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.
The presence of heavy metal in food chains due to the rapid industrialization poses a serious threat on the environment. Therefore, detection and monitoring of heavy metals contamination are gaining more attention nowadays. However, the current analytical methods (based on spectroscopy) for the detection of heavy metal contamination are often very expensive, tedious and can only be handled by trained personnel. DNA biosensors, which are based on electrochemical transduction, is a sensitive but inexpensive method of detection. The principles, sensitivity, selectivity and challenges of electrochemical biosensors are discussed in this review. This review also highlights the major advances of DNA-based electrochemical biosensors for the detection of heavy metal ions such as Hg(2+), Ag(+), Cu(2+) and Pb(2+).
Crosslinked chitosan beads were grafted with N-vinyl-2-pyrrolidone (NVP) using ammonium persulfate (APS) as free radical initiator. Important variables on graft copolymerization such as temperature, reaction time, concentration of initiator and concentration of monomer were optimized. The results revealed optimum conditions for maximum grafting of NVP on 1g crosslinked chitosan as follows: reaction temperature, 60°C; reaction time, 2h and concentrations of APS and NVP of 2.63×10-1M and 26.99×10-1M, respectively. The modified chitosan beads were characterized by FTIR spectroscopy, 13C NMR, SEM and BET to provide evidence of successful crosslinking and grafting reactions. The resulting material (cts(x)-g-PNVP) was evaluated as adsorbent for the removal of Cu(II) ions from aqueous solutions in a batch experiment. The Langmuir and Freundlich adsorption models were also applied to describe the equilibrium isotherms. The results showed that the adsorption of the copper ions onto the beads agreed well with Langmuir model with the maximum capacity (qmax) of 122mgg-1.
In this study, dye-sensitized solar cells (DSSCs) has been assembled with poly(1-vinylpyrrolidone-co-vinyl acetate) (P(VP-co-VAc)) gel polymer electrolytes (GPEs) which have been incorporated with binary salt and an ionic liquid. The potential of this combination was studied and reported. The binary salt system GPEs was having ionic conductivity and power conversion efficiency (PCE) that could reach up to 1.90 × 10(-3) S cm(-1) and 5.53%, respectively. Interestingly, upon the addition of the ionic liquid, MPII into the binary salt system the ionic conductivity and PCE had risen steadily up to 4.09 × 10(-3) S cm(-1) and 5.94%, respectively. In order to know more about this phenomenon, the electrochemical impedance studies (EIS) of the GPE samples have been done and reported. Fourier transform infrared studies (FTIR) and thermogravimetric analysis (TGA) have also been studied to understand more on the structural and thermal properties of the GPEs. The Nyquist plot and Bodes plot studies have been done in order to understand the electrochemical properties of the GPE based DSSCs and Tafel polarization studies were done to determine the electrocatalytic activity of the GPE samples.
Capacitive deionization (CDI) is a promising procedure for removing various charged ionic species from brackish water. The performance of graphene-based material in capacitive deionization is lower than the expectation of the industry, so highly-crumpled, few-layered graphene (HCG) and highly-crumpled nitrogen-doped graphene (HCNDG) with high surface area have been introduced as promising candidates for CDI electrodes. Thus, HCG and HCNDG were prepared by exfoliation of graphite in the presence of liquid-phase, microwave-assisted methods. An industrially-scalable, cost-effective, and simple approach was employed to synthesize HCG and HCNDG, resulting in few-layered graphene and nitrogen-doped graphene with large specific surface area. Then, HCG and HCNDG were utilized for manufacturing a new class of carbon nanostructure-based electrodes for use in large-scale CDI equipment. The electrosorption results indicated that both the HCG and HCNDG have fairly large specific surface areas, indicating their huge potential for capacitive deionization applications.
