Synthesis and fluorescence properties of novel 1,10‐phenanthroline‐functionalized polyaryletherketone and its rare earth complexes

1,10‐Phenanthroline‐functionalized polyaryletherketone (PPEK) was synthesized by the amidation reaction of 5‐amino‐1,10‐phenanthroline with polyaryletherketone containing pendant acyl chloride groups. Subsequently, a series of novel rare earth coordination polymers (with rare earths Eu³⁺, Tb³⁺, Sm³⁺ and Dy³⁺) were prepared, using PPEK as macromolecular ligand and the small 1,10‐phenanthroline (Phen) molecule as synergistic ligand. Their structures were characterized using Fourier transform infrared spectroscopy, elemental analysis and X‐ray diffraction, which confirmed that both PPEK and Phen participated in the coordination reaction with the rare earth ions, and that the rare earth ions could disperse homogeneously in the polymer matrix. The rare earth coordination polymers were soluble in polar solvents such as N,N‐dimethylformamide, N,N‐dimethylacetamide and N‐methylpyrrolidone, and could be easily cast into transparent tough thin films. Fluorescence measurements indicated that all the coordination polymers exhibited the intense characteristic fluorescence of the corresponding rare earth ions under ultraviolet excitation, showing their application potential in optical display devices. Copyright © 2010 Society of Chemical Industry     

Synthesis of functionalized polymeric adsorbent selective to cobalt

Amino derivative of chloromethylated polystyrene resin was synthesized and functionalized by 1,10‐phenanthroline (1,10‐Phen) to yield a novel adsorbent, namely 4‐methylamino‐[N,N‐bis(2,2^′)‐1,10‐phenanthroline] polystyrene ( 4‐MABPPS ). The complete development of novel adsorbent along with its characterization is described in detail. The adsorption ability and selectivity of 4‐MABPPS were investigated for cobalt and zirconium ions so as to efficiently separate cobalt ion impurities from zircalloy cladding material of nuclear reactors. The experimental results showed selective uptake of cobalt by the adsorbent in the presence of zirconium. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of functionalized ion‐imprinted phenolic polymer for efficient removal of copper ions

In this work, an ion‐imprinted polymeric material based on functionalized phenolic resin was developed for the efficient selective removal of Cu²⁺ ions from aqueous solution. p‐Aminophenol‐isatin Schiff base ligand (HPIS) was first synthesized and combined with Cu²⁺ ions to prepare the corresponding complex [Cu(PIS)₂]. The Schiff base ligand along with its copper complex was fully investigated and characterized before anchoring in a base‐catalyzed condensation copolymerization with formaldehyde and resorcinol. The Cu²⁺ ions were removed from the obtained resin construction and the resulting Cu²⁺ ion‐imprinted material (Cu‐PIS) was employed for the selective extraction of Cu²⁺ ions under different pH values, initial concentrations and contact time conditions. The optimum pH for the removal process was chosen as 6 and the maximum adsorption capacity was 187 ± 1 mg g^–1. Also, the kinetics showed a better fit with the pseudo‐second‐order equations. The selectivity of the prepared Cu‐PIS was also evaluated in a multi‐ionic species containing Ni²⁺, Cd²⁺, Pb²⁺, Co²⁺ besides Cu²⁺ ions and the determined parameters confirmed a superior recognition capability toward the imprinted Cu²⁺ ions. © 2019 Society of Chemical Industry     

Synthesis and structural characterization of a new polysiloxane with second‐order nonlinear optical effect

A new polysiloxane ( P2 ), with a high density of the indole‐based chromophore and carbazolyl side groups, was prepared. Thus a polysiloxane ( P1 ), with indole and carbazolyl groups as side chains, was first synthesized through a hydrosilylation reaction, and then the post‐azo coupling of p‐nitrobenzenediazonium fluoroborate toward the indole ring gave the mulifunctional indole‐based chromophore‐functionalized polysiloxane ( P2 ). Molecular structural characterization for the polymers was determined by ¹H‐NMR, IR, and UV–visible spectra, gel permeation chromatography, and differential scanning calorimetry. The polymers were easily soluble in common organic solvents. The poled film of P2 revealed a resonant d₃₃ value of 27 pm/V by second‐harmonic generation measurements. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 769–774, 2004     

