As a remedy for environmental pollution, a versatile synthetic approach has been developed to prepare polyvinyl alcohol (PVA)/nitrogen-doped carbon dots (CDs) composite film (PVA-CDs) for removal of toxic cadmium ions. The CDs were first synthesized using carboxymethylcellulose (CMC) of oil palms empty fruit bunch wastes with the addition of polyethyleneimine (PEI) and then the CDs were embedded with PVA. The PVA-CDs film possess synergistic functionalities through increasing the content of hydrogen bonds for chemisorption compared to the pure CDs. Optical analysis of PVA-CDs film was performed by ultraviolet-visible and fluorescence spectroscopy. Compared to the pure CDs, the solid-state PVA-CDs displayed a bright blue color with a quantum yield (QY) of 47%; they possess excitation-independent emission and a higher Cd2+ removal efficiency of 91.1%. The equilibrium state was achieved within 10 min. It was found that adsorption data fit well with the pseudo-second-order kinetic and Langmuir isotherm models. The maximum adsorption uptake was 113.6 mg g-1 at an optimal pH of 7. Desorption experiments showhe that adsorbent can be reused fruitfully for five adsorption-desorption cycles using 0.1 HCl elution. The film was successfully applied to real water samples with a removal efficiency of 95.34% and 90.9% for tap and drinking water, respectively. The fabricated membrane is biodegradable and its preparation follows an ecofriendly green route.
In this study, a potentiometric sensor composed of palm shell activated carbon modified with trioctylmethylammonium thiosalicylate (TOMATS) was used for the potentiometric determination of mercury ions in water samples. The proposed potentiometric sensor has good operating characteristics towards Hg (II), including a relatively high selectivity; a Nernstian response to Hg (II) ions in a concentration range of 1.0 × 10(-9) to 1.0 × 10(-2) M, with a detection limit of 1 × 10(-10) M and a slope of 44.08 ± 1.0 mV/decade; and a fast response time (~5 s). No significant changes in electrode potential were observed when the pH was varied over the range of 3-9. Additionally, the proposed electrode was characterized by good selectivity towards Hg (II) and no significant interferences from other cationic or anionic species.
Solid polymer blend electrolyte membranes (SPBEM) composed of chitosan and dextran with the incorporation of various amounts of lithium perchlorate (LiClO4) were synthesized. The complexation of the polymer blend electrolytes with the salt was examined using FTIR spectroscopy and X-ray diffraction (XRD). The morphology of the SPBEs was also investigated using field emission scanning electron microscopy (FESEM). The ion transport behavior of the membrane films was measured using impedance spectroscopy. The membrane with highest LiClO4 content was found to exhibit the highest conductivity of 5.16 × 10-3 S/cm. Ionic (ti) and electronic (te) transference numbers for the highest conducting electrolyte were found to be 0.98 and 0.02, respectively. Electrochemical stability was estimated from linear sweep voltammetry and found to be up to ~2.3V for the Li+ ion conducting electrolyte. The only existence of electrical double charging at the surface of electrodes was evidenced from the absence of peaks in cyclic voltammetry (CV) plot. The discharge slope was observed to be almost linear, confirming the capacitive behavior of the EDLC. The performance of synthesized EDLC was studied using CV and charge-discharge techniques. The highest specific capacitance was achieved to be 8.7 F·g-1 at 20th cycle. The efficiency (η) was observed to be at 92.8% and remained constant at 92.0% up to 100 cycles. The EDLC was considered to have a reasonable electrode-electrolyte contact, in which η exceeds 90.0%. It was determined that equivalent series resistance (Resr) is quite low and varies from 150 to 180 Ω over the 100 cycles. Energy density (Ed) was found to be 1.21 Wh·kg-1 at the 1st cycle and then remained stable at 0.86 Wh·kg-1 up to 100 cycles. The interesting observation is that the value of Pd increases back to 685 W·kg-1 up to 80 cycles.