Vanadium(IV) and vanadium(V) can be determined by using differential pulse cathodic stripping voltammetry technique (DPCSV). Cupferron (ammonium N-nitrosophenylhydroxylamine) was used as ligand to form complex compounds with vanadium ions in Britton-Robinson buffer (BRB) solution. At concentration lower than 1.0×10(-6) M, both V(IV) and V(V) cupferron complexes showed a single cathodic peak at -0.576 V in BRB of pH 4; thus V(IV) and V(V) ions cannot be differentiated at low concentration. However, the ionic species of vanadium can be differentiated at high concentration in the presence of cupferron. Parameters including pH of BRB solution, initial potential and accumulation potential were optimized. Under the optimized parameters, the limit of detection (LOD) was 0.09 nM, and the peak current was linear in the concentration range 0.01-0.9 µM total vanadium ions. The determination of V(IV) and V(V) ions was carried out at higher concentration in the sample using calibration plot method. At higher concentration range of 10-60 µM V(IV) and V(V) ions were determined with LOD of 1.2 and 1.1 µM, respectively. The developed method was successfully applied to 10,00,000 fold diluted Benfield sample and 0.6227 M total vanadium ions were determined. The determination of V(IV) and V(V) ions were also successfully carried out in artificial sample as well as Benfield sample (dilution factor, 10,000). The concentration of V(IV) and V(V) ions was 22.52 µM and 38.91 µM, respectively, giving total vanadium concentration of 0.6143 M in Benfield sample.
In this study, a sensitive and cost-effective electrochemically reduced graphene oxide (ErGO) on graphite reinforced carbon (GRC) was developed for the detection of lead (Pb(II)) ions present in the real-life samples. A film of graphene oxide (GO) was drop-casted on GRC and their electrochemical properties were investigated using cyclic voltammetry (CV), amperometry and square wave voltammetry (SWV). Factors influencing the detection of Pb(II) ions, such as grades of GRC, constant applied cathodic potential (CACP), concentration of hydrochloric acid and drop-casting drying time were optimised. GO is irreversibly reduced in the range of -0.7 V to -1.6 V vs Ag/AgCl (3 M) in acidic condition. The results showed that the reduction behaviour of GO contributed to the high sensitivity of Pb(II) ions detection even at nanomolar level. The ErGO-GRC showed the detection limit of 0.5 nM and linear range of 3-15 nM in HCl (1 M). The developed electrode has potential to be a good candidate for the determination of Pb(II) ions in different aqueous system. The proposed method gives a good recovery rate of Pb(II) ions in real-life water samples such as tap water and river water.
A flexible solid polymer electrolyte (SPE) system based on poly(ε-caprolactone) (PCL), a FDA approved non-toxic and biodegradable material in the effort to lower environmental impact was prepared. Ammonium thiocyanate (NH4SCN) and ethylene carbonate (EC) were incorporated as the source of charge carriers and plasticizing agent, respectively. When 50wt.% of ethylene carbonate (EC) was added to PCL-NH4SCN system, the conductivity increased by two orders from of 3.94×10(-7)Scm(-1) to 3.82×10(-5)Scm(-1). Molecular vibrational analysis via infrared spectroscopy had been carried out to study the interaction between EC, PCL and NH4SCN. The relative percentage of free ions, ion pairs and ion aggregates was calculated quantitatively by deconvoluting the SCN(-) stretching mode (2030-2090cm(-1)). This study provides fundamental insight on how EC influences the free ion dissociation rate and ion mobility. The findings are also in good agreement to conductivity, differential scanning calorimetry and X-ray diffraction results. High dielectric constant value (89.8) of EC had made it an effective ion dissociation agent to dissociate both ion pairs and ion aggregates, thus contributing to higher number density of free ions. The incorporation of EC had made the polymer chains more flexible in expanding amorphous domain. This will facilitate the coupling synergy between ionic motion and polymer segmental motion. Possible new pathway through EC-NH4(+) complex sites for ions to migrate with shorter distance has been anticipated. This implies an easier ion migration route from one complex site to another.
A unique feature of the space radiation environment is the presence of high-energy charged particles, including (56)Fe ions, which can present a significant hazard to space flight crews during and following a mission. (56)Fe irradiation-induced cognitive changes often involve alterations in hippocampal function. These alterations might involve changes in spine morphology and density. In addition to irradiation, performing a cognitive task can also affect spine morphology. Therefore, it is often hard to determine whether changes in spine morphology and density are due to an environmental challenge or group differences in performance on cognitive tests. In this study, we tested the hypothesis that the ability of exploratory behavior to increase specific measures of hippocampal spine morphology and density is affected by (56)Fe irradiation. In sham-irradiated mice, exploratory behavior increased basal spine density in the CA1 region of the hippocampus and the enclosed blade of the dentate gyrus. These effects were not seen in irradiated mice. In addition, following exploratory behavior, there was a trend toward a decrease in the percent stubby spines on apical dendrites in the CA3 region of the hippocampus in (56)Fe-irradiated, but not sham-irradiated, mice. Other hippocampal regions and spine measures affected by (56)Fe irradiation showed comparable radiation effects in behaviorally naïve and cognitively tested mice. Thus, the ability of exploratory behavior to alter spine density and morphology in specific hippocampal regions is affected by (56)Fe irradiation.
