Templated synthesis of silver nanoparticles in amphiphilic poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) comb copolymer

In this study, poly(vinylidene fluoride‐co‐chlorotrifluoroethylene)‐graft‐poly(oxyethylene methacrylate), P(VDF‐co‐CTFE)‐g‐POEM, an amphiphilic comb copolymer with hydrophobic P(VDF‐co‐CTFE) backbone and hydrophilic POEM side chains at 73:27 wt % was synthesized. The POEM side chains were grafted from the P(VDF‐co‐CTFE) mainchain backbone via atom transfer radical polymerization (ATRP) using direct initiation of the chlorine atoms in CTFE units. Synthesis of microphase‐separated P(VDF‐co‐CTFE)‐g‐POEM comb copolymer was successful, as confirmed by nuclear magnetic resonance (¹H NMR), FTIR spectroscopy, and transmission electron microscopy (TEM). Nanocomposite films were prepared using the comb copolymer as a template film and the in situ reduction of AgCF₃SO₃ precursor to silver nanoparticles under UV irradiation. Silver nanoparticles with 4–8 nm in average size were in situ created in the solid state template film, as revealed by TEM, UV–visible spectroscopy, and wide angle X‐ray scattering (WAXS). Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) presented the selective incorporation and the in situ growth of silver nanoparticles within the hydrophilic POEM domains of microphase‐separated comb copolymer film. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 702–709, 2008     

Preparation of highly sensitive sensors based on polystyrene microspheres for the detection and removal of Hg2+ ions

Detection and the simultaneous removal of mercury ions are of vital importance. In this study, fluorescent monomers, small molecular sensors, were first synthesized using 4‐bromo‐naphthalic anhydride as precursor. These double bond bearing sensors were then grafted to polystyrene (PS) microspheres through dispersion polymerization. The sensors still retained their detecting ability when they were anchored on the surfaces of PS microspheres. Upon the addition of Hg²⁺ ions to the PS microspheres, both the color and the fluorescence intensity changed, which could be employed to detect Hg²⁺ ions. The absorption capacity of the two kinds of PS microspheres reached 0.557 mg g^?1 and 0.628 mg g^?1 respectively. The PS microspheres still remain their fluorescence and absorption even used for five times. These polymeric highly sensitive chemosensors may see their applications in purification of polluted environments. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4592–4600     

Use of unmodified silver nanoparticles (AgNPs) as colorimetric Hg(II) sensor: A new approach to sensitive and high sample throughput determination of Hg(II) under high influence of ionic suppression

Facile unmodified silver nanoparticles (AgNPs) as colorimetric sensor for determination of Hg(II) ions in aqueous samples were developed using UV-Vis spectrophotometry. Abrupt change in absorbance of the AgNPs was observed, which progressively decreased and slightly shifted to the blue wavelength as the concentration of Hg(II) increased. It appears that the AgNPs were oxidized by Hg(II), resulting in disintegration of the AgNPs and Hg(0). Deposition of Hg(0) on the surface of AgNPs also occurred, resulting in amalgam particles of mercury (Hg-Ag). Interestingly, the developed approach showed a significant enhancement in the Hg(II) analytical sensitivity when formic acid was doped onto the AgNPs, with the linearity range of 0.01–10 mg L^?1 (r² = 0.999) providing the quantitative detection limit of 0.007 mg L^?1 (3SD blank/slope of the calibration curve). Greater selectivity toward Hg(II) over other ions and colour dyes was also observed, likely a result of stabilization by polyvinylpyrrolidone (PVP), which kept the AgNPs well-stabilized and dispersed in the bulk aqueous environment making them resistant to ionic suppression. Under using a 96-well microplate and a smartphone equipped with homemade application as a colorimetric analyzer under controlled lighting, high sample throughput (128 sample h^?1, n = 4) was achieved, establishing its potential for practical analysis. The percentage recoveries of spiked aqueous samples obtained from the microplate-based system were in acceptable range, in agreement with the values obtained from the UV-Vis spectrophotometry-based system. The proposed colorimetric sensor has been shown to provide a rapid, simple, sensitive and selective detection of Hg(II) ions in various aqueous samples.     

