Simultaneous removal of Cu2+ and Cr3+ ions from aqueous solution based on Complexation with Eriochrome cyanine‐R and derivative spectrophotometric method

TiO₂ nanoparticles deposited on activated carbon (TiO₂–NP–AC) was prepared and characterized by XRD and SEM analysis. Subsequently, simultaneous ultrasound‐assisted adsorption of Cu²⁺ and Cr³⁺ ions onto TiO₂‐NPs‐AC after complexation via eriochrome cyanine R (ECR) has been investigated with UV–Vis and FAA spectrophotometer. Spectra overlapping of the ECR‐Cu and ECR‐Cr complex was resolve by derivative spectrophotometric technique. The effects of various parameters such as initial Cu²⁺ (A) and Cr³⁺ (B) ions concentrations, TiO₂‐NPs‐AC mass (C), sonication time (D) and pH (E) on the removal percentage were investigated and optimized by central composite design (CCD). The optimize conditions were set as: 4.21 min, 0.019 mg, 20.02 and 13.22 mg L^?1 and 6.63 for sonication time, TiO₂–NP–AC mass, initial Cr³⁺ and Cu²⁺ ions concentration and pH, respectively. The experimental equilibrium data fitting to Langmuir, Freundlich, Temkin and Dubinin–Radushkevich models show that the Langmuir model is a good and suitable model for evaluation and the actual behavior of adsorption process and maximum adsorption capacity of 105.26 and 93.46 mg g^?1 were obtained for Cu²⁺ and Cr³⁺ ions, respectively. Kinetic evaluation of experimental data showed that the adsorption processes followed well pseudo second order and intraparticle diffusion models.     

A Photoelectrochemical Biosensor Fabricated using Hierarchically Structured Gold Nanoparticle and MoS2 on Tannic Acid Templated Mesoporous TiO2

In a tannic acid assisted synthesis of mesoporous TiO₂, tannic acid was used as a cost effective and non‐toxic template for pore formation. Meanwhile, a gold nanoparticles (Au NPs) deposited TiO₂ nanocomposite was coated on an indium tin oxide electrode for the fabrication of a photoelectrochemical (PEC) biosensing system. Upon the formation of anatase structure, the electrode was coated with MoS₂ for effective visible light absorption. The mesoporous structure led to an enhanced surface area by improving Au NPs and glucose oxidase adsorption. Incorporation of Au NPs led to an enhanced photonic efficiency due to the generation of Schottky barriers. The obtained nanocomposite was used for the light‐driven, real‐time, and selective PEC glucose sensing. Under visible light irradiation, the enzyme immobilized electrodes yielded significant photocurrent improvement owing to the releasing electron donor H₂O₂. The obtained PEC biosensor demonstrated acceptable reproducibility and stability with a sensitivity of 4.42 μA mM^?1 cm^?2 and a low detection limit of 1.2 μM glucose. Also, the linear measurement range was found to be 0.004–1.75 mM glucose. The results indicated that the proposed production method of mesoporous TiO₂ will pave the way for a green chemistry based porous material production, along with the extension of the implementation of semiconductors in PEC biosensing systems.     

Electrochemical Quantification of Lead Adsorption on TiO2 Nanoparticles

This work describes a rapid easy-to-use electrochemical method for quantifying lead (Pb²⁺) adsorption on metal oxide nanoparticles (NPs), demonstrated here for titanium dioxide (TiO₂). The method was able to quantify Pb²⁺ adsorption for concentrations as low as 0.95 μM, and up to 200 μM in NP dispersions, and to differentiate ion uptake in the presence and absence of a natural organic material, humic acid (HA). The method was selective for Pb²⁺ against Cu²⁺, As³⁺, Zn²⁺, Cd²⁺ and Cr³⁺ ions when measured in the specific potential range from −0.4 to −0.6 V and was successfully demonstrated in water and home-collected dust.     