Template Synthesis of Iminodiacetic Acid Polysiloxane Immobilized Ligand Systems and their Metal Uptake Capacity

Porous solid polysiloxane ligand systems bearing an iminodiacetic acid chelating ligand of the general formula P-IDA (where P- represents [Si-O] _n polysiloxane network and IDA represent an organofunctional group) were achieved in two-step reaction. The first step includes a template synthesis of 3-iodopropylpolysiloxane (P-I) or 3-aminopropylpolysiloxane (P-MA) by hydrolytic polycondensation of TEOS and the corresponding silane agent in the presence of CTAB as a surfactant. The second step includes a modification of 3-iodopropylpolysiloxane with diethyliminodiacetate or 3-aminopropylpolysiloxane with ethylchloroacetate to produce IDA-functionalized polysiloxane ligand systems P-IDA-I & P-IDA-II respectively. It was found that the modified IDA-functionalized polysiloxane ligand systems exhibited higher capacities for uptake of the metal ions (Ni ²⁺, Cu ²⁺ and Pb ²⁺) than those prepared without surfactants.     

Synergistic Extraction of Lanthanides(III) by Mixtures of N‐p‐Methoxybenzoyl‐N‐phenylhydroxylamine and 1,10‐Phenanthroline

Abstract

We conducted a study on the equilibrium extraction behavior of the trivalent lanthanide ions (M³⁺), La, Pr, Eu, Ho, and Yb, from tartrate aqueous solutions into chloroform solutions containing N‐p‐methoxybenzoyl‐N‐phenylhydroxylamine (Methoxy‐BPHA, HL) and 1,10‐phenanthroline (phen). The synergistic species extracted was found to be {ML₂(phen) (HL)}⁺(1/2)Tar^2?, where Tar^2? is tartrate ion. The extraction constants were calculated. The extraction separation behavior and extractability of lanthanides are discussed in comparison with the self‐adducted chelate, ML₃(HL)₂, which was extracted in the absence of phen, and synergistic extraction by mixtures of other extractants such as 2‐thenoyltrifluoroacetone, and neutral donors.     

Polythiophene based fluorescent probe for copper ions with high sensitivity

Two new conjugated polymers poly{3‐({4‐[(2‐hydrazino‐2‐oxoethyl)(methyl)amino]cyclohexylidene}methyl)thiophene}( P1 ) and poly{3‐({4‐[(3‐hydrazino‐3‐oxopropyl)(methyl)amino]cyclohexylidene}methyl)thiophene}( P2 ) were synthesized, and their optical properties were investigated. P1 exhibited excellent selectivity toward Cu²⁺ ions in 50% water solution, the fluorescence color of P1 changed distinctly from greenyellow to colorless in the presence of Cu²⁺ under UV‐light, while introduction of other metal ions could not induce such significant variation. Moreover, highly sensitive detection of Cu²⁺ ions was demonstrated in 90% water solution. Its high metal‐chelating capability allowed Cu²⁺ recognition with a detection limit of 3.2 × 10^?10 M. These results indicated that this kind of nonionic polymer containing multidentate ligand could be used as a highly selective and sensitive chemosensor for Cu²⁺ detection. The proposed binding mode of P1 with Cu²⁺ was supported by DFT calculation using Gaussian 03. Unlike P1 , P2 showed no obvious fluorescent change in the presence of various metal ions due to its space steric hindrance resulted from N/O distribution on the side chain of P2 . © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42440.     