Hydroxyl‐terminated hyperbranched aromatic poly(ether‐ester)s: Synthesis,characterization, end‐group modification,and optical properties

Novel AB₂‐type monomers such as 3,5‐bis(4‐methylolphenoxy)benzoic acid ( monomer 1 ), methyl 3,5‐bis(4‐methylolphenoxy) benzoate ( monomer 2 ), and 3,5‐bis(4‐methylolphenoxy)benzoyl chloride ( monomer 3 ) were synthesized. Solution polymerization and melt self‐polycondensation of these monomers yielded hydroxyl‐terminated hyperbranched aromatic poly(ether‐ester)s. The structure of these polymers was established using FTIR and ¹H NMR spectroscopy. The molecular weights (M_w) of the polymers were found to vary from 2.0 × 10³ to 1.49 × 10⁴ depending on the polymerization techniques and the experimental conditions used. Suitable model compounds that mimic exactly the dendritic, linear, and terminal units present in the hyperbranched polymer were synthesized for the calculation of degree of branching (DB) and the values ranged from 52 to 93%. The thermal stability of the polymers was evaluated by thermogravimetric analysis, which showed no virtual weight loss up to 200 °C. The inherent viscosities of the polymers in DMF ranged from 0.010 to 0.120 dL/g. End‐group modification of the hyperbranched polymer was carried out with phenyl isocyanate, 4‐(decyloxy)benzoic acid and methyl red dye. The end‐capping groups were found to change the thermal properties of the polymers such as T_g. The optical properties of hyperbranched polymer and the dye‐capped hyperbranched polymer were investigated using ultraviolet‐absorption and fluorescence spectroscopy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5414–5430, 2008     

Polyphenylene sulfide‐based adsorption resins: synthesis,characterization and adsorption performance for Hg(II) and As(V)

A series of novel adsorption resins were synthesized via the chloromethylation of polyphenylene sulfide (PPS) resin and subsequent functional group conversion reaction. Their chemical structure, thermal stability, and morphology were systematically characterized by the Fourier transform infrared spectroscopy, elemental analysis, Raman spectroscopy, thermogravimetric analysis, scanning electron microscope, and energy dispersive spectrometer, respectively. The experimental results showed that the thioureido, mercapto, aminopyridine, and quaternary ammonium groups had been respectively introduced into PPS matrix, the functional group content of PPS‐based mercapto resin (HS‐PPS), aminopyridine resin (AP‐PPS), and quaternary ammonium resin (QA‐PPS) were about 2.20, 1.71, and 2.61 mmol g^?1, respectively. The adsorptive performance for Hg (II) and As (V) were studied by batch adsorptive method; the adsorption capacities of the HS‐PPS and AP‐PPS resin for Hg (II) were 210.65 and 169.06 mg g^?1. The adsorption capacity of the QA‐PPS resin was 88 mg g^?1 for As (V). Copyright © 2017 John Wiley & Sons, Ltd.     

Thermal and pH‐sensitive gold nanoparticles from H‐shaped block copolymers of (PNIPAM/PDMAEMA)‐b‐PEG‐b‐(PNIPAM/PDMAEMA)

Well‐defined H‐shaped pentablock copolymers composed of poly(N‐isopropylacrylamide) (PNIPAM), poly(N,N‐dimethylaminoethylacrylamide) (PDMAEMA), and poly(ethylene glycol) (PEG) with the chain architecture of (A/B)‐b‐C‐b‐(A/B) were synthesized by the combination of single‐electron‐transfer living radical polymerization, atom‐transfer radical polymerization, and click chemistry. Single‐electron‐transfer living radical polymerization of NIPAM using α,ω azide‐capped PEG macroinitiator resulted in PNIPAM‐b‐PEG‐b‐PNIPAM with azide groups at the block joints. Atom‐transfer radical polymerization of DMAEMA initiated by propargyl 2‐chloropropionate gave out α‐capped alkyne‐PDMAEMA. The H‐shaped copolymers were finally obtained by the click reaction between PNIPAM‐b‐PEG‐b‐PNIPAM and alkyne‐PDMAEMA. These copolymers were used to prepare stable colloidal gold nanoparticles (GNPs) in aqueous solution without any external reducing agent. The formation of GNPs was affected by the length of PDMAEMA block, the feed ratio of the copolymer to HAuCl₄, and the pH value. The surface plasmon absorbance of these obtained GNPs also exhibited pH and thermal dependence because of the existence of PNIAPM and PDAMEMA blocks. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Zn(II), Cd(II) and Hg(II) complexes of 8-aminoquinoline.: Structure,spectra and photoluminescence property

