free cellulase.
The presence of at least two ionizable active center groups has been detected by a study of the effect of pH upon catalysis of hydrolysis of L-alanyl-beta-naphthylamide by human liver alanine aminopeptidase and upon the inhibition of hydrolysis by inhibitors and substrate analogs. Octanoic acid, octylamine, and peptide inhibitors have been found to be competitive inhibitors and are therefore thought to bind the active center. L-Phe was previously shown to bind the active center since it was found to be a competitive inhibitor of the hydrolysis of tripeptide substrates (Garner, C. W., and Behal, F. J. (1975), Biochemistry 14, 3208). A plot of pKm vs. pH for the substrate L-Ala-beta-naphthylamide showed that binding decreased below pH 5.9 and above 7.5, the points at which the theoretical curve undergoes an integral change in slope. These points are interpreted as the pKa either of substrate ionizable groups or binding-dependent enzyme active center groups. Similar plots of pKm vs. pH for L-alanyl-p-nitroanilide (as substrate) and pKi vs. pH for L-Leu-L-Leu-L-Leu and D-Leu-L-Tyr (as inhibitors) gave pairs fo pKa values of 5.8 and 7.4, 6.0 and 7.5, and 5.7 and 7.5, respectively. All the above substrates (and D-Leu-L-Tyr) have pKa values near 7.5; therefore, the binding-dependent group with a pKa value near 7.5 is possibly this substrate group. Similar plots of pKi vs. pH for the inhibitors L-Phe, L-Met, L-Leu, octylamine, and octanoic acid had only one bending point at 7.7, 7.6, 7.4, 6.3, and 5.9, respectively. Amino acid inhibitors, octylamine, and octanoic acid have no groups with pKa values between 5 and 9. These data indicate that there are two active center ionizable groups with pKa values of approximately 6.0 and 7.5 which are involved in substrate binding or inhibitory amino acid binding but not in catalysis since Vmax was constant at all pH values tested.
In this study, a minimum-run resolution IV and central composite design have been developed to optimize tetracycline removal efficiency over mesoporous carbon derived from the metal-organic framework MIL-53 (Fe) as a self-sacrificial template. Firstly, minimum-run resolution IV, powered by the Design-Expert program, was used as an efficient and reliable screening study for investigating a set of seven factors, these were: tetracycline concentration (A: 5-15 mg/g), dose of mesoporous carbons (MPC) (B: 0.05-0.15 g/L), initial pH level (C: 2-10), contact time (D: 1-3 h), temperature (E: 20-40 °C), shaking speed (F: 150-250 rpm), and Na+ ionic strength (G: 10-90 mM) at both low (-1) and high (+1) levels, for investigation of the data ranges. The 20-trial model was analyzed and assessed by Analysis of Variance (ANOVA) data, and diagnostic plots (e.g., the Pareto chart, and half-normal and normal probability plots). Based on minimum-run resolution IV, three factors, including tetracycline concentration (A), dose of MPC (B), and initial pH (C), were selected to carry out the optimization study using a central composite design. The proposed quadratic model was found to be statistically significant at the 95% confidence level due to a low P-value (<0.05), high R2 (0.9078), and the AP ratio (11.4), along with an abundance of diagnostic plots (3D response surfaces, Cook's distance, Box-Cox, DFFITS, Leverage versus run, residuals versus runs, and actual versus predicted). Under response surface methodology-optimized conditions (e.g., tetracycline concentration of 1.9 mg/g, MPC dose of 0.15 g/L, and pH level of 3.9), the highest tetracycline removal efficiency via confirmation tests reached up to 98.0%-99.7%. Also, kinetic intraparticle diffusion and isotherm models were systematically studied to interpret how tetracycline molecules were absorbed on an MPC structure. In particular, the adsorption mechanisms including "electrostatic attraction" and "π-π interaction" were proposed.
