Ru(II)(tpy)2‐functionalized hydrogels: Synthesis,reversible responsiveness,and coupling with the belousov‐zhabotinsky reaction

This work aims at developing an approach to Ru(II)(Tpy)₂‐functionalized hydrogels and exploring the coupling of the hydrogels with the Belousov‐Zhabotinsky (BZ) reaction. Based on free radical polymerization, two synthetic routes are developed. The first one is the direct gelation by copolymerization of acrylamide as hydrophilic component and Ru(II)(Tpy)₂ as the functional group. The second one is carried out through a combined approach. A terpyridine‐containing hydrogel is first prepared and then post‐functionalized by coordination between Ru(III)(Tpy)Cl₃ and terpyridine groups in the hydrogel network. Utilizing the synthetic hydrogels, the reversible redox responsiveness, the coupling with the BZ reaction, the occurrence and the self‐oscillating properties of the BZ reaction in the hydrogel networks are studied. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2214–2222     

Magnetic properties of a polyfluorene derivative containing complexed neodymium ions

Poly[9,9′‐dihexylfluorene‐2,7‐diyl)‐6,6″‐(2,2′:6′,2″‐terpyridine)] (LaPPS75) and its complexes with neodymium were synthesized and characterized. Magnetic measurements showed that the noncomplexed polymer presented a ferromagnetic contribution due to the formation of π stacking, and that in absence of those, the ferromagnetic behavior is suppressed. The pristine polymer, the complexed one and a low‐molecular‐weight model compound with the same structure of the complexed site in the parent polymer were studied. The observed behavior found is presented and discussed, the most important finding was that when a conjugated chain is used as a host for the metallic ion, an amplification of four times for the magnetization is achieved, using the same metallic content for complexed polymer and model compound for comparison. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 304–311     

Nucleation of gold nanoparticles on latex particle surfaces

Gold particles were nucleated on functionalized (i.e., sulfonate or imidazole groups) latex particle surfaces. Gold ions were associated with the functional groups present on the surface of the latex particles by metal‐ligand formation and were then reduced to nucleate gold particles on the particle surface. The use of imidazole groups favored the metal‐ligand formation more effectively compared with sulfonic acid groups, so gold nucleation was investigated on the surface of imidazole‐functionalized model latex particles. The desorption of gold atoms or their surface migration first occurred during the reduction process and then gold nanoparticles were nucleated. The utilization of strong reductants, such as NaBH₄ and dimethylamine borane (DMAB) under mildly acidic conditions (i.e., pH 4) led to the deprotonation of imidazole‐rich polymer chains present on the surface of the model latex particles followed by deswelling of hydrophilic polymer surface layers. As a result, well‐dispersed gold nanoparticles were embedded in the hydrophilic polymer surface. On the other hand, the use of weak reductants led to the formation of localized gold aggregates on the surface of the latex particles. The removal of residual styrene monomer is very important because gold ions can be coordinated with the vinyl groups present in styrene monomer and would then be reduced by nucleophilic water addition. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 912–925, 2008     

Synthesis and Fe(III)‐complexation ability of polyurethane bearing kojic acid skeleton in the main chain prepared by polyaddition of aliphatic hydroxyl groups without protection of phenolic hydroxyl groups

Polyaddition of a kojic acid dimer and diisocyanates yielded polyurethane with metal‐coordination ability owing to the phenolic hydroxyl groups of kojic acid. Although the kojic acid dimer contains two phenolic and two aliphatic hydroxyl groups, 1,5‐diazabicyclo[4.3.0]non‐5‐ene catalyzed polymerization proceeded through highly selective reactions of the aliphatic hydroxyl groups without any protection of the phenolic hydroxyl groups. The resulting polymers complexed with FeCl₃, and specific colorizations were observed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Terpyridine‐substituted,fluorescent polymers and their chelation with zinc ion: The ligand‐to‐metal ratio and optical properties