The reaction of 8-aminoquinoline (8-aq) with M(NO₃)₂ and M(ClO₄)₂ (where M = Zn, Cd and Hg) has synthesized complexes of the composition [M(8-aq)₂(H₂O)₂](X)₂ (X = NO₃, ClO₄) whereas MCl₂ has isolated M(8-aq)Cl₂ type non-ionic compounds. The reaction of M(OAc)₂, 8-aq and NaN₃/NH₄CNS in a 1:1:2 mole ratio has separated polynuclear complexes of the composition [M(8-aq)(Y)₂]_n (Y = N₃, NCS). The complexes have been characterized by spectroscopic data and have been structurally confirmed by single crystal X-ray diffraction study in some representative cases. The X-ray structure of [Zn(8-aq)₂(H₂O)₂](NO₃)₂ shows C–H–π, and π–π interactions and forms a H-bonded sheet (with interactions between the oxygen of NO₃ and C(9)–H of 8-aq/coordinated H₂O). A novel one-dimensional cadmium(II) azido complex, [Cd(8-aq)(N₃)₂]n (9), in which the azido takes on an end-on (EO) bridging mode, has been synthesized and characterized. The presence of π–π interactions result in a supramolecular two-dimensional behaviour for the structure. The complexes are photoluminescent at room temperature.     

Oxygen Plask-TLC Microdetermination of Binary and Ternary Mixtures of Hg(II), Cu(II) and Cd in their Organic Compounds and Some Pharmaceutical Preparations

Abstract

Binary and ternary mixtures of the organic compounds of the title elements are decomposed either by wet digestion in the Kjeldahl flasks or through combustion in the oxygen flask using 1:1 HNO₃ soln. as absorbent and Pt gauze as sample holder. An aliquot of 15 μl of each decomposed mixture is separated on thin layer plate, using silica gel (G 60) as stationary phase and a mixture of 100 ml benzene: 80 ml acetone : 20 ml DMF as a mobile phase in normal saturation system at 25°C. The spots areas are determined, from which the individual concentrations of the cations are calculated. Parallely the spots are scratched from the plates and are eluted with water. Their concentrations are measured in the UV-region, for Hg(II) at 205 nm, for Cu(II) at 203 and for Cd at 201 nm. Concentrations are obtained from previously constructed calibration curves which are linear for Hg(II) in the range 0.0 – 0.375 ppm, for Cu(II) in the range 0.0 – 3.811 ppm and for Cd from 0.7 – 13.48 ppm.     

Potentiometric determination of silver(I), palladium(II) and gold(III) in mixtures by use of an iodide-selective electrode

Two procedures are proposed for the potentiometric determination of Ag(I), Pd(II) and Au(III) in binary mixtures, by titration with potassium iodide solution, and use of a commercial iodide electrode as sensor. In the first procedure, two aliquots of the mixture are titrated, at pH 2.0 ± 0.2 and 9.0 ± 0.2, adjusted with dilute sulphuric acid and ammonia solution. At pH 2.0, the titrant reacts with both metals, whereas at pH 9.0, Ag(I) is the only reactant. The second procedure utilizes titration of two aliquots of the mixture in the presence and absence of a selective masking agent. The methods have been applied to the determination of these metals in some jewellery alloys.     