This research aimed to improve the stability of Chlorella-Alginate Beads (CABs) by zeolite molecular sieves 13X. Dissolution time of synthesized Zeolite-Algal-Alginate Beads (ZABs) in a chelating agent revealed a significant improvement on the beads stability (78.5 ± 0.5 min) compared to the control beads (51.5 ± 0.5 min) under the optimum conditions of zeolite/alginate (1.5:1), pH 5 and 2% of beads. Monitoring cell growth during 5 days of incubation showed good biocompatibility of zeolite 13X. Scanning electron microscopy (SEM) indicated rough surface and spherical shapes of ZABs. Energy dispersive X-ray spectroscopy (EDX) and Fourier transform infrared spectroscopy (FTIR) of ZABs confirmed the presence of zeolite 13X within the matrix. The zeta potential value of ZABs indicated that the beads were relatively stable. The findings of this research showed that zeolite molecular sieves 13X have the potential to improve the stability of algal-alginate beads compared to common beads.
Ion-imprinting polymers (IIPs) materials draw the great recognition because of the powerful selectivity to the desired metal ions. Therefore, the ion-imprinting polymer (Ce-IIP) was prepared by using cerium metal with amidoxime ligand as the complexing agent, in addition ethylene glycol dimethacrylate (EGDMA) and 2,2-azobisisobutyronitrile (AIBN) are crosslinking agent and free radical initiator, respectively. Aqueous HCl was applied to leach the cerium ions from the imprinted polymer for the creation of cavities of template, which is utilized for further cerium ions adsorption with high selectivity. The Ce-IIP was characterized by using ICP-MS, FE-SEM and also solid state analysis by UV-vis NIR spectroscopy. FT-IR study confirmed the complexation of the Ce-IIP was successful. The optimum pH was found to be 6 and the highest adsorption capacity was estimated about 145 mg g-1. Thus, the prepared Ce-IIP gave very good selectivity to cerium ions in the presence of lanthanide ions and also Ce-IIP can be reused 10 times without a substantial loss in adsorption capacity.
Small sized electrocatalysts, which can be obtained by rapid nucleation and high supersaturation are imperative for outstanding methanol oxidation reaction (MOR). Conventional microwave synthesis processes of electrocatalysts include ultrasonication, stirring, pH adjustment, and microwave irradiation of the precursor mixture. Ethylene glycol (EG), which serves as a reductant and solvent was added during the ultrasonication or stirring stage. However, this step and pH adjustment resulted in unintended multi-stage gradual nucleation. In this study, the microwave reduction approach was used to induce rapid nucleation and high supersaturation in order to fabricate small-sized reduced graphene oxide-supported palladium (Pd/rGO) electrocatalysts via the delayed addition of EG, elimination of the pH adjustment step, addition of sodium carbonate (Na₂CO₃), prior microwave irradiation of the EG mixed with Na₂CO₃, and addition of room temperature precursor mixture. Besides its role as a second reducing agent, the addition of Na₂CO₃ was primarily intended to generate an alkaline condition, which is essential for the high-performance of electrocatalysts. Moreover, the microwave irradiation of the EG and Na₂CO₃ mixture generated highly reactive free radicals that facilitate rapid nucleation. Meanwhile, the room temperature precursor mixture increased supersaturation. Results showed improved electrochemically active surface area (78.97 m² g-1, 23.79% larger), MOR (434.49 mA mg-1, 37.96% higher) and stability.
The objective of this research is to examine the relationship between the color changes of phenol red and the growth of cancer cells, i.e., HeLa and DU145 cells, over a specific period of time. Normal mouse skin fibroblasts (L929 cells) were used as a reference. In this research, the color changes of phenol red due to the acidification of the cell culture medium from the growth of the cells over a period of nine hours showed potential colorimetric characteristics of cancer cells. The color changes of phenol red were observed using visible absorbance spectroscopy. The transformation of the absorbance spectra into coefficients of determination against the examined range of wavelengths created a distinctive spectral signature that signifies phenol red discoloration in cancer and normal cell culture lines.
Contaminant removal from water involves various technologies among which adsorption is considered to be simple, effective, economical, and sustainable. In recent years, nanocomposites prepared by combining clay minerals and polymers have emerged as a novel technology for cleaning contaminated water. Here, we provide an overview of various types of clay-polymer nanocomposites focusing on their synthesis processes, characteristics, and possible applications in water treatment. By evaluating various mechanisms and factors involved in the decontamination processes, we demonstrate that the nanocomposites can overcome the limitations of individual polymer and clay components such as poor specificity, pH dependence, particle size sensitivity, and low water wettability. We also discuss different regeneration and wastewater treatment options (e.g., membrane, coagulant, and barrier/columns) using clay-polymer nanocomposites. Finally, we provide an economic analysis of the use of these adsorbents and suggest future research directions.
