A weak ion-exchange membrane (P-COOH) was synthesized by alkaline hydrolysis of a polyacrylonitrile nanofiber membrane prepared by electrospinning process. The P-COOH membrane was characterized for its physical properties and its application for purification of lysozyme from chicken egg white was investigated. The lysozyme adsorption efficiency of the P-COOH membrane operating in a stirred cell contactor (Millipore, Model 8010) was evaluated. The effects of key parameters such as the feed concentration, the rotating speed, the flow rate of feed and the operating pressure were studied. The results showed successful purification of lysozyme with a high recovery yield of 98% and a purification factor of 63 in a single step. The purification strategy was scaled-up to the higher feedstock loading volume of 32.7 and 70 mL using stirred cell contactors of Model 8050 and 8200, respectively. The scale-up processes achieved similar purification results, proving linear scalability of the purification technique adopted.
Novel diethanolamine-grafted high-methoxyl pectin (DGP)-arabic gum (AG) modified montmorillonite (MMT) composites were developed for intragastric ziprasidone HCl (ZIP) delivery by combining floating and mucoadhesion mechanisms. The ZIP-loaded clay-biopolymer matrices were accomplished by ionotropic gelation protocol utilizing zinc acetate in the presence or absence of covalent crosslinker, glutaraldehyde (GA). Various formulations exhibited excellent drug entrapment efficiency (DEE, %) and sustained drug release profiles, which were influenced by the polymer-blend (DGP:AG) ratios, reinforcing filler (MMT) existence and crosslinking procedure. The optimal composites (F-3) demonstrated DEE of 61% and Q8h of 52% with outstanding buoyancy, mucin adsorption ability and biodegradability. The release profile of F-3 was best fitted in the Korsmeyer-Peppas model with Fickian diffusion driven mechanism. The mucin adsorption to composites F-3 followed Freundlich isotherms. The molar mass between crosslinks of composites (F-3) calculated employing Flory-Rehner equation was increased with temperature. Moreover, the thermal, X-ray and infrared analyses confirmed a compatible environment of drug in the composites, except certain extent of transformation of the crystalline drug to its amorphous form. The SEM studies revealed the spherical morphology of the composites. Thus, the newly developed DGP-AG-MMT composites are appropriate for gastroretentive ZIP delivery over an extended period of time.
The filling of halloysite nanotubes with active compounds solubilized in aqueous solvent was investigated theoretically and experimentally. Based on Knudsen thermogravimetric data, we demonstrated the water confinement within the cavity of halloysite. This process is crucial to properly describe the driving mechanism of halloysite loading. In addition, Knudsen thermogravimetric experiments were conducted on kaolinite nanoplates as well as on halloysite nanotubes modified with an anionic surfactant (sodium dodecanoate) in order to explore the influence of both the nanoparticle morphology and the hydrophobic/hydrophilic character of the lumen on the confinement phenomenon. The analysis of the desorption isotherms allowed us to determine the water adsorption properties of the investigated nanoclays. The pore sizes of the nanotubes' lumen was determined by combining the vapor pressure of the confined water with the nanoparticles wettability, which was studied through contact angle measurements. The thermodynamic description of the water confinement inside the lumen was correlated to the influence of the vacuum pumping in the experimental loading of halloysite. Metoprolol tartrate, salicylic acid and malonic acid were selected as anionic guest molecules for the experimental filling of the positively charged halloysite lumen. According to the filling mechanism induced by the water confinement, the vacuum operation and the reduced pressure enhanced the loading of halloysite nanotubes for all the investigated bioactive compounds. This work represents a further and crucial step for the development of halloysite based nanocarriers being that the filling mechanism of the nanotube's cavity from aqueous dispersions was described according to the water confinement process.