Thioether‐Functionalized Corn Oil Biosorbents for the Removal of Mercury and Silver Ions from Aqueous Solutions

Heavy‐metal contamination is one of the most important environmental problems faced in the world, particularly in developing countries. Metals such as silver and mercury from drinking water, food, and air sources can accumulate in living organisms and present significant health concerns. Meanwhile, the demand for these metals in many industries continues to increase. In the present study, thioether‐functionalized corn oil (TFCO) from a photoinitiated thiol‐ene synthesis was utilized to remove Ag⁺ and Hg²⁺ ions from an aqueous solution. An aqueous solution containing AgNO₃ and Hg[NO₃]₂ was prepared and contacted directly with TFCO. After vortex mixing for 60 s, the experiment ran for 351 min with the aqueous phase being periodically sampled for the analysis of metal ions (M ⁿ⁺). Results showed that 88.9% of Ag⁺ and 99.6% of Hg²⁺ ions were removed from the aqueous phase by the TFCO. Mass balances indicated that the total M ⁿ⁺ concentration in the oil phase was 13.890 g kg^?1 under the conditions studied. TFCO exhibited higher selectivity for removing Hg²⁺ than for Ag⁺ ions. Analysis of the adsorption kinetics showed that a pseudosecond‐order model may be used to determine the rate of Ag⁺ ion sorption by the oil phase. The presence of the Hg²⁺ ions interfered with the adsorption of Ag⁺ ions from the aqueous solution.     

Synthesis of azo‐functionalized ion‐imprinted polymeric resin for selective extraction of nickel(II) ions

The work presented involved the fabrication and evaluation of an ion‐imprinted azo‐functionalized phenolic resin for selective extraction of Ni²⁺ ions from aqueous media. The azo‐containing ligand was first synthesized by coupling of a p‐aminophenol diazonium salt with resorcinol. The ligand was coordinated with Ni²⁺ ion template before condensation polymerization with formaldehyde and resorcinol was performed. The Ni²⁺ ions were extracted from the crosslinked resin matrix to finally afford the Ni²⁺ ion‐imprinted Ni‐PARF adsorbent. The synthetic steps were extensively investigated using elemental analysis and Fourier transform infrared, NMR and energy‐dispersive X‐ray spectroscopies. Also, the surface morphologies along with the surface areas of the adsorbent resin were evaluated using scanning electron microscopy and Brunauer–Emmett–Teller techniques, respectively. Batch experiments indicated that the pseudo‐second‐order kinetic equation provided the best fit with the experimentally obtained kinetic data and equilibrium was reached after 40 min. The isotherm studies were also in a good fit with the Langmuir model and the maximum adsorption capacities of Ni²⁺ ions with respect to both Ni‐PARF and control non‐imprinted C‐PARF adsorbents were around 260 and 100 mg g^?1, respectively. In the presence of Co²⁺, Cu²⁺, Zn²⁺ and Pb²⁺ as competing coexisting ions, the relative selectivity coefficients of Ni‐PARF for Ni²⁺ were, respectively, 84.91, 44.97, 30.41 and 32.20. Regeneration experiments indicated that after eight adsorption/desorption cycles, the Ni‐PARF adsorbent still maintained around 97% of its initial efficiency. © 2018 Society of Chemical Industry     

Acrylamide‐plasma treated electrospun polystyrene nanofibrous adsorbents for cadmium and nickel ions removal from aqueous solutions

The aim of this work was to prepare novel electrospun polystyrene (PS) nanofibrous samples functionalization with acrylamide monomer (AAm) as promising nanoadsorbents by the use of nitrogen gas plasma. To investigate the performance evaluation of the samples for adsorbing cadmium (Cd²⁺) and nickel (Ni²⁺) ions, a series of tests in terms of ATR‐FTIR spectroscopy, FE‐SEM, water contact angle (WCA) measurements and atomic adsorption spectroscopy were carried out. The ATR‐FTIR results showed that nitrogen (N₂) plasma was an efficient tool because of the formation of functionalized AAm‐PS nanofibrous samples by providing amide (?NCO) and amine (?NH?) groups onto their surfaces. The WCA measurements demonstrated that the N₂ plasma‐modified samples in the presence of AAm had a lower contact angle of 42.8º than the other samples. Moreover, FE‐SEM micrpgraph images of AAm‐treated PS nanofibrous samples indicated that approperiate amount of the functional groups onto the samples surfaces were deposited. Afterwards, AAS analysis along with Langmuir and Freundlich's isotherm models revealed that a high adsorption of the ions was occurred at pH 5 in the order Cd²⁺ (10 mg g^?1) > Ni²⁺ (4.9 mg g^?1) by using the nanoadsorbents dosage 1 g L^?1 and the metal ions concentration 25 mg L^?1. In addition, the obtained results exhibited the Cd²⁺ and Ni²⁺ ions removal efficiencies (%R) were increased up to 96% and 94%, respectively with raising the nanoadsorbents dosage. Moreover, the equilibrium adsorption of the ions showed the best fitting by the Freundlich's model. Finally, the desorption of the optimized samples for regenerating them owing to the effective removal of the ions has been confirmed by applying the recyclability test. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42944.     