Poly(triarylamine): Its synthesis,properties, and blend with polyfluorene for white‐light electroluminescence

A new high‐molecular‐weight poly(triarylamine), poly[di(1‐naphthyl)‐4‐anisylamine] (PDNAA), was successfully synthesized by oxidative coupling polymerization from di(1‐naphthyl)‐4‐anisylamine (DNAA) with FeCl₃ as an oxidant. PDNAA was readily soluble in common organic solvents and could be processed into freestanding films with high thermal decomposition and softening temperatures. Cyclic voltammograms of DNAA and PDNAA exhibited reversible oxidative redox couples at the potentials of 0.85 and 0.85 V, respectively, because of the oxidation of the main‐chain triarylamine unit. This suggested that PDNAA is a hole‐transporting material with an estimated HOMO level of 5.19 eV. The absorption maximum of a PDNAA film appeared at 370 nm, with an estimated band gap of 2.86 eV from the absorption edge. Unusual multiple photoluminescence maxima were observed at 546 nm, and this suggested its potential application in white‐light‐emission devices. Nearly white‐light‐emission devices could be obtained with either a bilayer‐structure approach {indium tin oxide/poly(ethylenedioxythiophene):poly(styrene sulfonate)/PDNAA/poly[2,7‐(9,9‐dihexylfluorene)] (PF)/Ca} or a polymer‐blend approach (PF/PDNAA = 95:5). The luminance yield and maximum external quantum efficiency of the light‐emitting diode with the PF/PDNAA blend as the emissive layer were 1.29 cd/A and 0.71%, respectively, and were significantly higher than those of the homopolymer. This study suggests that the PDNAA is a versatile material for electronic and optoelectronic applications. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1727–1736, 2007     

Complexation of N-bis[2-(1,2-dicarboxyethoxy)ethyl]aspartic acid with Cd(II), Hg(II) and Pb(II) ions in aqueous solution

The persistence of widely used chelating agents EDTA and DTPA in nature has been of concern and there is a need for ligands to replace them. In a search for environmentally friendly metal chelating ligands for industrial applications, complex formation equilibria of N-bis[2-(1,2-dicarboxyethoxy)ethyl]aspartic acid (BCA6) with Cd(II), Hg(II) and Pb(II) in aqueous 0.1 M NaNO₃ solution were studied at 25°C by potentiometric titration. Complexation was modeled and the stability constants of the different complexes were determined for each metal ion using the computer program SUPERQUAD. With all metal ions, stable ML^4? complexes dominated the complex formation. The stabilities of Cd(II), Hg(II) and Pb(II) chelates of BCA6 are remarkably lower than those of EDTA and DTPA. Environmental advantages of the use of BCA6 instead of EDTA and DTPA are better biodegradability and lower nitrogen content with a possibility to save chemicals and process steps in pulp bleaching.     

Interpretation of EPR and optical spectra of Ni(II) ions in crystalline lattices at ambient temperature

Many biologically important paramagnetic metal ions are characterized by electron paramagnetic resonance (EPR) spectroscopy to use as spin probes to investigate the structure and function of biomolecules. Though nickel(II) ions are an essential trace element and part of many biomolecules, the EPR properties are least understood. Herein, the EPR and optical absorption spectra measured at 300 K for Ni(II) ions diluted in two different diamagnetic hosts are investigated and reported. The EPR spectrum of a polycrystalline Ni/Mg(3-methylpyrazole)₆(ClO₄)₂ [Ni/MMPC] shows two transitions at X-band frequency (~9.5 GHz), suggesting the zero-field splitting parameter (D) is larger than the resonance field of the free electron (H_o). This incomplete and complex spectrum is successfully analyzed to obtain EPR parameters. The EPR spectrum of the polycrystalline Ni/Zn(pyrazole)₆(NO₃)₂ [Ni/ZPN] shows a triplet spectrum indicating D < H_o. A detailed analysis of single-crystal EPR data yielded the spin Hamiltonian parameters. The optical absorption spectra are deconvoluted to understand the symmetry of the coordination environment in the complex.     