Grafting of crosslinked chitosan with monomer, N-vinyl-2-pyrrolidone, has been carried out to investigate its adsorption capacity toward Orange G (OG) from aqueous solutions. The adsorption performance of modified chitosan (cts(x)-g-PNVP) was examined and compared with that of the unmodified chitosan. The effects of initial pH, contact time and initial dye concentration were investigated in a batch system. The experimental data were correlated with the Langmuir and Freundlich isotherm models. The maximum adsorption capacity of cts(x)-g-PNVP (63.7mgg-1) based on Langmuir equation was relatively higher than that of the unmodified chitosan (1.7mgg-1). The kinetic studies showed that the adsorption process was consistent with the pseudo-second order kinetic model. Interaction mechanisms between OG and cts(x)-g-PNVP were also proposed. The overall results suggested that the prepared cts(x)-g-PNVP stands a good candidate as adsorbent for removal of anionic dye from aqueous solutions.
In the present study, high-methoxyl pectin (HMP) was extracted from Hylocereus polyrhizus peel's using physico-chemical process. In addition, the hypolipidemic activity of HMP was investigated at different concentration and time corresponding to its adsorption ability. FTIR and contact angle analysis were used to determine the sorbent characterization. A high degree of esterification (63.8%) and the contact angle (95.5°) confirmed hydrophobic nature and resulting bad wetting of the HMP extract, respectively. The methoxyl content in the pectin acted as an affinity-precursor of the pectin towards cholesterol due to its increased hydrophobicity. The maximum equilibrium uptake capacity of cholesterol of 370.5mg/g (0.96mmol/g) was observed by HMP. The experimental data showed good fitting for Freundlich isotherm equation and followed pseudo-first-order kinetic model with a correlation coefficient (R2) of 0.89-0.97 due to physisorption mechanism. Intra-particle model confirmed that the cholesterol sorption rate by HMP was significantly influenced by external mass transfer (surface diffusion) and intra-particle diffusion (diffusion control). It was also revealed that the HMP extracted from Hylocereus polyrhizus peels possess a high affinity towards cholesterol, making it an ideal hypolipidemic agent.
In this study, two biomass-based adsorbents were used as new precursors for optimizing synthesis conditions of a cost-effective powdered activated carbon (PAC). The PAC removed dyes from an aqueous solution using carbonization and activation by KOH, NaOH, and H2SO4. The optimum synthesis, activation temperature, time and impregnation ratio, removal rate, and uptake capacity were determined. The optimum PAC was analyzed and characterized using Fourier-transform infrared spectroscopy (FTIR), x-ray diffraction (XRD), a field emission scanning electron microscope (FESEM), Zeta potential, and Raman spectroscopy. Morphological studies showed single-layered planes with highly porous surfaces, especially PAC activated by NaOH and H2SO4. The results showed that the experimental data were well-fitted with a pseudo-second-order model. Based on Langmuir isotherm, the maximum adsorption capacity for removing methylene blue (MB) was 769.23 mg g-1 and 458.43 mg g-1 for congo red (CR). Based on the isotherm models, more than one mechanism was involved in the adsorption process, monolayer for the anionic dye and multilayer for the cationic dye. Elovich and intraparticle diffusion kinetic models showed that rubber seed shells (RSS) has higher α values with a greater tendency to adsorb dyes compared to rubber seed (RS). A thermodynamic study showed that both dyes' adsorption process was spontaneous and exothermic due to the negative values of the enthalpy (ΔH) and Gibbs free energy (ΔG). The change in removal efficiency of adsorbent for regeneration study was observed in the seventh cycles, with a 3% decline in the CR and 2% decline in MB removal performance. This study showed that the presence of functional groups and active sites on the produced adsorbent (hydroxyl, alkoxy, carboxyl, and π - π) contributed to its considerable affinity for adsorption in dye removal. Therefore, the optimum PAC can serve as efficient and cost-effective adsorbents to remove dyes from industrial wastewater.
