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.
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.
Highly photocatalytically active copper chromite nanostructured material were prepared via a novel simple hydrothermal reaction between [Cu(en)2(H2O)2]Cl2 and [Cr(en)3]Cl3.3H2O at low temperature, without adding any pH regulator or external capping agent. The as-synthesized nanostructured copper chromite was analyzed by transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy, energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy. Results of the morphological investigation of the as-synthesized products illustrate that the shape and size of the copper chromite depended on the surfactant sort, reaction duration and temperature. Moreover, the photocatalytic behavior of as-obtained copper chromite was evaluated by photodegradation of acid blue 92 (anionic dye) as water pollutant.
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.
Copper(II) complex of quercetin Cu+Q, mixed ligand complexes, quercetin-Cu(II)-phenanthroline [Cu+Q(PHt)] and quercetin-Cu(II)-neocuproine [Cu+Q(Neo)] have been synthesized and characterized. From the FT-IR spectroscopic studies, it was evident that C-ring of quercetin is involved in the metal chelation in all the three copper complexes. C-ring chelation was further proven by UV-Visible spectra and the presence of Cu(II) from EPR spectroscopic investigations. These complexes were found to have osteogenic and angiogenic properties, observed through in vitro osteoblast differentiation and chick embryo angiogenesis assay. In osteoblast differentiation, quercetin-Cu(II) complexes treatment increased calcium deposition and alkaline phosphatase activity (ALP) activity at the cellular level and stimulated Runx2 mRNA and protein, ALP mRNA and type 1 collagen mRNA expression at the molecular level. Among the complexes, Q+Cu(PHt) showed more effects on osteoblast differentiation when compared to that of other two copper complexes. Additionally, Q+Cu(Neo) showed more effect compared to Q+Cu. Furthermore, the effect of these complexes on osteoblast differentiation was confirmed by the expression of osteoblast specific microRNA, pre-mir-15b. The chick embryo angiogenesis assay showed that angiogenic parameters such as blood vessel length, size and junctions were stimulated by these complexes. Thus, the present study demonstrated that quercetin copper(II) complexes exhibit as a pharmacological agent for the orthopedic application.
In this study, the Cu(II) and Cd(II) ions removal behavior of crosslinked chitosan beads grafted poly(methacrylamide) (abbreviated as crosslinked chitosan-g-PMAm) from single metal ion solutions was investigated. The modified chitosan beads presented a remarkable improvement in acid resistance. The batch experiments demonstrated that pH of solution played a significant role in adsorption. It was found that the adsorption of Cu(II) and Cd(II) were optimum at pH 4 and pH 5, respectively. The maximum adsorption capacities for Cu(II) and Cd(II) based on Langmuir equation were 140.9 mg g-1 and 178.6 mg g-1, respectively. Pseudo-second order gave a better fit for adsorption data with respect to linearity coefficients than pseudo-first order suggesting that chemisorption or electron transfer is the dominant mechanism of the metal ions onto crosslinked chitosan-g-PMAm. In addition, X-ray photoelectron spectroscopy (XPS) investigations revealed that adsorption of both metal ions took place on the surfaces of crosslinked chitosan-g-PMAm by chelation through CNH2, CO and CO groups. Overall, the modified chitosan has proved a promising adsorbent for removal of metal ions.
Hydroquinone (HQ), a phenolic compound is expansively used in many industrial applications and due to the utilization of HQ, water pollution tragedies frequently found by the improper handling and accidental outflows. When HQ is adsorbed directly through the skin that create toxic effects to human by affecting kidney, liver, lungs, and urinary tract and hence, a highly selective and sensitive technique is required for its quantification. Herein, we have developed the ultrasonic synthesis of copper oxide nanoflakes (CuO-NFs) using ultrasonic bath (20 kHz, 100 W) and successfully employed for the sensitive detection of the environmental hazardous pollutant HQ. The formed CuO-NFs were confirmed by X-ray diffraction, field emission scanning electron microscopy (FE-SEM), FT-IR spectroscopy and UV-visible spectroscopy and fabricated with the screen-printed carbon electrode (SPCE). The SEM images exhibited the uniform CuO-NFs with an average width of 85 nm. The linker-free CuO-NFs fabricated electrode showed the appropriate wide range of concentrations from 0.1 to 1400 µM and the limit of detection was found to be 10.4 nM towards HQ. The fabricated sensor having long term stability and sensitivity was successfully applied for the environmental and commercial real sample analysis and exhibited good recovery percentage, implying that the SPCE/CuO-NFs is an economically viable and benign robust scaffold for the determination of HQ.