Poly(ammonium/ pyridinium)-chitosan Schiff base as a smart biosorbent for scavenging of Cu2+ ions from aqueous effluents

Chitosan Schiff bases (CSBs) decorated with ammonium or pyridinium motifs for recyclable biosorption of Cu²⁺ ions from aqueous effluents were tailored by grafting of salicylaldehyde ionic liquids (Sal-ILs) onto chitosan surface. Biosorption capacity of poly(ionic-salicylidene) CSBs (PISCSB_1,2) was compared with chitosan and poly(neural-salicylidene) CSBs (PSCSB). The ionic salicylidene-functionalized chitosan, poly(pyridinium)-salicylidene chitosan Schiff base (PISCSB₂), exhibited excellent adsorption capacity (99.1%), in comparison to chitosan (85%) and PSCSB (95%). Biosorption of Cu²⁺ ions onto PSCSB followed pseudo-first-order kinetic model while onto chitosan (CS) and PISCSB_1,2 followed pseudo-second-order kinetic model. However, Cu²⁺ ions biosorption onto all biosorbents fitted Langmuir adsorption isotherm model. Negative values of ΔG^o and ΔH^o confirmed the spontaneity and exothermic behavior of adsorption process. The new biosorbents could be successfully regenerated in aqueous 0.01 M EDTA solution with negligible loss in their adsorption capacity. Consequently, our new chitosan-based biosorbents may offer promising green and renewable scavengers for Cu²⁺ ions from wastewater.     

CuCoO2 Nanoparticles as a Nanoprotease for Selective Proteolysis with High Efficiency at Room Temperature

Many nanoproteases contain tetravalent metal ions and catalyze peptide-bond hydrolysis only at high temperature (60 °C). Here, we report a new and effective strategy to explore nanoproteases from nanoparticles containing low valent metal ions. We found that flower-like CuCoO₂ nanoparticles (CuCoO₂ NPs) containing low valent Cu⁺ possessed excellent catalytic activity towards selective cleavage of peptide bonds with hydrophobic residues in bovine serum albumin (BSA) at room temperature. CuCoO₂ NPs exhibited excellent stability and had great reusability. CuCoO₂ NPs also hydrolyzed heat-denatured and surfactant-denatured BSA. Mechanism analysis revealed that the high Lewis acidity of Co³⁺ and the low valence of Cu⁺ were both essential for the high protease activity of CuCoO₂ NPs. The flower-like structure of CuCoO₂ NPs and the strong nucleophilicity of Cu⁺-bound hydroxyl endow them with excellent catalytic performance. The findings open a new way for the design and discovery of high-efficiency nanoproteases.     

A Facile Process for the Preparation of Three‐Dimensional Hollow Zn(OH)2 Nanoflowers at Room Temperature

A facile strategy has been developed to synthesize double‐shelled Zn(OH)₂ nanoflowers (DNFs) at room temperature. The nanoflowers were generated via conversion of Cu₂O nanoparticles (NPs) using ZnCl₂ and Na₂S₂O₃ by a simple process. Outward diffusion of the Cu²⁺, produced by an oxidation process on the surface of NPs, and the inward diffusion of Zn²⁺ by coordination and migration, eventually lead to a hollow cavity in the inner NPs with a double‐shelled 3D hollow flower shapes. The thickness of the inner and outer shells is estimated to be about 20 nm, and the thickness of nanopetals is about 7 nm. The nanoflowers have large surface areas and excellent adsorption properties. As a proof of potential applications, the DNFs exhibited an excellent ability to remove organic molecules from aqueous solutions.     

Sorption of Cu<Superscript>2+</Superscript> and Zn<Superscript>2+</Superscript> by Natural Biomaterial: Duck Feather

Feather fibers were modified by treatment with 5% tannic acid (TA) solution. Kinetics of the modification was investigated as a function of the reaction time. The maximum loading of TA on feather reached 8.3% after being treated by TA for 9 h. The adsorption of metal cations (Cu²⁺, Zn²⁺) by unmodified and TA-modified feather fibers was investigated as a function of fiber weight gain, temperature, and pH of the metal solution. The adsorption was enhanced at alkaline pH and ambient temperature and increased with the weight gain of TA. The maximum uptake of metal cations (Cu²⁺, 0.77 mmol/g; Zn²⁺, 0.95 mmol/g) was obtained by TA-modified feather at weight gain: 8.3%, pH 11, while at the acidic pH, the adsorption of metal cations by either unmodified or TA-modified feather was negligible. The influence of anions on the adsorption of metal cations was also studied. The uptake of Cu²⁺ from chloride was higher and faster than that from nitrate. Desorption of the metals was performed at acidic pH 2.5 for 48 h. The feather–TA–metal complexes exhibited higher stability for metal cations than the feather–metal complexes. All these experiments reveal that TA-modified feather fibers have good adsorption to metal cations and can be used as metal adsorbent in wastewater treatment.     