Activated carbons have been reported to be useful for adsorptive removal of the volatile anaesthetic sevoflurane from a vapour stream. The surface functionalities on activated carbons could be modified through aqueous oxidation using oxidising solutions to enhance the sevoflurane adsorption. In this study, an attempt to oxidise the surface of a commercial activated carbon to improve its adsorption capacity for sevoflurane was conducted using 6 mol/L nitric acid, 2 mol/L ammonium persulfate, and 30 wt per cent (wt%) of hydrogen peroxide (H2O2). The adsorption tests at fixed conditions (bed depth: 10 cm, inlet concentration: 528 mg/L, and flow rate: 3 L/min) revealed that H2O2 oxidation gave desirable sevoflurane adsorption (0.510 ± 0.005 mg/m2). A parametric study was conducted with H2O2 to investigate the effect of oxidation conditions to the changes in surface oxygen functionalities by varying the concentration, oxidation duration, and temperature, and the Conductor-like Screening Model for Real Solvents (COSMO-RS) was applied to predict the interactions between oxygen functionalities and sevoflurane. The H2O2 oxidation incorporated varying degrees of both surface oxygen functionalities with hydrogen bond (HB) acceptor and HB donor characters under the studied conditions. Oxidised samples with enriched oxygen functionalities with HB acceptor character and fewer HB donor character exhibited better adsorption capacity for sevoflurane. The presence of a high amount of oxygen functional groups with HB donor character adversely affected the sevoflurane adsorption despite the enrichment of oxygen functional groups with HB acceptor character that have a higher tendency to adsorb sevoflurane.
Congo red (CR) is an anionic azo dye widely used in many industries including pharmaceutical, textile, food and paint industries. The disposal of huge amount of CR into the various streams of water has posed a great threat to both human and aquatic life. Therefore, it has become an important aspect of industries to remove CR from different water sources. Molecular imprinting technology is a very slective method to remove various target pollutant from environment. In this study a precipitation polymerization was employed for the effective and selective removal of CR from contaminated aqueous media. A series of congo red molecularly imprinted polymers (CR-MIPs) of uniform size and shape was developed by changing the mole ratio of the components. The optimum ratio (0.1:4: 20, template, functional monomer and cross-linking monomer respectively) for CR1-MIP from synthesized polymers was able to rebind about 99.63% of CR at the optimum conditions of adsorption parameters (contact time 210 min, polymer dosage 0.5 g, concentration 20 ppm and pH 7). The synthesized polymers were characterized by various techniques such as Fourier Infra-red spectroscopy (FTIR), scanning electron microscopy (SEM), Thermogravimetric analysis (TGA), energy-dispersive X-ray spectroscopy (EDX), and Brumauer-Emmett-Teller (BET). The polymer particles have successfully removed CR from different aqueous media with an efficiency of about ~ 90%.
A unique nanocomposite was fabricated using negatively charged manganese dioxide nanoparticles, poly (3,4-ethylenedioxythiophene) and reduced graphene oxide (MnO2/PEDOT/rGO). The nanocomposite was deposited on a glassy carbon electrode (GCE) functionalized with amino groups. The modified GCE was used to electrochemically detect dopamine (DA). The surface morphology, charge effect and electrochemical behaviours of the modified GCE were characterized by scanning electron microscopy, energy dispersive X-ray analysis (EDX), cyclic voltammetry and electrochemical impedance spectroscopy, respectively. The MnO2/PEDOT/rGO/GCE exhibited excellent performance towards DA sensing with a linear range between 0.05 and 135 µM with a lowest detection limit of 30 nM (S/N = 3). Selectivity towards DA was high in the presence of high concentrations of the typical interferences ascorbic acid and uric acid. The stability and reproducibility of the electrode were good. The sensor accurately determined DA in human serum. The synergic effect of the multiple components of the fabricated nanocomposite were critical to the good DA sensing performance. rGO provided a conductive backbone, PEDOT directed the uniform growth of MnO2 and adsorbed DA via pi-pi and electrostatic interaction, while the negatively charged MnO2 provided adsorption and catalytic sites for protonated DA. This work produced a promising biosensor that sensitively and selectively detected DA.