Silica‐based iminodiacetic acid functionalized adsorbent for Ni hydrometallurgical extraction of nickeliferous laterite

A novel silica‐based iminodiacetic acid functionalized adsorbent was fabricated and then used to nickel hydrometallurgical extraction for low‐grade nickeliferous laterites. The surface morphology of the adsorbent was characterized by scanning electron microscopy. The adsorption experiment indicated a maximum nickel load capacity of about 0.45 mmol/g. Analysis of adsorption thermodynamic and kinetics revealed a spontaneous adsorption process driven by entropy increase, and limited by film diffusion. Semi‐industrial scale column experiments revealed that the Ni²⁺ in the acidic leach liquor of low‐grade nickeliferous laterites may be efficiently extracted by the iminodiacetic acid functionalized adsorbent, if the Fe³⁺ ions existing in the acidic leach liquor were previously reduced to be Fe²⁺ by sodium sulfite. This environmentally safe adsorbent may supplant the traditional solvent extraction process for low‐grade nickeliferous laterites. © 2012 American Institute of Chemical Engineers AIChE J, 2012     

C,N‐Pyridylpyrazole‐Based Ligands: Synthesis and Preliminary Use in Metal Ion Extraction

Abstract

The synthesis of new N‐donor pyridylpyrazole ligands with a functionalized arm is described. The complexation capabilities of these compounds towards bivalent metal ions (Hg²⁺, Cd²⁺, Pb²⁺, Cu²⁺, and Zn²⁺) and alkali metal ions (K⁺, Na⁺, and Li⁺) were investigated using the liquid‐liquid extraction process. The percentage limits of extraction were determined by atomic absorption measurements.     

Removal of phosphate ions with a chemically modified chitosan/metal‐ion complex

The adsorption of metal ions (Mo⁶⁺, Cu²⁺, Fe²⁺, and Fe³⁺) was examined on chemically modified chitosans with a higher fatty acid glycidyl (CGCs), and the adsorption of Cu²⁺ was examined on ethylenediamine tetraacetic acid dianhydride modified CGCs (EDTA‐CGCs) synthesized by the reaction of the CGCs with ethylenediamine tetraacetic acid dianhydride. The adsorption of phosphate ions onto the resulting substrate/metal‐ion complex was measured. Mo⁶⁺ depicted remarkable adsorption toward the CGCs, although all the Mo⁶⁺ was desorbed under the adsorption conditions of the phosphate ions. The other metal ions were adsorbed to some extent on CGCs by chelating to the amino group in the substrate, except for CGC‐1, which had the highest degree of substitution (83.9%). Considerable amounts of Fe²⁺ were adsorbed onto CGCs; however, only a limited number of phosphate ions was adsorbed onto the substrate/metal‐ion complex. As a result, the following adsorbent/metal‐ion complexes gave higher adsorption ability toward phosphate ions: CGC‐4/Cu²⁺, CGC‐4/Fe³⁺, and EDTA‐CGC‐3/Fe³⁺. Where, CGC‐3 is a chemically modified chitosan with the degree of substitution of 26.5 percentage, and CGC‐4 is one with the degree of substitution of 16.0 percentage. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and magnetic properties of novel fully conjugated polymeric complexes containing 1,10‐phenanthroline