Preparation of core-shell magnetic Fe3O4@SiO2-dithiocarbamate nanoparticle and its application for the Ni2+, Cu2+ removal

A typical superparamagnetic nanoparticles-based dithiocarbamate absorbent (Fe₃O₄@SiO₂-DTC) with core-shell structure was applied for aqueous solution heavy metal ions Ni²⁺, Cu²⁺ removal.     

4-Mercaptophenylacetic acid functionalized Mn2+-doped ZnS nanoparticles fluorescence quenching caused by the addition of Cu2+

This paper reports that 4-mercaptophenylacetic acid functionalized Mn²⁺-doped ZnS nanoparticles (4-MPAA-ZnS-Mn²⁺ NPs) as fluorescent probes for the detection of copper ions in solution. The fluorescence quenching was due to the aggregation of copper ions with 4-MPAA-ZnS-Mn²⁺ NPs. These aggregations were confirmed by using UV lamp, UV–visible spectroscopy and dynamic light scattering (DLS). These 4-MPAA-ZnS-Mn²⁺ NPs were applied as fluorescent probes to detect copper ions in aqueous solution.     

Signal‐Induced Release of Guests from a Photolatent Metal–Phenolic Supramolecular Cage and Its Hybrid Assemblies

The coordination chemistry of plant polyphenols and metal ions can be used for coating various substrates and for creating modular superstructures. We herein explored this chemistry for the controlled release of guests from mesoporous silica nanoparticles (MSNs). The selective adsorption of tannic acids (TAs) on MSN silica walls opens the MSN mesoporous channels without disturbing mass transport. The channel may be closed by the coordination of TA with Cu^II ions. Upon exposure to light, photolysis of Trojan horse guests (photoacid generators, PAGs) leads to acid generation, which enables the release of payloads by decomposing the outer coordination shell consisting of TA and Cu^II. We also fabricated a modular assembly of MSNs on glass substrates. The photoresponsive release characteristics of the resulting film are similar to those of the individual MSNs. This method is a fast and facile strategy for producing photoresponsive nanocontainers by non‐covalent engineering of MSN surfaces that should be suitable for various applications in materials science.     

Copper and Nickel Removal from Aqueous Solutions Using New Chelating Poly[Acrylamide/N‐vinyl pyrrolidone/3‐(2‐hydroxyethyl carbamoyl)acrylic acid] Hydrogels

New poly[Acrylamide/N‐vinyl pyrrolidone/3‐(2‐hydroxyethyl carbamoyl)acrylic acid], poly [AAm/NVP/HECA], chelating hydrogels with different composition of HECA monomer have been prepared via free radical solution polymerization using N,N‐methylene bisacrylamide as a crosslinker. The hydrogels obtained were loaded with metal ions and characterized by FT‐IR spectroscopy, Scanning Electron Microscope (SEM) and Thermogravimatric analysis (TGA). The removal of Cu²⁺ and Ni²⁺ from aqueous solutions by the hydrogel was examined by a batch equilibrium method. The influence of treatment time, pH, initial concentration of the metal ions and HECA content in the feed compositions on the amount of adsorbed metal ions was studied. Swelling of the hydrogel was also carried out in distilled water and metal ion solutions. The removal of the metal ions followed the following order: Ni²⁺>Cu²⁺. The amount of metal ions removed increased with increasing HECA content in the feed composition, treatment time, pH of the medium and initial concentration of metal ions. The desorption of metal ions were carried out using 1 N HCl and 0.5 N H₂SO₄. The poly[AAm/NVP/HECA] hydrogels could be used many times without significantly decreasing their adsorption capacity.     