Immobilisation of aptameric ligands on solid stationary supports for effective binding of target molecules requires understanding of the relationship between aptamer-polymer interactions and the conditions governing the mass transfer of the binding process. Herein, key process parameters affecting the molecular anchoring of a thrombin-binding aptamer (TBA) onto polymethacrylate monolith pore surface, and the binding characteristics of the resulting macroporous aptasensor were investigated. Molecular dynamics (MD) simulations of the TBA-thrombin binding indicated enhanced Guanine 4 (G4) structural stability of TBA upon interaction with thrombin in an ionic environment. Fourier-transform infrared spectroscopy and thermogravimetric analyses were used to characterise the available functional groups and thermo-molecular stability of the immobilised polymer generated with Schiff-base activation and immobilisation scheme. The initial degradation temperature of the polymethacrylate stationary support increased with each step of the Schiff-base process: poly(Ethylene glycol Dimethacrylate-co-Glycidyl methacrylate) or poly(EDMA-co-GMA) [196.0 °C (±1.8)]; poly(EDMA-co-GMA)-Ethylenediamine [235.9 °C (±6.1)]; poly(EDMA-co-GMA)-Ethylenediamine-Glutaraldehyde [255.4 °C (±2.7)]; and aptamer-modified monolith [273.7 °C (±2.5)]. These initial temperature increments reflected in the associated endothermic energies were determined with differential scanning calorimetry. The aptameric ligand density obtained after immobilisation was 480 pmol/μL. Increase in pH and ionic concentration affected the surface charge distribution and the binding characteristics of the aptamer-modified disk-monoliths, resulting in the optimum binding pH and ionic concentration of 8.0 and 5 mM Mg2+, respectively. These results are critical in understanding and setting parametric constraints indispensable to develop and enhance the performance of aptasensors.
A novel nanoparticle (NPs) iron oxyhydroxide modified with rice husk (RH + FeOOH) was synthesized with wet chemical method. Batch study was performed to investigate fluoride removal and adsorption capacity. The RH + FeOOH NPs were characterized by using Fourier transform infrared spectroscopy, X-ray powder diffraction, Brunauer-Emmett-Teller, scanning electron microscope with energy dispersion, transmission electron microscope, and particle size analyzer. By varying parameters, batch adsorption with adsorption capacity was performed such as contact time, stirring rate, adsorbent dosage, temperature, initial concentration, and pH. The BET surface area and the pore volume of the FeOOH and RH + FeOOH were found to be 157 m2 g-1, 195 m2 g-1 and 0.136 m2 g-1, 0.224 m2 g-1. Based on kinetic study, pseudo-second-order was followed by regression coefficient (R2) 0.99. Langmuir isotherm model showed the best adsorption capacity of 26 mg g-1. Moreover, the RH + FeOOH showed best affinity towards fluoride removal and may act as an excellent adsorbent for fluoride treatment from aqueous solution. Synthesis and Fluoride Adsorption Mechanism of Iron Oxyhydroxide Modified with rice husk.
The effect of physicochemical treatment on pectin yield, degree of esterification, along with the kinetics and thermodynamics characteristics was investigated in the present study. Several extraction parameters were observed to have impacted the yield and degree of esterification significantly, and the best extraction condition was as follows: agitation rate of 250 rpm, temperature of 70 °C, extraction time of 120 min, pH 2, and liquid to solid ratio of 10 v/w which has resulted in 28.20% of pectin yield, with DE (degree of esterification) of 57.00%. A theoretical model which describes the extractability, dissolution and degradation rate of pectin to predict the maximal yield at the maximal time was established to study the extraction kinetics of pectin from HPP. The kinetic analysis from Panchev's model shows the extraction rate was found highest at LSR 10 with ymax 30.85%. The calculated activation energy for pectin dissolution and degradation was found to be 4.532 kJ/mol and 28.054 kJ/mol, respectively. The thermodynamic study has suggested that the process was endothermic, spontaneous and reversible. These results suggest that the physical and chemical treatment applied could be an efficient technique for the extraction of pectin from Hylocereus polyrhizus peels.