A novel fully conjugated polymer containing 1,10‐phenanthroline (DAPcDOD) was first synthesized by the polycondensation of 2,7‐dimethyl‐2,4,6‐octatriene‐1,8‐dial with 5,6‐diamine‐1,10‐phenanthroline. Three polymeric complexes were first prepared by the reaction of DAPcDOD with NiSO₄, CoCl₂, and FeSO₄, respectively. The structures of the polymer and the complexes were characterized by IR, ¹H‐NMR, and elemental analysis. The magnetic behaviors of these complexes were measured as a function of magnetic field strength (0–50 kOe) at 5 K and as a function of temperature (5–300 K) at a magnetic field strength of 30 kOe. The results show that DAPcDOD–Ni²⁺ and DAPcDOD–Co²⁺ were soft ferromagnets, whereas DAPcDOD–Fe²⁺ exhibited the features of an antiferromagnet. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synergistic Extraction of Lanthanides(III) with N‐p‐Methoxybenzoyl‐N‐Phenylhydroxylamine and Neutral Nitrogen Donors

Abstract

We investigated the extraction equilibrium behavior of a series of trivalent lanthanide ions, (M³⁺), La, Pr, Eu, Ho, and Yb, from tartrate aqueous solutions using a chloroform solution containing N‐p‐methoxybenzoyl‐N‐phenylhydroxylamine (Methoxy‐BPHA or HL) combined with an adductant, 1,10‐phenanthroline (phen) or 2,2′‐bipyridyl (bipy). The synergistic species extracted were found to be {ML₂(phen)(HL)}⁺(1/2)Tar^2? and {ML₂(bipy)(HL)₂}⁺(1/2)Tar^2?, where Tar^2? is the tartrate ion. The stoichiometry, the extraction constants, and the separation factors of these systems were determined. We discuss the extractability and the separation factors in comparison with self‐adduct chelates, ML₃(HL)_2,(o), which were formed in the absence of phen or bipy.     

Synthesis,photochemical characterization,and thermal stability of a series of substituted formamidines as ultraviolet light absorbers

The three‐step reactions of ethyl 4‐aminobenzoate, formic acid, and halohydrocarbons afforded 10 N‐substituted‐N,N′‐diaryl‐formamidine derivatives ( F1 – 10 ) as ultraviolet absorbers. These N‐substituted formamidines were characterized by ¹H NMR, ¹³C NMR, FT‐IR, and ESI‐MS spectroscopies. The UV–vis absorbance and fluorescence properties of the compounds F1 – 10 were investigated in different solvents and in the presences of different metal ions. The effects of the amount of Al³⁺, Pb²⁺, Zr⁴⁺ ions on the UV–vis absorbance and fluorescence properties of compound F1 were also investigated. Moreover, the thermal stability of the compounds F1 – 10 was evaluated as well as the intermediate N,N′‐bis(4‐ethoxycarbonylphenyl)‐formamidine. J. VINYL ADDIT. TECHNOL., 25:E108–E113, 2019. © 2019 Society of Plastics Engineers     

Electrochemical properties of ferrocene modified polysiloxane/chitosan nanocomposite and its application to glucose sensor

A ferrocene functionalized polysiloxane was synthesized and its composite with chitosan was prepared. The electrochemical properties in solution and in immobilized states were examined for both the ferrocene functionalized polysiloxane and its composite with chitosan. The composite film exhibits a reversible redox wave at E°′ = +360 mV vs. Ag/AgCl which is 110 mV more negative than that of the ferrocene functionalized polysiloxane film. It can be explained by the introduction of chitosan to enhance the hydrophilicity of the film and increase mass transport rate in aqueous condition. The composite film shows a very facile electron transport behavior with an apparent diffusion coefficient of 3.5 × 10⁻⁶ cm²/s. The scanning electron microscopic analysis of the film, which is in dried state, reveals that the ferrocene polysiloxane forms average 500 nm size spheres and those are evenly distributed in the chitosan matrix to give a homogeneous nanocomposite. The significantly large value of the apparent diffusion coefficient of the ferrocene moieties in the composite film can be explained by the introduction of highly hydrophilic character to the film originated from the high water-uptake capability of chitosan to give solution-like behaviors of the film in solution. The composite is found to be a useful platform to host enzymes to make biosensors and glucose sensing capability is demonstrated.     