Soluble, fluorescent, terpyridine‐substituted, conjugated polymers were prepared and characterized. The polymer chains included a defined oligo(phenylenevinylene) fragment, on which the terpyridine‐functional group was attached. The polymers were blue‐fluorescent with emission peaks at 400–427 nm in tetrahydrofuran solutions. Upon chelation with the Zn(II) cation, the emission maxima were shifted to a longer wavelength by as much as 113 to 506–526 nm. A model compound was also prepared to aid the structural characterization. The ratio of terpyridine to Zn²⁺ in the polymer complex was found to be 1:1 on the basis of spectroscopic evidence, which included mass spectrometry, ¹H NMR, and Job titration. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2338–2345, 2006     

Thermally responsive complex polymer networks containing Fe3O4 nanoparticles: Composition/morphology/property relationship

In this research, the synthesis and properties of thermally responsive complex polymer networks containing Fe₃O₄ nanoparticles were studied. First, a stable ferrofluid containing Fe₃O₄ nanoparticles was synthesized via a coprecipitation method in the presence of a poly(acrylic acid) oligomer. This stable ferrofluid could mix well with water‐soluble monomers by the adjustment of its pH value. Second, a thermally responsive copolymer was synthesized in the presence of the ferrofluid containing Fe₃O₄ nanoparticles to obtain the complex polymer networks. By the adjustment of the pH value, the ferrofluid could remain stable in the polymerization system, in which N‐isopropylacrylamide (NIPAAm) and methacrylic acid (MAA) were used as comonomers to provide thermoresponsive properties and acid groups and ammonium persulfate and sodium metabisulfite were used as the redox initiator system. Several variables, such as the molar ratio of MAA to NIPAAm, the concentrations of the monomers and crosslinking agent, the addition of an ammonium solution, and the content of the ferrofluid, were studied in this polymerization. Their effects on the morphology, structure, polymerization rate, and thermal properties of the complex polymer networks were discussed. The swelling and thermoresponsive behaviors of the complex polymer networks containing Fe₃O₄ nanoparticles were also studied, and the composition–morphology–property relationship was established. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5923–5934, 2005     

Design and synthesis of fluorescent core–shell nanoparticles with tunable lower critical solution temperature behavior and metal‐enhanced fluorescence

In this article, the preparation of fluorescent nanohybrids with core–shell structure and metal‐enhanced fluorescence (MEF) effect was presented. The fluorescent core–shell nanohybrids were prepared using silver nanoparticles (AgNPs) as cores and fluorophore tethered thermoresponsive copolymers with tunable lower critical solution temperature (LCST) from 15 to 90 °C as shells. These thermoresponsive copolymers were synthesized by the random copolymerization of oligo(ethylene oxide) acrylate and di(ethylene oxide) ethyl ether acrylate using reversible addition–fragmentation chain transfer polymerization and grafted on to AgNPs surface via Ag–S coordination interaction. By thermal manipulation of polymer spacer between AgNPs and fluorophores, the tunable MEF was achieved. It was also revealed that the fluorescent nanohybrids would exhibit maximal MEF when the polymerization degree was tuned to 350. The manipulation of the solution temperatures below and above LCST resulted in switchable MEF behavior. In addition, the phase transition process of the thermoresponsive copolymer was also studied by MEF effect using this fluorescent core–shell nanohybrid design. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 87–95     

Magnetism,optical absorbance,and 19F NMR spectra of nafion films with self‐assembling paramagnetic networks

Magnetization, optical absorbance, and ¹⁹F NMR spectra of Nafion transparent films as received and doped with Mn²⁺, Co²⁺, Fe²⁺, and Fe³⁺ ions with and without treatment in 1H‐1,2,4‐triazole (trz) have been studied. Doping of Nafion with Fe²⁺ and Co²⁺ and their bridging to nitrogen of triazole yields a hybrid self‐assembling paramagnetic system that exhibits interesting magnetic and optical properties. These include spin crossover phenomena between high‐spin (HS) and low‐spin (LS) states in Nafion‐Fe²⁺‐trz and Nafion‐Co²⁺‐trz accompanied by thermochromic effects in the visible range induced by temperature. A large shift of the magnetization curve induced by a magnetic field in the vicinity of the HS ? LS, ～220 K, observed for Nafion‐Fe²⁺‐trz has a rate of ～6 K/kOe, which is about three orders of magnitude larger than that in bulk spin crossover Fe²⁺ materials. Selective response of ¹⁹F NMR signals on doping with paramagnetic ions demonstrates that NMR can be used as spatially resolved method to study Nafion film with paramagnetic network. Both chemical shift and width of ¹⁹F NMR signals show that SO groups of Nafion, Fe or Co ions, and nitrogen of triazole are bonded whereas they form a spin crossover system. Based on a model of nanosize cylinders proposed for Nafion [K. Schmidt‐Rohr and Q. Chen, Nat Mater (2008), 75], we suggest that paramagnetic ions are located inside these cylinders, forming self‐assembling magnetically and optically active nanoscale networks. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 50: 129–138, 2012     