Signal-Induced Release of Guests from a Photolatent Metal–Phenolic Supramolecular Cage and Its Hybrid Assemblies

The coordination chemistry of plant polyphenols and metal ions can be used for coating various substrates and for creating modular superstructures. We herein explored this chemistry for the controlled release of guests from mesoporous silica nanoparticles (MSNs). The selective adsorption of tannic acids (TAs) on MSN silica walls opens the MSN mesoporous channels without disturbing mass transport. The channel may be closed by the coordination of TA with Cu^II ions. Upon exposure to light, photolysis of Trojan horse guests (photoacid generators, PAGs) leads to acid generation, which enables the release of payloads by decomposing the outer coordination shell consisting of TA and Cu^II. We also fabricated a modular assembly of MSNs on glass substrates. The photoresponsive release characteristics of the resulting film are similar to those of the individual MSNs. This method is a fast and facile strategy for producing photoresponsive nanocontainers by non-covalent engineering of MSN surfaces that should be suitable for various applications in materials science.     

Trace metal speciation measurements in waters by the liquid binding phase DGT device

The speciation measurements of trace metals by the diffusive gradients in thin-films technique (DGT) using a poly(4-styrenesulfonate) (PSS) aqueous solution as a binding phase and a cellulose dialysis membrane (CDM) as a diffusive layer, CDM-PSS DGT, were investigated and showed good agreement with computer modelling calculations. The diffusion coefficients of ethylenediaminetetraacetic acid (EDTA) complexes with Cd²⁺ and Cu²⁺ were measured and compared with those of the inorganic metal ions. CDM-PSS DGT device was tested for speciation measurement in sample solutions containing EDTA, tannic acid (TA), glucose (GL), dodecylbenzenesulfonic acid (DBS) and humic acid (HA) as complexing ligands forming organic complexes with varying stability constants. Lower percentages of DGT labile copper concentrations over total filterable copper concentrations obtained from the deployments in freshwater sites indicated that copper complexes with organic matter were basically not measured by the devices.     

Competitive heavy metal removal by poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid‐co‐itaconic acid)

The competitive removal of Pb²⁺, Cu²⁺, and Cd²⁺ ions from aqueous solutions by the copolymer of 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid (AMPS) and itaconic acid (IA), P(AMPS‐co‐IA), was investigated. Homopolymer of AMPS (PAMPS) was also used to remove these ions from their aqueous solution. In the preparation of AMPS–IA copolymer, the molar percentages of AMPS and IA were 80 and 20, respectively. In order to observe the changes in the structures of polymers due to metal adsorption, FTIR spectra by attenuated total reflectancetechnique and scanning electron microscopy (SEM) pictures of the polymers were taken both before and after adsorption experiments. Total metal ion removal capacities of PAMPS and P(AMPS‐co‐IA) were 1.685 and 1.722 mmol Me²⁺/g_polymer, respectively. Experimental data were evaluated to determine the kinetic characteristics of the adsorption process. Competitive adsorption of Pb²⁺, Cu²⁺, and Cd²⁺ ions onto both PAMPS and P(AMPS‐co‐IA) was found to fit pseudo‐second‐order type kinetics. In addition, the removal orders in the competitive adsorption of these metal ions onto PAMPS and P(AMPS‐co‐IA) were found to be Cd²⁺ > Pb²⁺ > Cu²⁺ and Pb²⁺ > Cd²⁺ > Cu²⁺, respectively. Copyright © 2008 John Wiley & Sons, Ltd.     

Application of Crosslinked Ionic Poly(Vinyl Alcohol) Nanogel as Adsorbents for Water Treatment

Core-shell smart ionic nanogels based on poly(vinyl alcohol) (PVA) core and poly(N-isopropylacrylamide/acrylic acid) p(NIPAm-AAc) shell particles were successfully synthesized through a one-step surfactant-free emulsion polymerization method (SFEP). Different mole ratios of p(NIPAm-AAc) shells were synthesized. The morphologies of PVA/p(NIPAm-AAc) nanogels were investigated by transmission electron microscope (TEM). The data showed the formation of spherical nanoparticles and well-defined core-shell nanogels. PVA/p(NIPAm-AAc) core-shell nanogels were applied as a novel polymeric adsorbent to remove heavy metal pollutants from aqueous solution. Copper(II) (Cu²⁺) ions were selected as the target pollutant to evaluate these nanoparticles’ adsorption capability. The influence of the uptake conditions such as pH, weight ratio of nanoparticles, time, initial feed concentration, and adsorption temperature on the metal ion binding capacity of nanogels was also tested. Adsorption equilibrium data were calculated according to Langmuir and Freundlich isotherms. It was found that the sorption of Cu²⁺ was better suited to the Freundlich adsorption model than the Langmuir adsorption model. Also, the selectivity of the nanogels toward the different metal ions such lead (Pb²⁺) and cadmium (Cd²⁺) were tested. The maximum of Cu²⁺ ions adsorbed on to PVA/p(NIPAm-AAc) core-shell nanogels adsorbent was 94 mg/g obtained under simple and fast experimental conditions, indicating these nanogels can be used as effective and practical polymeric adsorbents.     