Influence of the Metal Ions Cr3+, Fe3+, Ni2+ and Cu2+ on the Stability and Oxygen Consumption of Acrylic and Methacrylic Acid

For the safe and trouble‐free operation of a manufacturing plant and the safe storage of acrylic, as well as methacrylic monomers, it is important to know the polymerization stability as a function of the process parameters (temperature, oxygen concentration, and impurities, e.g., metal ions). Contamination with metal ions can be caused by the corrosion of steel units. Therefore, the influence of the metal ions Cr³⁺, Fe³⁺, Ni²⁺ and Cu²⁺ in the concentration range of 0–10 ppm (g g^–1) on the polymerization behavior and the oxygen consumption of acrylic and methacrylic acid were examined in this work. It was shown that Cr³⁺, Ni²⁺, and Cu²⁺ ions extend the inhibition period of acrylic acid (AA) and methacrylic acid (MAA) and reduce the O₂ consumption. Fe³⁺ ions, however, cause a decrease of the inhibition period and in the case of AA an increase of the O₂ consumption, which leads, in the end, to a faster unintentional polymerization. Therefore, alloys which contain iron should be avoided as far as possible in the construction of AA plants. Fe³⁺‐ions show the opposite influence towards MAA, here the presence of Fe³⁺ shows a stabilizing effect.     

Wide‐range thermometry based on green up‐conversion luminescence of K3LuF6:Yb3+/Er3+ bulk oxyfluoride glass ceramics

Yb³⁺/Er³⁺ ions codoped bulk glass ceramics (GC) with embedded monoclinic K₃LuF₆ nanocrystals are reported for potential temperature‐sensing application by using the fluorescence intensity ratio method. Such GC with good transparency and enhanced up‐conversion were prepared by the simple conversional melt‐quenching method and subsequent annealing process. Optical, structural, and temperature‐sensing up‐conversion properties were characterized systematically. Optical spectroscopy analysis confirms the incorporation of Yb³⁺/Er³⁺ into the K₃LuF₆ crystalline lattice, resulting in enhanced up‐conversion luminescence. Compared to other Er³⁺‐doped typical systems, Er³⁺ ions in K₃LuF₆ GC present large energy gap (870 cm^?1) and high relative sensitivity (37.6 × 10^?4 K^?1 at 625 K), revealing that K₃LuF₆:Yb³⁺/Er³⁺ GC can be excellent candidates for optical thermometers.     

Preparation of thiourea functionalized polyvinyl alcohol‐coated magnetic nanoparticles and their application in Pb2+ ions adsorption

We have prepared a novel kind of magnetic nanoparticle with high adsorption capacity and good selectivity for Pb²⁺ ions by modifying the magnetic nanoparticles with polyvinyl alcohol (PVA) and thiourea. The resultant magnetic nanoparticles were used to adsorb Pb²⁺ ions from aqueous solution. The influence of the solution pH, the adsorption time, the adsorption temperature, coexisting ions, and the initial concentration of Pb²⁺ ions on the adsorption of Pb²⁺ ions were investigated. The results indicated that Pb²⁺ ions adsorption was an endothermic reaction, and adsorption equilibrium was achieved within 30 min. The optimal pH for the adsorption of Pb²⁺ ions was pH 5.5, and the maximum adsorption capacity of Pb²⁺ ions was found to be 220 mg/g. Moreover, the coexisting cations such as Ca²⁺, Co²⁺, and Ni²⁺ had little effect on adsorption of Pb²⁺ ions. The regeneration studies showed that thiourea functionalized PVA‐coated magnetic nanoparticles could be reused for the adsorption of Pb²⁺ ions from aqueous solutions over five cycles without remarkable change in the adsorption capacity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40777.