Preparation of a Yb(III)‐Incorporated porous polymer by post‐Coordination: Enhancement of gas adsorption and catalytic activity

We synthesized a Yb(III)‐incorporated microporous polymer (Yb‐ADA) and studied its gas adsorption property and catalytic activity. The adamantane‐based porous polymer (ADA) was obtained from an ethynyl‐functionalized adamantane derivative and 2,5‐dibromoterephthalic acid through Sonogashira–Hagihara cross‐coupling. ADA had two carboxyl groups which were used for Yb(III) coordination under basic conditions. The Brunauer‐Emmett‐Teller (BET) surface area of ADA was 970 m² g^?1. As Yb(III) ions were incorporated into ADA, the surface area of the polymer (Yb‐ADA) was reduced to 885 m² g^?1. However, Yb‐ADA exhibited a significantly enhanced CO₂ adsorption capacity despite the reduction of surface area. The CO₂ uptakes of ADA and Yb‐ADA were 1.56 and 2.36 mmol g^?1 at 298 K, respectively. The H₂ uptake of ADA also increased after coordination with Yb(III) from 1.15 to 1.40 wt % at 77 K. Yb‐ADA showed high catalytic activity in the acetalization of 4‐bromobenzaldehyde and furfural with trimethyl orthoformate and could be reused after recovery without severe loss of activity. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5291–5297     

Hyperbranch‐polyethyleniminated functional polymers. I. Synthesis,characterization of novel ABA type of dumbbell‐like polyethyleniminated polyoxypropylenediamines,and their complexing properties with copper(II) ions in aqueous solution

Novel ABA‐type dumbbell‐like water‐soluble copolymers [D230(EI)₄, D400(EI)₄, and D400(EI)₈] were synthesized by introducing ethylenimine (EI) groups into both sides of polyoxypropylenediamines via a simple in situ ethylamination of polyoxypropylenediamine with 2‐chloroethylamine hydrochloride. The structures of the resultant polymers were identified by Fourier transform infrared spectroscopy and ¹H NMR. The percentages of primary, secondary, and tertiary amine present were determined by the potentiometric titration method after treatments with the appropriate chemicals of salicylaldehyde and acetic anhydride. The surface tension and solubilizing behavior of pyrene in the presence of these polymers in aqueous medium were also investigated, and the efficiency to reduce the surface tension and solubilizing behavior of pyrene depends on the attachments of EI to polymer backbone. The chelating properties of these polymers were examined quantitatively by ultraviolet–visible (UV–vis) spectroscopy in the presence of Cu²⁺ ions in aqueous solution, and continuous variation analysis revealed that the most stable complex is formed at the normality ratio of [N]/[Cu²⁺] = 3.0. UV–vis spectroscopy and transmission electron microscopy were used to evaluate the dumbbell‐like water‐soluble copolymer, D400(EI)₈, as a stabilizer for preparing colloidal noble metal nanoparticles (Au and Pt) in aqueous solution. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1360–1370, 2003     

Electro‐active Polymer Actuator Based on Sulfonated Polyimide with Highly Conductive Silver Electrodes Via Self‐metallization

We report here a facile synthesis of high performance electro‐active polymer actuator based on a sulfonated polyimide with well‐defined silver electrodes via self‐metallization. The proposed method greatly reduces fabrication time and cost, and obviates a cation exchange process required in the fabrication of ionic polymer‐metal composite actuators. Also, the self‐metallized silver electrodes exhibit outstanding metal‐polymer adhesion with high conductivity, resulting in substantially larger tip displacements compared with Nafion‐based actuators.