In this work, independent radial diffusion at arrayed nanointerfaces between two immiscible electrolyte solutions (nanoITIES) was achieved. The arrays were formed at nanopores fabricated by focused ion beam milling of silicon nitride (SiN) membranes, enabling the reproducible and systematic design of five arrays with different ratios of pore center-to-center distance (rc) to pore radius (ra). Voltammetry across water-1,6-dichlorohexane nanoITIES formed at these arrays was examined by the interfacial transfer of tetrapropylammonium ions. The diffusion-limited ion-transfer current increased with the ratio rc/ra, reaching a plateau for rc/ra ≥ 56, which was equivalent to the theoretical current for radial diffusion to an array of independent nanoITIES. As a result, mass transport to the nanoITIES arrays was greatly enhanced due to the decreased overlap of diffusion zones at adjacent nanoITIES, allowing each interface in the array to behave independently. When the rc/ra ratio increased from 13 to 56, the analytical performance parameters of sensitivity and limit of detection were improved from 0.50 (±0.02) A M(-1) to 0.76 (±0.02) A M(-1) and from 0.101 (±0.003) μM to 0.072 (±0.002) μM, respectively. These results provide an experimental basis for the design of arrayed nanointerfaces for electrochemical sensing.
Poly(hydroxamic acid) chelating ion-exchange resin was prepared from crosslinked poly(methacrylate) beads. The starting polymer was prepared by a suspension polymerization of methacrylate and divinyl benzene. Conversion of the ester groups into the hydroxamic acid was carried out by treatment with hydroxylamine in an alkaline solution. Hydroxamic acid capacity of the product was 2.71 mmol/g. The resin exhibited high affinity towards Fe(III) and Pb ions and its capacities for Fe(III), Pb, Cu, Ni and Co ions were pH dependent. The ability of the resin to carry out the separation of Fe(III)CuCo/Ni and PbNi ions is also reported.
One of the techniques to increase oil recovery from hydrocarbon reservoirs is the injection of low salinity water. It is shown that the injection of low salinity water changes the wettability of the rock. However, there are argumentative debates concerning low salinity water effect on changing the wettability of the oil/brine/rock system in the oil reservoirs. In this regard, molecular dynamics simulation (MDS) as a tool to simulate the phenomena at the molecular level has been used for more than a decade. In this study, the Zisman plot (presented by KRUSS Company) was simulated through MDS, and then, contact angle experiments for n-decane interactions on the Bentheimer substrate in the presence of different concentrations of sodium ions were conducted. MDS was then used to simulate experiments and understand the wettability trend based on free-energy calculations. Hereafter, a new model was developed in this study to correlate free energies with contact angles. The developed model predicted the experimental results with high accuracy (R2 ∼ 0.98). A direct relation was observed between free energy and water contact angle. In contrast, an inverse relation was noticed between the ion concentration and the contact angle such that an increase in the ion concentration resulted in a decrease in the contact angle and vice versa. In other terms, increasing brine ionic concentrations in the presence of n-decane is linked to a decrease in free energies and an increase in the wetting state of a sandstone. The comparison between the developed model's predicted contact angles and experimental observations showed a maximum deviation of 14.32%, which is in satisfactory agreement to conclude that MDS can be used as a valuable and economical tool to understand the wettability alteration process.
This work demonstrates a high-performance hybrid asymmetric supercapacitor (HASC) workable in very high current density of 30 A g-1 with in-situ pyrolytic processed sulfur-doped graphitic carbon nitride/cobalt disulfide (S-gC3N4/CoS2) materials and bio-derived carbon configuration and achievement of high electrochemical stability of 89% over 100,000 cycles with the coulombic efficiency of 99.6%. In the electrochemical studies, the S-gC3N4/CoS2-II electrode showed a high specific capacity of 180 C g-1 at 1 A g-1 current density in the half-cell configuration. The HASC cell was fabricated using S-gC3N4/CoS2-II material and orange peel derived activated carbon as a positive and negative electrode with a maximum operating cell potential of 1.6 V, respectively. The fabricated HASC delivered a high energy density of 26.7 Wh kg-1 and power density of 19.8 kW kg-1 in aqueous electrolyte. The prominent properties in specific capacity and cycling stability could be attributed to the CoS2 nanoparticles engulfed into the S-gC3N4 framework which provides short transport distance of the ions, strong interfacial interaction, and improving structural stability of the S-gC3N4/CoS2-II materials.