Carboxymethyl sago starch-acid hydrogel was prepared via irradiation technique to remove divalent metal ions (Pb, Cu and Cd) from their aqueous solution. The hydrogel was characterized by using Fourier Transform Infrared (FT-IR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The removal of these metal ions was analyzed by using inductively coupled plasma-optic emission spectra (ICP-OES) to study the amount of metal uptake by the hydrogel. Parameters of study include effect of pH, amount of sample, contact time, initial concentration of metal solution and reaction temperature. FTIR spectroscopy shows the CMSS hydrogel absorption peaks at 1741cm(-1), 1605cm(-1) and 1430cm(-1) which indicates the substitution of carboxymethyl group of modified sago starch. The degradation temperature of CMSS hydrogel is higher compared to CMSS due to the crosslinking by electron beam radiation and formed a porous hydrogel. From the data obtained, about 93.5%, 88.4% and 85.5% of Pb, Cu and Cd ions has been respectively removed from their solution under optimum condition.
Development of new materials for different applications especially as bio-composites has received great attention. This study concentrates on development of a biopolymer based on chitosan (CT) and halloysite nanotubes (HNT) and evaluates the copper removal intake as a potential application of this bio-composite. In this study, CT/HNT beads were prepared by ultrasonic-assisted extrusion-dripping method for the first time. Two sources of HNTs (i.e. Dragonite and Matauri Bay) were added into a chitosan solution (2wt.%) at various loading fractions (25, 50, 75wt.%). The effect of ultrasound as a mixing device was also studied by varying the amplitude at constant frequency of 25%, 50% and 75%. Characteristics and physical properties of the prepared CT/HNT beads were also analyzed by SEM, FTIR, TGA and BET the results show that introducing HNT to chitosan increases the adsorption capacity toward copper ions; however HNT loading fraction above 50wt.% resulted in a decrease in adsorption capacity attributed to limited accessibility of the amino groups. The adsorption capacity of the CT/HNT beads prepared from Dragonite source had a larger adsorption capacity of 14.2mg/g as compared to that of Matauri Bay, 10.55mg/g. It was observed that the adsorption capacity of the beads toward copper ions decreased when the loading fraction of HNT is increased at constant ultrasound amplitude. The result of this study helps to understand the links between the characteristics and adsorption abilities of CT/HNT beads.
Staphylococcus aureus is a Gram-positive pathogen that causes potentially life-threatening nosocomial- and community-acquired infections, such as osteomyelitis and endocarditis. Staphylococcus aureus has the ability to form multicellular, surface-adherent communities called biofilms, which enables it to survive in various sources of stress, including antibiotics, nutrient limitations, heat shock, and immune responses. Biofilm-forming capacity is now recognized as an important virulence determinant in the development of staphylococcal device-related infections. In light of the projected increase in the numbers of elderly patients who will require semi-permanent indwelling medical devices such as artificial knees and hips, we can anticipate an expanded need for new agents and treatment options to manage biofilm-associated infections in an expanding at-risk population. With better understanding of staphylococcal biofilm formation and growth, novel strategies that target biofilm-associated infections caused by S. aureus have recently been described and seem promising as future anti-biofilm therapies.
Purification of lipase produced by L. mesenteroides subsp. mesenteroides ATCC 8293 was conducted for the first time using a novel aqueous two-phase system (ATPS) composed of Triton X-100 and maltitol. The partitioning of lipase was optimized according to several parameters including pH, temperature, and crude load. Results showed that lipase preferentially migrated to the Triton X-100 rich phase and optimum lipase partitioning was achieved in ATPS at TLL of 46.4% and crude load of 20% at 30 °C and pH 8, resulting in high lipase purification factor of 17.28 and yield of 94.7%. The purified lipase showed a prominent band on SDS-PAGE with an estimated molecular weight of 50 kDa. The lipase was stable at the temperature range of 30⁻60 °C and pH range of 6⁻11, however, it revealed its optimum activity at the temperature of 37 °C and pH 8. Moreover, lipase exhibited enhanced activity in the presence of non-ionic surfactants with increased activity up to 40%. Furthermore, results exhibited that metals ions such as Na⁺, Mg2+, K⁺ and Ca2+ stimulated lipase activity. This study demonstrated that this novel system could be potentially used as an alternative to traditional ATPS for the purification and recovery of enzymes since the purified lipase still possesses good process characteristics after undergoing the purification process.