Synthesis of gold nanocomposite via chemisorption of gold nanoparticles with poly(p‐methylstyrene) containing multiple bonding groups on the chain side

Styrenic nanocomposite containing gold nanoparticles (AuNPs) has been synthesized by anchoring polymer molecules containing multiple functional groups onto the gold surface. p‐Methylstyrene was first anionically polymerized and the resulting polymer was chlorinated with sodium hypochlorite in the presence of a phase transfer catalyst. The chlorinated poly(p‐methylstyrene) was next reacted with methylthiomethyllithium, which had been prepared via a metalation reaction of dimethyl sulfide with n‐butyllithium, to form a styrenic polymer containing thioether groups on the sides of the molecule. These thioether groups on the chain sides afforded more chemisorption sites per molecule to AuNPs. The nanocomposite was analyzed using NMR, TEM, UV‐VIS, TGA, and XPS. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4710–4720, 2005     

Poly(triphenylamine)s derived from oxidative coupling reaction: Substituent effects on the polymerization,electrochemical, and electro‐optical properties

A series of triphenylamine‐based polymers containing electron‐donating methoxy (? OCH₃) and electron‐withdrawing cyano or nitro (? CN or ? NO₂) substituents in the main chains have been designed and investigated. These conjugated polymers ( P1 – P3 ) could be readily prepared by oxidative coupling polymerization from monomers ( M1 – M3 ) using FeCl₃ as an oxidant. The P2 and P3 exhibited moderate high T_g values (203–205 °C) and thermal stability. These polymers in NMP solution showed UV–vis absorption around 288–404 nm and photoluminescence peaks around 435–492 nm. P1 – P3 showed reversible oxidation redox couples at E_onset = 0.67, 0.99, and 1.00 V in solution of 0.1 M tetrabutylammonium perchlorate (TBAP)/acetonitrile (CH₃CN), respectively. M3 and P3 exhibited reversible reduction redox couples at E_onset = ?1.04 and ?1.03 V. These polymers also revealed electrochromic characteristic changing color at different potential. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 285–294, 2009     

New acrylamide‐based monomer containing metal chelating units: Homopolymer grafted magnetite nanoparticles via ATRP for the magnetic removal of Co(II) ions

In this research, we synthesized and characterized a new acrylamide‐based monomer containing pyridine and 1,3,4‐oxadiazole moieties, N‐(4‐(5‐(pyridin‐2‐yl)‐1,3,4‐oxadiazol‐2‐yl)phenyl)acrylamide (POPA). Poly(POPA)‐grafted magnetite nanoparticles were then obtained via surface‐initiated atom transfer radical polymerization. The grafted nanoparticles were characterized by Fourier transform infrared analysis, scanning electron microscopy, wide angle X‐ray diffraction, and vibrating sample magnetometry. The amount of the grafted polymer was 126 mg/g, as calculated from thermo gravimetric analysis experiment. The capability of poly(POPA)‐g‐magnetite nanoparticles (MNPs) to remove Co(II) cations, under optimal time period, pH and adsorbent mass, was shown by atomic absorption. The adsorption kinetics obeyed the pseudo–second‐order kinetic equation, and the adsorption isotherm was best described by the Freundlich model with a maximum adsorption capacity of 59.90 mg/g. In addition, the poly(POPA)‐g‐MNPs were regenerated by simply washing with an aqueous 0.1M HCl solution, and no considerable decrease was observed in the extraction efficiency following the test of up to 7 cycles. These findings suggest that poly(POPA)‐g‐MNPs are stable and reusable adsorbent, and they could be potentially applied to water treatments for an efficient removal of Co(II) cations.     