The reaction of diethyl 2,5-bis(tert-butyl)phenoxy-3,6-dihydroxyterephthalate (1) with tetraethylene glycol di(p-toluenesulfonate) under high-dilution conditions afforded several isolated products. Two products were identified as macrocycles with one being the 1 + 1 crown ether derivative 3 (10% yield), and the second being the 2 + 2 crown ether compound D3 (19% yield). The X-ray structure for 3 was determined with the asymmetric unit observed to comprise half of the molecule. The small crown ether ring of 3 interacts with K+ or H+ ions in MeOH, but binding is weak and the macrocyclic cavity is too small to fully encapsulate the K+ ion. Transesterification of compounds 1, its methylated version 2 and 3 with diols such as ethylene glycol or 1,4-butandiol produced monomers (M1-M3) which were reacted with terephthaloyl chloride. Short oligomers were produced (PolyM1-PolyM3) rather than extensive polymeric materials and all displayed solid state fluorescence. The absorption and fluorescence properties of M1-M2 and their polymers can be related to subtle structural changes. The Stokes shift for M2 of 15 627 cm-1 in DCM is one of the largest observed for a simple organic chromophore in fluid solution.
Currently, the development of the sodium-ion (Na-ion) batteries as an alternative to lithium-ion batteries has been accelerated to meet the energy demands of large-scale power applications. The difficulty of obtaining suitable electrode materials capable of storing large amount of Na-ion arises from the large radius of Na-ion that restricts its reversible capacity. Herein, Mn2O3 powders are synthesised through the thermal conversion of MnCO3 and reported for the first time as an anode for Na-ion batteries. The phase, morphology and charge/discharge characteristics of Mn2O3 obtained are evaluated systematically. The cubic-like Mn2O3 with particle sizes approximately 1.0-1.5 µm coupled with the formation of Mn2O3 sub-units on its surface create a positive effect on the insertion/deinsertion of Na-ion. Mn2O3 delivers a first discharge capacity of 544 mAh g-1 and retains its capacity by 85% after 200 cycles at 100 mA g-1, demonstrating the excellent cyclability of the Mn2O3 electrode. Therefore, this study provides a significant contribution towards exploring the potential of Mn2O3 as a promising anode in the development of Na-ion batteries.
Heavy metal ions contamination has become more serious which is caused
by the releasing of toxic waterfrom industrial area and landfill that are very
harmful to all living organism especially human and can even cause death
if contaminated in small amount of heavy metal concentration. Currently,
peoples are using classic method namely electrochemical treatment,
chemical oxidation/reduction, chemical precipitation and reverse osmosis
to eliminate the metal ions from toxic water. Unfortunately, these methods
are costly and not environmentally friendly as compared to bioadsorption
method, where agricultural waste is used as biosorbent to remove heavy
metals. Two types of agricultural waste used in this research namely oil
palm mesocarp fiber (Elaesis guineensis sp.) (OPMF) and mangrove bark
(Rhizophora apiculate sp.) (MB) biomass. Through chemical treatment,
the removal efficiency was found to improve. The removal efficiency is
examined based on four specification namely dosage, of biosorbent to
adsorb fourtypes of metalsion explicitly nickel, lead, copper, and chromium.
The research has found that the removal efficiency of MB was lower than
OPMF; whereas, the multiple metals ions removal efficiency decreased in
the order of Pb2+ > Cu2+ > Ni2+ > Cr2+.