This study aimed to enhance the crystallizability of bio-based succinic acid for its efficient recovery while maintaining the end product at the highest purity. Immobilization of Actinobacillus succinogenes was initially evaluated based on three different carriers: volcanic glass, clay pebbles, and silica particles. The adsorption capacity of metabolites with a low concentration (10 g/L) and a high concentration (40 g/L) was investigated. It was demonstrated that clay pebbles adsorbed the least succinic acid (
This study examined the potential of untreated and alkali-pretreated sugarcane bagasse (SCB) in cellulase, reducing sugar (RS) and fungal biomass production via solid state fermentation (SSF) using Pycnoporus sanguineus. The impact of the composition, structure and cellulase adsorption ability of SCB on the production of cellulase, RS and fungal biomass was investigated. From the morphological and compositional analyses, untreated SCB has relatively more structural changes with a higher percentage of depolymerisation on the cellulose, hemicellulose and lignin content compared to alkali-pretreated SCB. Thus, untreated SCB favoured the production of cellulase and fungal biomass whereas alkali-pretreated SCB yielded a higher amount of RS. The composition and morphology of untreated SCB did not encourage RS production and this suggested that RS produced during SSF might be consumed in a faster rate by the more abundantly grown fungus. Besides that, alkali-pretreated SCB with higher cellulase adsorption ability could have adsorbed the cellulase produced and resulted in a lower cellulase titre. In short, the production of specific bioproducts via SSF is dependent on the structure and composition of the substrate applied.
In view of several disadvantages as well as adverse effects associated with the use of chemical processes for producing esters, alternative techniques such as the utilization of enzymes on multi-walled carbon nanotubes (MWCNTs), have been suggested. In this study, the oxidative MWCNTs prepared using a mixture of HNO3 and H2SO4 (1:3 v/v) were used as a supportive material for the immobilization of Candida rugosa lipase (CRL) through physical adsorption process. The resulting CRL-MWCNTs biocatalysts were utilized for synthesizing geranyl propionate, an important ester for flavoring agent as well as in fragrances. Enzymatic esterification of geraniol with propionic acid was carried out using heptane as a solvent and the efficiency of CRL-MWCNTs as a biocatalyst was compared with the free CRL, considering the incubation time, temperature, molar ratio of acid:alcohol, presence of desiccant as well as its reusability. It was found that the CRL-MWCNTs resulted in a 2-fold improvement in the percentage of conversion of geranyl propionate when compared with the free CRL, demonstrating the highest yield of geranyl propionate at 6h at 55°C, molar ratio acid: alcohol of 1:5 and with the presence of 1.0g desiccant. It was evident that the CRL-MWCNTs biocatalyst could be reused for up to 6 times before a 50% reduction in catalytic efficiency was observed. Hence, it appears that the facile physical adsorption of CRL onto F-MWCNTs has improved the activity and stability of CRL as well as served as an alternative method for the synthesis of geranyl propionate.
Clean, safe and readily available water is very crucial in everyday life, especially for health, hygiene, and the productivity of the community. Unfortunately, increase in contaminants in water supplies from human activities and industrialization is very worrying. Conventional wastewater treatment includes the usage of alum that will affect health with prolonged consumption. This research was carried out to focus on the development of wastewater treatment system using adsorbent from Moringa oleifera seeds. Adsorbent was successfully synthesized from the seeds of Moringa oleifera. Characterization of the sample was made using X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscope (SEM), while the effectiveness of water treatment was analyzed using Turbidity Meter. Then, all samples were tested against kaolin wastewater. XRD results showed that all the adsorbent samples were amorphous in nature. FTIR results indicated that there were hydroxyl group and carboxylic group in the sample representing numerous oxygen-riddled functional groups on the surface. From SEM results, it was clearly shown that the pore structure and size of Moringa oleifera affected the capability of adsorption where the smaller the size, the more effective the sample. Turbidity test showed that the sample that worked best for wastewater treatment was adsorbent from Moringa oleifera seeds in size of 125µm that was heated for 4 hours with 93.76% turbidity removal. Therefore, this study proved that the adsorbent from Moringa oleifera seeds is very suitable for high turbidity wastewater treatment. Further studies investigating the combination of conventional activated carbon with adsorbent from Moringa oleifera seeds should be conducted before these samples are made available for further use so that we can compare which sample works best for wastewater treatment.