The solubility limitations of phenolic acids in many lipidic environments are now greatly improved by their enzymatic esterification in ionic liquids (ILs). Herein, four different ILs were tested for the esterification of dihydrocaffeic acid with hexanol and the best IL was selected for the synthesis of four other n-alkyl esters with different chain-lengths. The effect of alkyl chain length on the anti-oxidative properties of the resulted purified esters was investigated using β-carotene bleaching (BCB) and free radical scavenging method DPPH and compared with butylated hydroxytoluene (BHT) as reference compound. All four esters (methyl, hexyl, dodecyl and octadecyl dihydrocaffeates) exhibited relatively strong radical scavenging abilities. The scavenging activity of the test compounds was in the following order: methyl ester>hexyl ester⩾dodecyl ester>octadecyl ester>BHT while the order for the BCB anti-oxidative activity was; BHT>octadecyl ester>dodecyl ester>hexyl ester>methyl ester.
In this study, effect of degree of deacetylation on property and adsorption capacity of chitosan/polyvinyl Alcohol electrospun membrane has been investigated. Resulting nanofibers were characterized by FESEM, FTIR, XRD, TGA, tensile testing, weight loss test and adsorption test. FESEM result shows, finer nanofiber was fabricated from 42h hydrolyzed chitosan and PVA blend solution. FTIR and XRD result showed a strong interaction between chitosan and polyvinyl alcohol. Higher tensile strength was observed for the nanofiber having 42h hydrolyzed chitosan. Blend solution of chitosan/PVA having low DD chitosan had higher viscosity. The nanofibrous membrane was stable in distilled water, acidic and basic medium. The isotherm study shows that the adsorption capacity (qm) of nanofiber containing higher DD chitosan was higher for Cr(VI). In contrary, the membrane containing chitosan with lower DD showed the higher adsorption capacity for Fe(III) and methyl orange. Moreover, the effect of DD on removal percentage of adsorbate was dependent on the initial concentration of the adsorbate.
Graphene is a new carbon-based material that is of interest in separation science. Graphene has extraordinary properties including nano size, high surface area, thermal and chemical stability, and excellent adsorption affinity to pollutants. Its adsorption mechanisms are through non-covalent interactions (π-π stacking, electrostatic interactions, and H-bonding) for organic compounds and covalent interactions for metal ions. These properties have led to graphene-based material becoming a desirable adsorbent in a popular sample preparation technique known as solid phase extraction (SPE). Numerous studies have been published on graphene applications in recent years, but few review papers have focused on its applications in analytical chemistry. This article focuses on recent preconcentration of trace elements, organic compounds, and biological species using SPE-based graphene, graphene oxide, and their modified forms. Solid phase microextraction and micro SPE (µSPE) methods based on graphene are discussed.
Poly(ethyl hydrazide)-grafted oil palm empty fruit bunch fibre (peh-g-opefb) was successfully prepared by heating poly(methyl acrylate)-grafted opefb (pma-g-opefb) at 60 °C for 4 h with a solution of hydrazine hydrate (15% v/v) in ethanol. The Fourier transform infrared spectrum of the product shows a secondary amine peak at 3267 cm⁻¹, with amide carbonyl peaks at 1729 cm⁻¹ and 1643 cm⁻¹. The chelating ability of peh-g-opefb was tested with copper ion in aqueous solution. A batch adsorption study revealed that maximum adsorption of copper ion was achieved at pH 5. An isotherm study showed the adsorption follows a Langmuir model, with a maximum adsorption capacity of 43.48 mg g-1 at 25 °C. A kinetic study showed that the adsorption of copper ion rapidly reaches equilibrium and follows a pseudo-second-order kinetic model, with a constant rate of 7.02 × 10⁻⁴ g mg⁻¹ min⁻¹ at 25 °C. The Gibbs free energy, ∆G⁰, value is negative, indicating a spontaneous sorption process. Entropy, ∆S⁰, gives a positive value, indicating that the system is becoming increasingly disordered after the adsorption of copper ion. A positive enthalpy value, ∆H⁰, shows that the endothermic process takes place during the adsorption and is more favourable at high temperatures.