The present work proposed a novel approach for transferring high-risk heavy metals tometal complexes via green chemistry remediation. The method of remediation of heavy metals developed in the present work is a great challenge for global environmental sciences and engineering because it is a totally environmentally friendly procedure in which black tea extract solution is used. The FTIR study indicates that black tea contains enough functional groups (OH and NH), polyphenols and conjugated double bonds. The synthesis of copper complex was confirmed by the UV-vis, XRD and FTIR spectroscopic studies. The XRD and FTIR analysis reveals the formation of complexation between Cu metal complexes and Poly (Vinyl Alcohol) (PVA) host matrix. The study of optical parameters indicates that PVA-based hybrids exhibit a small optical band gap, which is close to inorganic-based materials. It was noted that the absorption edge shifted to lower photon energy. When Cu metal complexes were added to PVA polymer, the refractive index was significantly tuned. The band gap shifts from 6.2 eV to 1.4 eV for PVA incorporated with 45 mL of Cu metal complexes. The nature of the electronic transition in hybrid materials was examined based on the Taucs model, while a close inspection of the optical dielectric loss was also performed in order to estimate the optical band gap. The obtained band gaps of the present work reveal that polymer hybrids with sufficient film-forming capability could be useful to overcome the drawbacks associated with conjugated polymers. Based on the XRD results and band gap values, the structure-property relationships were discussed in detail.
Laccases, oxidative copper-enzymes found in fungi and bacteria were used as the basis in the design of nona- and tetrapeptides. Laccases are known to be excellent catalysts for the degradation of phenolic xenobiotic waste. However, since solvent extraction of laccases is environmentally-unfriendly and yields obtained are low, they are less preferred compared to synthetic catalysts. The histidine rich peptides were designed based on the active site of laccase extracted from Trametes versicolor through RCSB Protein Data Bank, LOMETS and PyMol software. The peptides were synthesized using Fmoc-solid phase peptide synthesis (SPPS) with 30-40% yield. These peptides were purified and characterized using LC-MS (purities >75%), FTIR and NMR spectroscopy. Synthesized copper(II)-peptides were crystallized and then analyzed spectroscopically. Their structures were elucidated using 1D and 2D NMR. Standards (o,m,p-cresol, 2,4-dichlorophenol) catalysed using laccase from Trametes versicolor (0.66 U/mg) were screened under different temperatures and stirring rate conditions. After optimizing the degradation of the standards with the best reaction conditions reported herein, medications with phenolic and aromatic structures such as ibuprofen, paracetamol (acetaminophen), salbutamol, erythromycin and insulin were screened using laccase (positive control), apo-peptides and copper-peptides. Their activities evaluated using GC-MS, were compared with those of peptide and copper-peptide catalysts. The tetrapeptide was found to have the higher degradation activity towards salbutamol (96.8%) compared with laccase at 42.8%. Ibuprofen (35.1%), salbutamol (52.9%) and erythromycin (49.7%) were reported to have the highest degradation activities using Cu-tetrapeptide as catalyst when compared with the other medications. Consequently, o-cresol (84%) was oxidized by Tp-Cu while the apo-peptides failed to oxidize the cresols. Copper(II)-peptides were observed to have higher catalytic activity compared to their parent peptides and the enzyme laccase for xenobiotic degradation.
This research optimized the adsorption performance of rice husk char (RHC4) for copper (Cu(II)) from an aqueous solution. Various physicochemical analyses such as Fourier transform infrared spectroscopy (FTIR), field-emission scanning electron microscopy (FESEM), carbon, hydrogen, nitrogen, and sulfur (CHNS) analysis, Brunauer-Emmett-Teller (BET) surface area analysis, bulk density (g/mL), ash content (%), pH, and pHZPC were performed to determine the characteristics of RHC4. The effects of operating variables such as the influences of aqueous pH, contact time, Cu(II) concentration, and doses of RHC4 on adsorption were studied. The maximum adsorption was achieved at 120 min of contact time, pH 6, and at 8 g/L of RHC4 dose. The prediction of percentage Cu(II) adsorption was investigated via an artificial neural network (ANN). The Fletcher-Reeves conjugate gradient backpropagation (BP) algorithm was the best fit among all of the tested algorithms (mean squared error (MSE) of 3.84 and R2 of 0.989). The pseudo-second-order kinetic model fitted well with the experimental data, thus indicating chemical adsorption. The intraparticle analysis showed that the adsorption process proceeded by boundary layer adsorption initially and by intraparticle diffusion at the later stage. The Langmuir and Freundlich isotherm models interpreted well the adsorption capacity and intensity. The thermodynamic parameters indicated that the adsorption of Cu(II) by RHC4 was spontaneous. The RHC4 adsorption capacity is comparable to other agricultural material-based adsorbents, making RHC4 competent for Cu(II) removal from wastewater.