Cuprous oxide nanospheres as probes for light scattering imaging analysis of live cells and for conformation identification of proteins

A facile solution-phase synthesis route of highly uniform Cu₂O nanospheres (Cu₂O NPs) with the size of 57.7 ± 4.7 nm was developed, and then the nanoparticles were applied to live cell imaging under a common dark-field microscope. Starting from copper(II) salts, the synthesis of Cu₂O NPs was made in the presence of cetyltrimethylammonium bromide (CTAB) by reducing the copper(II) with sodium borohydride (NaBH₄) in aqueous medium and by aging process in the air. Monitoring of morphology evolution process of Cu₂O NPs with scanning electron microscopy (SEM) and measuring of the UV-visible spectra showed that the synthesis of Cu₂O NPs follows the reduction-oxidation coupled process of Cu²⁺ into Cu⁰ species at first and then the resulted Cu⁰ species into Cu₂O NPs in the air. Light scattering (LS) features have been measured with a common spectrofluorometer and a common dark-field microscope, and it was found that the as-prepared Cu₂O NPs display strong blue scattering light and can be applied for cell imaging. If incubated with human bone marrow neuroblastoma, transferrin-conjugated Cu₂O NPs can get into the cells and show strong pure blue light in cytoplasm. Further investigations showed that the Cu₂O NPs could be applied for probes for conformation of proteins.     

Highly Luminescent Colloidal Eu3+‐Doped KZnF3 Nanoparticles for the Selective and Sensitive Detection of CuII Ions

This article describes a green synthetic approach to prepare water dispersible perovskite‐type Eu³⁺‐doped KZnF₃ nanoparticles, carried out using environmentally friendly microwave irradiation at low temperature (85 °C) with water as a solvent. Incorporation of Eu³⁺ ions into the KZnF₃ matrix is confirmed by strong red emission upon ultraviolet (UV) excitation of the nanoparticles. The nanoparticles are coated with poly(acrylic acid) (PAA), which enhances the dispersibility of the nanoparticles in hydrophilic solvents. The strong red emission from Eu³⁺ ions is selectively quenched upon addition of Cu^II ions, thus making the nanoparticles a potential Cu^II sensing material. This sensing ability is highly reversible by the addition of ethylenediaminetetraacetic acid (EDTA), with recovery of almost 90 % of the luminescence. If the nanoparticles are strongly attached to a positively charged surface, dipping the surface in a Cu^II solution leads to the quenching of Eu³⁺ luminescence, which can be recovered after dipping in an EDTA solution. This process can be repeated for more than five cycles with only a slight decrease in the sensing ability. In addition to sensing, the strong luminescence from Eu³⁺‐doped KZnF₃ nanoparticles could be used as a tool for bioimaging.     

Tannic Acid Modified Electrochemical Biosensor for Glucose Sensing Based on Direct Electrochemistry

A novel glucose biosensor was constructed through the immobilization of glucose oxidase (GOx) on gold nanoparticles (Au NPs) deposited, and chemically reduced graphene oxide (rGO) nanocomposite. In the synthesis, tannic acid (TA) was used for the reduction of both graphene oxide, and Au³⁺ to rGO, and Au NPs, respectively. Also, by harnessing the π‐π interaction between graphene oxide and TA, and protein‐TA interaction, a novel nanocomposite for the fabrication of a third generation biosensor was successfully constructed. Upon the oxidation of TA to quinone, which is easily reducible at the negative potential range, enhanced electron transfer was obtained. The cyclic voltammetry (CV) results demonstrated a pair of well‐defined and quasi‐reversible redox peaks of active site molecule of GOx. The biosensor exhibited a linear response to glucose concentrations varying from 2 to 10 mM with a sensitivity of 18.73 mA mM⁻¹ cm⁻². The fabricated biosensor was used for the determination of glucose in beverages.