The main objectives of this study are to synthesize a new solid-supported ionic liquid (SSIL) that has a covalent bond between the solid support, i.e., activated silica gel, with thiosalicylate-based ionic liquid and to evaluate the performance of this new SSIL as an extractant, labelled as Si-TS-SSIL, and to remove Pb(II) ions from an aqueous solution. In this study, 1-methyl-3-(3-trimethoxysilylpropyl) imidazolium thiosalicylate ([MTMSPI][TS]) ionic liquid was synthesized and the formation of [MTMSPI][TS] was confirmed through structural analysis using NMR, FTIR, IC, TGA, and Karl Fischer Titration. The [MTMSPI][TS] ionic liquid was then chemically immobilized on activated silica gel to produce a new thiosalicylate-based solid-supported ionic liquid (Si-TS-SSIL). The formation of these covalent bonds on Si-TS-SSIL was confirmed by solid-state NMR analysis. Meanwhile, BET analysis was performed to study the surface area of the activated silica gel and the prepared Si-TS-SSIL (before and after washing with solvent) with the purpose to show that all physically immobilized [MTMSPI][TS] has been washed off from Si-TS-SSIL, leaving only chemically immobilized [MTMSPI][TS] on Si-TS-SSIL before proceeding with removal study. The removal study of Pb(II) ions from an aqueous solution was carried out using Si-TS-SSIL as an extractant, whereby the amount of Pb(II) ions removed was determined by AAS. In this removal study, the experiments were carried out at a fixed agitation speed (400 rpm) and fixed amount of Si-TS-SSIL (0.25 g), with different contact times ranging from 2 to 250 min at room temperature. The maximum removal capacity was found to be 8.37 mg/g. The kinetics study was well fitted with the pseudo-second order model. Meanwhile, for the isotherm study, the removal process of Pb(II) ions was well described by the Freundlich isotherm model, as this model exhibited a higher correlation coefficient (R2), i.e., 0.99, as compared to the Langmuir isotherm model.
The Cr(III) sorption experiments onto Kappaphycus alvarezii waste biomass were conducted at different pH values (2-6) under the conditions of initial metal concentration of 10-50 mg/L and the chemical compositions of Cr-Cu and Cr-Cd. The Cr(III) sorption capacities were slightly dependent on pH, and the maximum sorption capacity was 0.86 mg/g at pH 3. The sorption capacities increased with increase in the initial metal concentration, whereas it was suppressed by the presence of Cu(II) and Cd(III) in the solution. The Cr(III) sorption equilibrium was evaluated using Langmuir, Freundlich and BET isotherms. The sorption mechanisms were characterised using scanning electron microscopy and Fourier transform infrared spectroscopy. The main mechanisms were ion exchange coupled with a complexation mechanism. Kappaphycus alvarezii waste biomass represents a potential for Cr(III) ion removal from aqueous solution.