A copper-1,4-naphthalenedicarboxylic acid-based organic framework (Cu-NDCA MOF) with different morphologies was synthesized by solvothermal synthetic route via a simple protonation-deprotonation approach. The synthesized Cu-NDCA MOFs were analyzed by diverse microscopic and spectral techniques. The FE-SEM and TEM image results exhibited the flake-like (FL), partial anisotropic (PAT), and anisotropic (AT)-Cu-NDCA MOFs formation obtained at different pH (3.0, 7.0, and 9.0) of the reaction medium. The AT-Cu-NDCA MOF/GC electrode not only increases the electroactive surface area but also boosts the electron transfer rate reaction compared to other modified electrodes (PAT- and FL-Cu-NDCA MOFs/GCEs). Under the optimized conditions, the modified electrode (AT-Cu-NDCA MOF) exhibited a sharp oxidation peak (+ 0.46 V vs. Ag/AgCl) and higher current response for rutin. The electrode provides a wide linear range from 1 × 10-9 to 50 × 10-6 M, a low detection limit of 1.21 × 10-10 M, LOQ of 0.001 μM, and sensitivity of 0.149 μA μM-1 cm-2. The AT-Cu-NDCA MOF/GC electrode exhibited good stability (RSD = 3.52 ± 0.02% over 8 days of storage), and excellent reproducibility (RSD = 2.62 ± 0.02% (n = 3)). The modified electrode was applied to the determination of rutin in apple, orange, and lemon samples with good recoveries (99.79-99.91, 99.24-99.69, and 99.53-99.83, respectively). Graphical abstract Anisotropic structure of Cu-NDCA MOFs and its modification on glassy carbon electrode for ultra-sensitive determination of rutin in fruit samples.
A study on the modification of rice husk by various carboxylic acids showed that tartaric acid modified rice husk (TARH) had the highest binding capacities for Cu and Pb. The carboxyl groups on the surface of the modified rice husk were primarily responsible for the sorption of metal ions. A series of batch experiments using TARH as the sorbent for the removal of Cu and Pb showed that the sorption process was pH dependent, rapid and exothermic. The sorption process conformed to the Langmuir isotherm with maximum sorption capacities of 29 and 108 mg/g at 27 +/- 2 degrees C for Cu and Pb, respectively. The uptake increased with agitation rate. Decrease in sorbent particle size led to an increase in the sorption of metal ions and this could be explained by an increase in surface area and hence binding sites. Metal uptake was reduced in the presence of competitive cations and chelators. The affinity of TARH for Pb is greater than Cu.
The ability of Pycnoporus sanguineus to adsorb heavy metals from aqueous solution was investigated in fixed-bed column studies. The experiments were conducted to study the effect of important design parameters such as column bed height, flow rate and initial concentration of solution. The breakthrough profiles were obtained in these studies. A mathematical model based on external mass transfer and pore diffusion was used for the prediction of mass transfer coefficient and effective diffusivity of metals in macro-fungi bed. Experimental breakthrough profiles were compared with the simulated breakthrough profiles obtained from the mathematical model. Bed Depth Service Time (BDST) model was used to analyse the experimental data and evaluated the performance of biosorption column. The BDST model parameters needed for the design of biosorption columns were evaluated for lead, copper and cadmium removal in the column. The columns were regenerated by eluting the metal ions using 0.1 M hydrochloric acid solution after the adsorption studies. The columns were subjected to repeated cycles of adsorption of same metal ions and desorption to evaluate the removal efficiency after adsorption-desorption.
Denture marking is accepted as a means of identifying dentures and persons in geriatric institutions, or post-mortem during war, crimes, civil unrest, natural and mass disasters. Labelling on the acrylic resin component of the denture can easily be damaged or destroyed by fire but on cobalt-chromium components it would be more resistant. A copper vapour laser (CVL) can be used to label the cobalt-chromium components of dentures and metal restorations easily, and legibly, and miniaturised for the incorporation of more personal particulars necessary for the identification of the deceased person. The CVL beam is focussed by its optics and delivered to the material surface by the two-axis scanner mounted with mirrors. A personal computer controls the movement of the scanner and the firing of the CVL. The high peak power of the pulsed CVL is focussed to very high energy density producing plasma ablation of the alloy surface. Very fine markings of a few microns width can be produced enabling the storage of detailed information of the deceased person on a metal surface for the purpose of rapid identification.