Batik industryiswell known intheEast Coast of Malaysia, particularly in Terengganu and Kelantan. This industry consumes a lot of waterforthe batik making processwhich contributes tohigh dischargeof wastewater containingexcess dye pollutants. Hence,in this study, ananionic clayofnickel/aluminium-layered double hydroxide (NiAL) was investigatedas a potential adsorbent for the removal of anionic dyeof Eriochrome Black T (EBT). The NiAL was synthesized via self-assemblymethod and characterization of NiALwas carried outusing powder X-ray diffraction (PXRD) and Fourier transform infrared spectrophotometer (FTIR). The composition and morphology of NiAL was further analyzed using carbon, hydrogen, nitrogen, sulphur elemental analyzer (CHNS), thermogravimetric analyzer (TGA) and scanning electron microscope (SEM).The potential of NiAL as an adsorbent for the removal ofEBT in aqueous solution was tested at different dosages of NiAL. Theadsorptionabilitywasanalyzedby using two common adsorption isotherms, which were Langmuir and Freundlich models. The adsorption of EBT onto NiAL was governedby Freundlich isotherm model indicating that the adsorption occurs in heterogeneous system.
Cylinder-shaped NaY zeolite was used as an adsorbent for eradicating both heavy metal ions (Cu2+, Zn2+, Ni2+, and Co2+) and proteins from the waste streams. As a pseudo-metal ion affinity adsorbent, NaY zeolite was used in the capture of heavy metal ions in the first stage. The amount (molar basis) of metal ions adsorbed onto NaY zeolite decreased in the order of Cu2+ > Zn2+ > Co2+ > Ni2+. Bovine serum albumin (BSA) was utilized as a model of proteins used in the waste adsorption process by NaY zeolite. The adsorption capacities of NaY zeolite and Cu/NaY zeolite for BSA were 14.90 mg BSA/g zeolite and 84.61 mg BSA/g zeolite, respectively. Moreover, Cu/NaY zeolite was highly stable in the solutions made of 2 M NaCl, 500 mM imidazole or 125 mM EDTA solutions. These conditions indicated that the minimal probability of secondary contamination caused by metal ions and soluble proteins in the waste stream. This study demonstrates the potential of Cu/NaY zeolite complex as an efficient pseudo-metal chelate adsorbent that could remove metal ions and water-soluble proteins from wastewater concurrently.
Toxic metals in the industrial wastewaters have been liable for drastic pollution hence a powerful and economical treatment technology is needed for water purification. For this reason, some pure cellulosic materials were derived from waste fiber to obtain an economical adsorbent for wastewater treatment. Conversion of cellulose into grafting materials such as poly(methyl acrylate)-grafted cellulose was performed by free radical grafting process. Consequently, poly(hydroxamic acid) ligand was produced from the grafted cellulose. The intermediate products and poly(hydroxamic acid) ligand were analyzed by FT-IR, FE-SEM, TEM, EDX, and XPS spectroscopy. The adsorption capacity (qe) of some toxic metals ions by the polymer ligand was found to be excellent, e.g., copper capacity (qe) was 346.7 mg·g-1 at pH 6. On the other hand, several metal ions such as cobalt chromium and nickel also demonstrated noteworthy sorption capacity at pH 6. The adsorption mechanism obeyed the pseudo second-order rate kinetic model due to the satisfactory correlated experimental sorption values (qe). Langmuir model isotherm study showed the significant correlation coefficient with all metal ions (R2 > 0.99), indicating that the single or monolayer adsorption was the dominant mode on the surface of the adsorbent. This polymer ligand showed good properties on reusability. The result shows that the adsorbent may be recycled for 6 cycles without any dropping of starting sorption capabilities. This polymeric ligand showed outstanding toxic metals removal magnitude, up to 90-99% of toxic metal ions can be removed from industrial wastewater.
A new sol-gel hybrid methyltrimethoxysilane-chloropropyltriethoxysilane was prepared as sorbent for solid-phase extraction. The extraction efficiency of the prepared sol-gel hybrid methyltrimethoxysilane-chloropropyltriethoxysilane was assessed by using three selected organophosphorus pesticides, namely, chlorpyrifos, profenofos, and malathion. Gas chromatography-mass spectrometry was used for detection of organophosphorus pesticides. Several vital parameters were optimized to identify the best extraction conditions. Under the optimum extraction conditions, solid-phase extraction-methyltrimethoxysilane-chloropropyltriethoxysilane method showed good linearity range (0.05-1 μg/mL) with coefficient of determination more than 0.995. The limits of detection obtained were in the range of 0.01-0.07 μg/mL and limits of quantification ranging from 0.03 to 0.21 μg/mL. The limits of detection obtained for the developed method were 2.3-6.5× lower than the limits of detection of commercial octadecyl silica sorbent. Real samples analysis was carried out by applying the developed method on red apple and purple grape samples. The developed method exhibited good recoveries (88.33-120.7%) with low relative standard deviations ranging from 1.6 to 3.3% compared to commercial octadecyl silica sorbent, which showed acceptable recoveries (70.3-100.2%) and relative standard deviations (6.3-8.8%). The solid-phase extraction-methyltrimethoxysilane-chloropropyltriethoxysilane method is presented as an alternative extraction method for determination of organophosphorus pesticides.