One‐pot synthesis of soluble and fluorescent aliphatic hyperbranched poly(amide‐imide) with solvent‐dependent emission

Aliphatic hyperbranched poly(amide‐imide) was facilely prepared by employing a functional thiolactone‐maleimide monomer. Highly efficient, selective and quantitative properties of amine‐maleimide Michael addition and aminolysis of a thiolactone guaranteed the generation of an ABB' thiol‐yne intermediate without side products, followed by consecutive thiol‐yne click reaction in one‐pot. The hyperbranched structure of the poly(amide‐imide) was confirmed by NMR spectroscopy and triple‐detector GPC/SEC analysis. Additionally, due to the presence of aminosuccinimide fluorophores and intrinsic physical property of hyperbranched polymers, this aliphatic hyperbranched poly(amide‐imide) possessed solvent‐dependent emission and presented good solubility in various organic solvents. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2053–2060     

Simultaneous synthesis of silver nanoparticles and poly(2,5‐dimethoxyaniline) in poly(styrene sulfonic acid)

Silver nanoparticles were formed in situ along with poly(2,5‐dimethoxyaniline) (PDMA) in an interconnected network matrix (reactor), comprising the electronic conductive polymer, PDMA, and a polyelectrolyte, poly(styrene sulfonic acid) (PSS), through the simultaneous reduction of Ag⁺ ions and polymerization of 2,5‐dimethoxyaniline. In situ ultraviolet‐visible spectroscopy showed that peaks corresponding to the plasmon resonance of silver nanoparticles at 411 nm and the polaronic transition of PDMA at 438 nm provided evidences for the simultaneous formation of silver nanoparticles and PDMA. Transmission electron microscopy and size distribution analysis revealed the presence of spherical silver nanoparticles with an average diameter of 12 nm in the composite. X‐ray photoelectron spectroscopy showed that the amine units in PDMA changed to imine units upon the formation of silver nanoparticles. A comprehensive mechanism for the formation of the PDMA‐PSS‐Ag nanocomposite is proposed. A 10‐fold increase in the conductivity was noticed for the PDMA–PSS–Ag nanocomposite (1 S/cm) in comparison with the PDMA–PSS composite (0.1 S/cm). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3843–3852, 2006     

Polymeric Hg(II) and dimeric oxo-bridged manganese(II) complexes derived from N′-(2-methyl-benzoyl)-hydrazinecarbodithioic acid methyl ester: Synthesis, spectral and structural characterization

Reaction of N′-(2-methyl-benzoyl)-hydrazinecarbodithioic acid methyl ester (H₂mbhe) with HgCl₂ and Mn(OAc)₂·4H₂O yielded the polymeric [Hg₃(tot)₂(μ-SCH₃)₄]_n (1) and dimeric [Mn₂(Hmbhe)₂(μ-mbmst)₂]CHCl₃ (2), respectively. These complexes have been synthesized and their structures investigated by elemental analyses, NMR, IR, UV-Vis and single crystal X-ray data. In one unit of the polymeric structure of complex 1, two Hg(II) are similar bonded to an exocyclic sulfur of oxadiazole and three sulfur of SCH₃ whereas one Hg(II) is two coordinate linked to two SCH₃ fragments. Thus, complex 1 shows the presence of tetrahedral as well as linear Hg(II) in the same molecule. The dimeric octahedral complex 2 contains thiadiazolyl hydrazide moiety (mbmst) formed from H₂mbhe under thermal condition which is bonded in a tetradentate manner by two nitrogens and one bidentate bridged oxygen between two Mn(II) centers. In the solid state both complexes are stabilized by intermolecular hydrogen bonding and form supramolecular architecture.     

Bipyridyl/carbazolate silver(I) and gold(I) N-heterocyclic carbene complexes: A systematic study of geometric constraints and electronic properties

A series of silver(I) and gold(I) carbene complexes of the type [M(L)(2,2′-bipyridine)][PF₆] (L = 1-benzyl-3-(2-pyridylmethyl)benzimidazolylidene; M = Ag ( 1 ); M = Au ( 3 )) and [M(L)(carbazole)] (M = Ag ( 2 ); M = Au ( 4 )) were synthesized and analyzed using a range of spectroscopic and crystallographic techniques. Inspection of the solid-state structures of 1 , 2 and 4 revealed a number of intermolecular noncovalent interactions. In the solid-state structure adopted by 1 , π–π and Ag–Ag interactions directed the complexes to orient in a head-to-tail fashion. The photophysical properties were found to be influenced by the ancillary ligands in solution as well as in the solid-state. Calculations were performed to support the aforementioned structural and optoelectronic assignments.