To overcome the critical limitations of liquid-electrolyte-based dye-sensitized solar cells, quasi-solid-state electrolytes have been explored as a means of addressing long-term device stability, albeit with comparatively low ionic conductivities and device performances. Although metal oxide additives have been shown to augment ionic conductivity, their propensity to aggregate into large crystalline particles upon high-heat annealing hinders their full potential in quasi-solid-state electrolytes. In this work, sonochemical processing has been successfully applied to generate fine Co3O4 nanoparticles that are highly dispersible in a PAN:P(VP-co-VAc) polymer-blended gel electrolyte, even after calcination. An optimized nanocomposite gel polymer electrolyte containing 3 wt % sonicated Co3O4 nanoparticles (PVVA-3) delivers the highest ionic conductivity (4.62 × 10-3 S cm-1) of the series. This property is accompanied by a 51% enhancement in the apparent diffusion coefficient of triiodide versus both unmodified and unsonicated electrolyte samples. The dye-sensitized solar cell based on PVVA-3 displays a power conversion efficiency of 6.46% under AM1.5 G, 100 mW cm-2. By identifying the optimal loading of sonochemically processed nanoparticles, we are able to generate a homogenous extended particle network that effectively mobilizes redox-active species through a highly amorphous host matrix. This effect is manifested in a selective 51% enhancement in photocurrent density (JSC = 16.2 mA cm-2) and a lowered barrier to N719 dye regeneration (RCT = 193 Ω) versus an unmodified solar cell. To the best of our knowledge, this work represents the highest known efficiency to date for dye-sensitized solar cells based on a sonicated Co3O4-modified gel polymer electrolyte. Sonochemical processing, when applied in this manner, has the potential to make meaningful contributions toward the ongoing mission to achieve the widespread exploitation of stable and low-cost dye-sensitized solar cells.
This study aimed to determine the best parameters (types of buffer, hydrolysis time and enzyme concentration) used to produce good quality of liquid protein hydrolysate from Yellowstripe scad in terms of high yield, protein content and concentration. The choice of buffer (sodium or potassium buffer), hydrolysis time (1 h, 2 h, 3 h or 4 h) and enzymes concentrations (0.5%, 1.0%, 1.5% and 2.0%) were investigated. The results obtained from two way ANOVA showed that these parameters had significant difference (p
In this work, voltammetric study based on cetyltrimethylammonium bromide (CTAB) as an ion-pairing agent for the determination of iodine level in iodized table salt has been explored. CTAB was used as an intermediate compound between iodide (I-) and the electrode due to its ability to dissociate to produce cetyltrimethylammonium ions ([CTA]+). The [CTA]+ with a long hydrophobic alkyl chain can be directly adsorbed onto the surface of the working electrode, and this in turns coated the electrode with cationic charge and enhance the electrode ability to bind to iodide (I-) and other molecular iodine ions. A mixture of iodide and CTAB ([CTA]+I-) was prepared and potential of 1.0 V for 60.0 s was applied to pre-concentrate the solution on the working electrode causing the [CTA]+I- to oxidize to iodine (I2). The produced I2 immediately react with chloride ion (Cl-) from the electrolyte of hydrochloric acid (HCl) to produce I2Cl- and form ion-pair with CTA+ as [CTA]+I2Cl-. The linear calibration curve of the developed method towards iodide was in the concentration range of 0.5-4.0 mg/L with sensitivity of - 1.383 µA mg/L-1 cm-2 (R2 = 0.9950), limit of detection (LOD) of 0.3 mg/L and limit of quantification (LOQ) of 1.0 mg/L, respectively. The proposed method indicates good agreement with the standard method for iodine determination with recovery range from 95.0 to 104.3%. The developed method provided potential application as a portable on-site iodine detector.
Phosphoric acid impregnated activated carbon from date pits (DPAC) was prepared through single step activation. Prepared DPAC was studied for its structural, elemental, chemical, surface and crystal nature. Adsorption ability of the DPAC was assessed through divalent lead ions separation studies. Effect of adsorbent dosage, contact time, pH, operating temperature and initial feed concentration on lead removal by DPAC was studied. Maximum Pb(II) adsorption capacity of 101.35 mg/g was attained for a contact time of 30 min and pH of 6 at 30°C. Increase in initial feed concentration enhanced the adsorption ability of DPAC and the rise in adsorbent dosage resulted in improved Pb(II) removal efficiency. Thermodynamic studies revealed that the lead adsorption on DPAC was exothermic and instantaneous in nature. Kinetic and equilibrium studies confirmed the suitability of pseudo-second order and Langmuir isotherm for divalent lead ions binding on DPAC. Reusability studies showed that HCl was the effective regeneration medium and the DPAC could be reused for a maximum of 4 times with slight reduction in Pb(II) removal efficiency (<10%). Results indicated the promising use of date pits biomass as a low cost and efficient starting material to prepare activated carbon for divalent lead ions removal.
Matched MeSH terms: Ions/isolation & purification; Ions/pharmacokinetics; Heavy Ions