This work investigated the removal of boron from wastewater and its recovery by electrocoagulation and hydrothermal mineralization methods respectively. The experimental design was developed using Box-Behnken Model. An initial study was performed based on four preselected variables (pH, current density, concentration and time) using synthetic wastewater. Response surface methodology (RSM) was used to evaluate the effect of process variables and their interaction on boron removal. The optimum conditions were obtained as pH 6.3, current density 17.4 mA/cm(2), and time 89 min. At these applied optimum conditions, 99.7% boron removal from an initial concentration of 10.4 mg/L was achieved. The process was effectively optimized by RSM with a desirability value of 1.0. The results showed that boron removal efficiency enhanced with increase in current density and treatment time. Removal efficiency also increased when pH was increased from 4 to 7 and subsequently decreased at pH 10. Adsorption kinetics study revealed that the reaction followed pseudo second order kinetic model; evidenced by high correlation and goodness of fit. Thermodynamics study showed that mechanism of boron adsorption was chemisorption and the reaction was endothermic in nature. Furthermore, the adsorption process was spontaneous as indicated by negative values of the adsorption free energy. Treatment of real produced water using electrocoagulation resulted in 98% boron removal. The hydrothermal mineralization study showed that borate minerals (Inyoite, Takadaite and Nifontovite) can be recovered as recyclable precipitate from electrocoagulation flocs of produced water.
The application of simultaneous adsorption and biodegradation processes in the same reactor is known to be effective in the removal of both biodegradable and non-biodegradable contaminants in various kinds of wastewater. The objective of this study is to evaluate the efficacy of the two processes under sequencing batch reactor (SBR) operation in treating copper and cadmium-containing synthetic wastewater with powdered activated carbon (PAC) as the adsorbent. The SBR systems were operated with FILL, REACT, SETTLE, DRAW and IDLE periods in the ratio of 0.5: 3.5: 1.0: 0.75 :0.25 for a cycle time of 6 h. In the presence of 10 mg/L Cu(II) and 30 mg/L Cd(II), respectively, the average COD removal efficiencies were above 85% with the PAC dosage in the influent solution at 143 mg/L compared to around 60% without PAC addition. Copper(II) was found to exert a more pronounced inhibitory effect on the bioactivity of the microorganisms compared to Cd(II). It was observed that the combined presence of Cu(II) and Cd(II) did not exert synergistic effects on the microorganisms. Kinetic study conducted for the REACT period showed that the addition of PAC had minimized the inhibitory effect of the heavy metals on the bioactivity of microorganisms.
Recently, deep eutectic solvents (DESs) have shown their new and interesting ability for chemistry through their involvement in variety of applications. This study introduces carbon nanotubes (CNTs) functionalized with DES as a novel adsorbent for Hg(2+) from water. Allyl triphenyl phosphonium bromide (ATPB) was combined with glycerol as the hydrogen bond donor (HBD) to form DES, which can act as a novel CNTs functionalization agent. The novel adsorbent was characterized using Raman, FTIR, XRD, FESEM, EDX, BET surface area, TGA, TEM and Zeta potential. Response surface methodology was used to optimize the removal conditions for Hg(2+). The optimum removal conditions were found to be pH 5.5, contact time 28 min, and an adsorbent dosage of 5 mg. Freundlich isotherm model described the adsorption isotherm of the novel adsorbent, and the maximum adsorption capacity obtained from the experimental data was 186.97 mg g(-1). Pseudo-second order kinetics describes the adsorption rate order.