A new dibenzotetraaza[14]annulene bearing two 3,3-dimethylindolenine fragments at the meso positions (LH(2)), has been synthesized through a nontemplate method. X-ray crystallography shows that the whole molecule is planar. The basicity of the indolenine ring permits the macrocycle to be protonated external to the core and form LH(4)(2+)·2Cl(-). Yet another structural modification having strong C-H···π interactions was found in the chloroform solvate of LH(2). The latter two modifications are accompanied by a degree of nonplanar distortion. The antiaromatic core of the macrocycle can accommodate a number of metal ions, Mn(III), Fe(III), Co(II), Ni(II) and Cu(II), to form complexes of [Mn(L)Br], [Mn(L)Cl], [Fe(LH(2))Cl(2)](+)·Cl(-), [Co(L)], [Ni(L)], and [Cu(L)]. In addition, the reaction of LH(2) with the larger Pd(II) ion leads to the formation of [Pd(2)(LH(2))(2)(OAc)(4)] wherein the macrocycle acts as a semiflexible ditopic ligand to coordinate pairs of metal ions via its indolenine N atoms into dinuclear metallocycles. The compounds LH(2), [Co(L)], and [Ni(L)] are isostructural and feature close π-stacking as well as linear chain arrangements in the case of the metal complexes. Variable temperature magnetic susceptibility measurements showed thermally induced paramagnetism in [Ni(L)].
In this study, poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) dual-layer membranes filled with 0-3 wt% cellulose nanowhisker (CNWs) were fabricated with aim to remove metal ions from wastewater. An integrated method was employed in the membrane fabrication process by combining water vapor-induced and crystallization-induced phase inversions. The membrane thickness was measured in between 11 and 13 μm, which did not pose significant flux deviation during filtration process. The 3% CNW filled membrane showed prominent and well-laminated two layers structure. Meanwhile, the increase in CNWs from 0 to 3% loadings could improve the membrane porosity (43-74%) but reducing pore size (2.45-0.54 μm). The heat resistance of neat membrane enhanced by 1% CNW but decreased with loadings of 2-3% CNWs due to flaming behavior of sulphated nanocellulose. Membrane with 3% CNW displayed the tensile strength (23.5 MPa), elongation at break (7.1%), and Young's modulus (0.75 GPa) as compared to other samples. For wastewater filtration performance, the continuous operation test showed that 3% CNW filled membrane exhibited the highest removal efficiency for both cobalt and nickel metal ions reaching to 83% and 84%, respectively. We concluded that CNWs filled dual-layer membranes have potential for future development in the removal of heavy metal ions from wastewater streams.
This paper presents the adsorption capacity of a biosorbent derived from the inner part of durian (Durio zibethinus) rinds, which are a low-cost and abundant agro-waste material. The durian rind sorbent has been successfully utilized to remove lanthanum (La) and yttrium (Y) ions from their binary aqueous solution. The effects of several adsorption parameters including contact time, pH, concentrations of La and Y, and temperature on the removal of La and Y ions were investigated. The adsorption isotherm and kinetics of the metal ions were also evaluated in detail. Both La and Y ions were efficiently adsorbed by the biosorbent with optimum adsorption capacity as high as 71 mg La and 35 mg Y per gram biosorbent, respectively. The simultaneous adsorption of La and Y ions follows Langmuir isotherm model, due to the favorable chelation and strong chemical interactions between the functional groups on the surface of the biosorbent and the metal ions. The addition of oxygen content after adsorption offers an interpretation that the rare-earth metal ions are chelated and incorporated most probably in the form of metal oxides. With such high adsorption capacity of La and Y ions, the durian rind sorbent could potentially be used to treat contaminated wastewater containing La and Y metal ions, as well as for separating and extracting rare-earth metal ions from crude minerals.
An organometallic/silica nanocomposite of a 1D cylindrical assembly of a trinuclear gold(I)-pyrazolate complex ([Au(3)Pz(3)]) that was confined inside the nanoscopic channels of hexagonal mesoporous silica ([Au(3)Pz(3)]/silica(hex)), emitted red light with a luminescence center at 693 nm upon photoexcitation at 276 nm owing to a Au(I)-Au(I) metallophilic interaction. When a film of [Au(3)Pz(3)]/silica(hex) was dipped into a solution of Ag(+) in tetrahydrofuran (THF), the resulting nanocomposite material (Ag@[Au(3)Pz(3)]/silica(hex)) emitted green light with a new luminescence center at 486 nm, which was characteristic of a Au(I)-Ag(I) heterometallic interaction. Changes in the emission/excitation and XPS spectra of Ag@[Au(3)Pz(3)]/silica(hex) revealed that Ag(+) ions permeated into the congested nanochannels of [Au(3)Pz(3)]/silica(hex), which were filled with the cylindrical assembly of [Au(3)Pz(3)].