     

Coordination of nickel and copper dithiolate to 2,2′‐bipyridine‐based π‐conjugated polymers

π‐Conjugated polymers (Poly1–Poly3) containing a 2,2′‐bipyridine (bpy) unit were subjected to coordination to nickel and copper dithiolate for the purpose of manipulating the photophysical properties. The absorption maximum peak of Poly1 [maximum wavelength (λ_max) = 446 nm] redshifted by 36 nm upon the coordination of bpy to NiCl₂, which produced Poly1–NiCl₂. A further bathochromic shift was observed in the spectrum of Poly1–mntNi [mntNi = (maleonitrile dithiolate)nickel; λ_max = 499 nm] bearing the dithiolate ligand, which stemmed from the extension of the conjugated system over the nickel dithiolate moiety through the bpy unit. An increase in the [Ni]/[bpy] ratio in Poly1–mntNi rendered the original maximum peak at 446 nm smaller and the lower energy charge‐transfer peak at 499 nm larger; the isosbestic points remained at 380 and 475 nm. The green fluorescence (λ_max = 504 nm) emitted from Poly1 markedly diminished upon the coordination of nickel dithiolate because of the effective energy transfer. The absorption maximum peak of Poly1–mntNi in chloroform at 499 nm blueshifted to 471 nm when the volume ratio of the chloroform/N,N‐dimethylformamide solvent reached 10:90. The coordination of nickel dithiolate to Poly2 and Poly3 also brought about redshifts of the absorption maximum peaks of as much as 55 and 61 nm, respectively. The absorption maximum peak of Poly1–(phenyldithiolate)nickel(pdtNi) (λ_max = 474 nm) redshifted by 28 nm in comparison with that of Poly1, whereas the magnitude of the shift of Poly1–bis(thiophenoxide)nickel(btpNi) bearing two thiophenoxide ligands was 20 nm. Poly1–mntCu with a tetrahedral copper center was also investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2631–2639, 2004     

Synthesis of π‐conjugated polymer containing both thiophene and phosphole sulfide in the main chain by simultaneous post‐element transformation of organotitanium polymer

The synthesis and unique optoelectronic features of a π‐conjugated polymer containing both thiophene and 1‐phenylphosphole sulfide units (multiple heteroles) in the main chain by the post‐element transformation of a regioregular organometallic polymer possessing titanacyclopentadiene‐2,5‐diyl unit are described. The π‐conjugated polymer containing multiple heteroles was obtained in 73% yield by the simultaneous reaction of the organotitanium polymer with sulfur monochloride and dichlorophenylphosphine (0.6 equiv each), whose number‐average molecular weight (M_n) and the molecular‐weight distribution (M_w/M_n) were estimated to be 11,000 and 3.4, respectively, by the size exclusion chromatography (SEC). The π‐conjugated polymer thus obtained was found to have the high HOMO and the low LUMO energy levels due to the electron‐rich thiophene and electron‐deficient phosphole sulfide units, respectively, as supported by its cyclic voltammetry (CV) analysis. Compared to a mixture of a polymer containing sole thiophene‐unit and that containing sole phosphole sulfide units, the π‐conjugated polymer‐containing multiple heteroles proved to exhibit interesting optical properties. For example, a specific emission peak was observed at 608 nm in the photoluminescence spectrum, which was not observed in the case of the thiophene‐containing polymer, the phosphole‐containing polymer, and their mixture. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2519–2525     

Multifunctional materials based on polyazomethines derived from 2,5‐dihydroxy‐1,4‐benzoquinone and siloxane diamines

New polyazomethines have been synthesized by the reaction between 2,5‐dihydroxy‐1,4‐benzoquinone and siloxane diamines differing by the siloxane sequence length. A dimer has also been prepared as a model compound. The products were characterized by spectral (FTIR and ¹H‐NMR) and elemental analyses, GPC, viscosity measurements, solubility tests, and transmission electron microscopy (TEM). The different properties have been investigated by adequate techniques: thermal (DSC and TGA), spectral (UV–vis and fluorescence spectroscopy), redox (Differential Pulse Voltammetry). pH‐sensitivity and metal complexing ability were also evaluated. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1862–1872, 2008     