The sorption characteristics of Cr(VI) and Cu(II) by ethylenediamine modified rice hull from single and binary metal ion solutions were evaluated under various experimental conditions. Optimal Cr(VI) and Cu(II) removal from single metal ion solutions occurred at pH 2.0 and 5.5, respectively. Simultaneous removal of Cr(VI) and Cu(II) occurred at pH greater than 3.0. The sorption kinetics of Cr(VI) and Cu(II) from single and binary metal ion solutions were studied with reference to metal concentration, agitation rate and particle size. Sorption of Cr(VI) was more rapid than Cu(II). The kinetics of metal ion sorption fitted a pseudo-second order expression. The variation in the initial uptake rates was very small at an agitation rate beyond 150 rpm and sorption was generally independent of particle size. Equilibrium sorption data could be fitted into the Langmuir isotherm equation. Maximum sorption capacities of ethylenediamine modified rice hull for Cr(VI) at pH 2 and Cu(II) at pH 4 in single metal solutions were 0.45 and 0.06 mmol g(-1), respectively. This corresponds to an enhancement factor of 2.6 and 3 fold for Cr(VI) and Cu(II), respectively, compared to natural rice hull. A synergistic effect was observed for sorption of these ions in binary metal solutions.
Wastewater treatment systems employing simultaneous adsorption and biodegradation processes have proven to be effective in treating toxic pollutants present in industrial wastewater. The objective of this study is to evaluate the effect of Cu(II) and the efficacy of the powdered activated carbon (PAC) and activated rice husk (ARH) in reducing the toxic effect of Cu(II) on the activated sludge microorganisms. The ARH was prepared by treatment with concentrated nitric acid for 15 h at 60-65 degrees C. The sequencing batch reactor (SBR) systems were operated with FILL, REACT, SETTLE, DRAW and IDLE modes in the ratio of 0.5:3.5:1:0.75:0.25 for a cycle time of 6 h. The Cu(II) and COD removal efficiency were 90 and 85%, respectively, in the SBR system containing 10 mg/l Cu(II) with the addition of 143 mg/l PAC or 1.0 g PAC per cycle. In the case of 715 mg/l ARH or 5.0 g ARH per cycle addition, the Cu(II) and COD removal efficiency were 85 and 92%, respectively. ARH can be used as an alternate adsorbent to PAC in the simultaneous adsorption and biodegradation wastewater treatment process for the removal of Cu(II). The specific oxygen uptake rate (SOUR) and kinetic studies show that the addition of PAC and ARH reduce the toxic effect of Cu(II) on the activated sludge microorganisms.
A predictive model of a virgin coconut oil (VCO) nanoemulsion system for the topical delivery of copper peptide (an anti-aging compound) was developed using an artificial neural network (ANN) to investigate the factors that influence particle size. Four independent variables including the amount of VCO, Tween 80: Pluronic F68 (T80:PF68), xanthan gum and water were the inputs whereas particle size was taken as the response for the trained network. Genetic algorithms (GA) were used to model the data which were divided into training sets, testing sets and validation sets. The model obtained indicated the high quality performance of the neural network and its capability to identify the critical composition factors for the VCO nanoemulsion. The main factor controlling the particle size was found out to be xanthan gum (28.56%) followed by T80:PF68 (26.9%), VCO (22.8%) and water (21.74%). The formulation containing copper peptide was then successfully prepared using optimum conditions and particle sizes of 120.7 nm were obtained. The final formulation exhibited a zeta potential lower than -25 mV and showed good physical stability towards centrifugation test, freeze-thaw cycle test and storage at temperature 25°C and 45°C.
A very simple and low-cost procedure has been adopted to synthesize efficient copper (Cu), silver (Ag) and copper-silver (Cu-Ag) mixed nanoparticles on the surface of pure cellulose acetate (CA) and cellulose acetate-copper oxide nanocomposite (CA-CuO). All nanoparticles loaded onto CA and CA-CuO presented excellent catalytic ability, but Cu-Ag nanoparticles loaded onto CA-CuO (Cu0-Ag0/CA-CuO) exhibited outstanding catalytic efficiency to convert 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) in the presence of NaBH4. Additionally, the Cu0-Ag0/CA-CuO can be easily recovered by removing the sheet from the reaction media, and can be recycled several times, maintaining high catalytic ability for four cycles.
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.