The objective of this study is to extract and characterize lignin from oil palm biomass (OPB) by dissolution in 1-butyl-3-methylimidazolium chloride ([bmim][Cl]), followed by the lignin extraction through the CO2 gas purging prior to addition of aluminum potassium sulfate dodecahydrate (AlK(SO4)2 · 12H2O). The lignin yield, Y(L) (%wt.) was found to be dependent of the types of OPB observed for all precipitation methods used. The lignin recovery, RL (%wt.) obtained from CO2-AlK(SO4)2 · 12H2O precipitation was, however dependent on the types of OPB, which contradicted to that of the acidified H2SO4 and HCl solutions of pH 0.7 and 2 precipitations. Only about 54% of lignin was recovered from the OPB. The FTIR results indicate that the monodispersed lignin was successfully extracted from the OPT, OPF and OPEFB having a molecular weight (MW) of 1331, 1263 and 1473 g/mol, and degradation temperature of 215, 207.5 and 272 °C, respectively.
As groundwater is a vital source of water for domestic and agricultural activities in Thanjavur city due to lack of surface water resources, groundwater quality and its suitability for drinking and agricultural usage were evaluated. In this study, 102 groundwater samples were collected from dug wells and bore wells during March 2008 and analyzed for pH, electrical conductivity, temperature, major ions, and nitrate. Results suggest that, in 90% of groundwater samples, sodium and chloride are predominant cation and anion, respectively, and NaCl and CaMgCl are major water types in the study area. The groundwater quality in the study site is impaired by surface contamination sources, mineral dissolution, ion exchange, and evaporation. Nitrate, chloride, and sulfate concentrations strongly express the impact of surface contamination sources such as agricultural and domestic activities, on groundwater quality, and 13% of samples have elevated nitrate content (>45 mg/l as NO(3)). PHREEQC code and Gibbs plots were employed to evaluate the contribution of mineral dissolution and suggest that mineral dissolution, especially carbonate minerals, regulates water chemistry. Groundwater suitability for drinking usage was evaluated by the World Health Organization and Indian standards and suggests that 34% of samples are not suitable for drinking. Integrated groundwater suitability map for drinking purposes was created using drinking water standards based on a concept that if the groundwater sample exceeds any one of the standards, it is not suitable for drinking. This map illustrates that wells in zones 1, 2, 3, and 4 are not fit for drinking purpose. Likewise, irrigational suitability of groundwater in the study region was evaluated, and results suggest that 20% samples are not fit for irrigation. Groundwater suitability map for irrigation was also produced based on salinity and sodium hazards and denotes that wells mostly situated in zones 2 and 3 are not suitable for irrigation. Both integrated suitability maps for drinking and irrigation usage provide overall scenario about the groundwater quality in the study area. Finally, the study concluded that groundwater quality is impaired by man-made activities, and proper management plan is necessary to protect valuable groundwater resources in Thanjavur city.
This work evaluates the performance of ionic liquid in supported liquid membrane (SLM) for the removal of phenol from wastewater. Ionic liquids are organic salts entirely composed of organic cations and either organic or inorganic anions. Due to the fact that the vapor pressure of ionic liquid is not detectable and they are sparingly soluble in most conventional solvents, they can be applied in SLM as the organic phase. In this work, 1-n-alkyl-3-methylimidazolium salts, [C(n)MIM](+)[X](-) have been investigated so as to determine an optimal supported ionic liquid membrane. The effect of operational parameters such as pH, stirring speed and the concentration of stripping agent has been studied, and an evaluation of different membrane supports were also carried out. With a minimal amount of the ionic liquid 1-Butyl-3-methylimidazolium hydrogensulfate, 85% phenol removal could be achieved by using polytetrafluoroethylene hydrophobic membrane filter in the SLM.