Polymers that Contain Ligated Metals in their Side Chain: Building a Foundation for Functional Materials in Opto‐Electronic Applications with an Emphasis on Lanthanide Ions

Organic polymers that contain ligated metals offer a variety of unique properties which include luminescence, electro‐ and photochemistry, catalysis, charge, magnetism, and thermochromism. These organic–inorganic hybrid materials have the potential to offer novel active matrixes for advanced devices. Continued progress in synthetic chemistry and molecular characterization will enable such advanced materials. Here the focus is restricted to side‐chain metal complexes with emissive properties that highlight the use of lanthanide ions as opposed to the often‐studied transition metal complexes.

     

Nearly monochromatic red electroluminescence from a nonconjugated polymer containing carbazole segments and phenanthroline [Eu(β‐diketonate)3] moieties

A novel nonconjugated copolymer (PVKEu) with carbazole segments and phenanthroline [Eu(β‐diketonate)₃] moieties was synthesized via free radical copolymerization, and characterized by FTIR, ¹H NMR spectroscopy, GPC, ICP, and elemental analysis. The copolymer exhibited good solubility, as well as good thermal stability and high glass transition temperature. The photoluminescence (PL) of this polymer in solution and in solid film has been studied. A multi‐layer device with the configuration of ITO/PEDOT: PSS (40 nm)/PVKEu (70 nm)/BCP (15 nm)/AlQ₃ (30 nm)/LiF/Al exhibited nearly monochromatic red emission at 615 nm and voltage‐independent spectral stability. Our results suggest that enhancing the ligand‐mediated energy transfer between the matrix polymer and europium complex is a potential method to improve the electroluminescence performance of the Eu‐chelated polymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 210–221, 2009     

Detrimental Ni(0) transfer in Kumada catalyst transfer polycondensation of benzo[2,1‐b:3,4‐b']dithiophene

This article deals with the Kumada Catalyst Transfer Polycondensation (KCTP) of 4,7‐dioctylbenzo[2,1‐b:3,4‐b']dithiophene ( BDP‐Oct ) using Ni(II) catalyst or In/cat combination. A combination of MALDI MS, GPC, and ³¹P NMR spectroscopy is used to reveal the failure of the KCTP of this particular monomer. Intermolecular transfer reactions to monomer appeared to prevent the formation of polymer. This result is remarkable, since isomeric benzo[1,2‐b:4,5‐b']dithiophene polymerizes in a controlled way. The presence of a “non‐aromatic double bond” in annulated monomers is discussed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1706–1712     

Magnetic properties of metal oxide clusters linked by flexible chain siloxane fragments

Oligomeric copperdiorganosiloxanes differing in organic environment at the silicon atoms and in the Si/Cu ratio were synthesized. The magnetic properties of all compounds were shown to deviate from the Curie law. Unlike rigid chain oligomers characterized by antiferromagnetic interaction, coordination metal oxide clusters linked by flexible chain siloxane fragments exhibit ferromagnetic properties. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1691–1694, September, 1999.     

Novel Metal‐Polyurethane Complexes with Enhanced Antimicrobial Activity

Summary: The silver coating of polymers has been intensively investigated in the last few decades as an effective non‐resistance‐inducing strategy to prevent medical device‐related infections. We have developed a completely new approach to incorporate silver ions in polymers by the synthesis of a carboxylated polyurethane able to coordinate Ag⁺. The obtained polymers possess mechanical properties suitable for the development of medical devices, without any risk of loss of activity. To minimize the risk of increasing antibiotic resistance, the metal ion‐containing polymers are loaded with ciprofloxacin, which possesses a different mechanism of antimicrobial action, thus a system able to inhibit Staphylococcus epidermidis and Pseudomonas aeruginosa growth for at least one month is developed.

SEM images showing a mature S. epidermidis biofilm on the surface of the carboxylated polyurethane (left) and the surface of the silver ion‐containing polyurethane free from bacterial colonization (right) after 48 h of incubation.