Polymeric Metal Complexes Research Articles

Metal-Polymer Complexes of Gallium/Gallium-68 with Copolymers of N-Vinylpyrrolidonewith N-Vinylformamideand N-Vinyliminodiacetic Acid: A Hint for Radiolabeling of Water-Soluble Synthetic Flexible Chain Macromolecules.

Copolymer of N-vinylpyrrolidone (VP) with vinylformamide (VFA) and N-vinyliminodiacetic acid (VIDA) was synthesized; its metal-polymer complexes (MPCs) with gallium were obtained. The complexes were characterized by size exclusion chromatography, hydrodynamic and optical methods, scanning electron microscopy, and spectral methods (UV, IR, 1Н NMR spectroscopy). It was demonstrated that in going from polymer to complex, hydrodynamic parameters of macromolecules change only slightly, although the polymer contains intramolecular Ga(VIDA)2 fragments in its structure. A new method for preparation of MPCs with gallium and gallium-68 radionuclide was suggested. The obtained metal-polymer complex is stable over a wide range of pH values as well as in the histidine challenge reaction. In vivo distribution experiments in intact animals showed high primary accumulation of thegallium-68 MPC in blood with subsequent excretion via urinary tract.

Полимерные комплексы никеля с лигандами саленового типа как многофункциональные компоненты катодов литий-ионных аккумуляторов

This work describes the method of preparation of composite lithium-ion battery cathodes that allows total replacement of conventional polymer binders and electroconductive carbon black additives with redox-active conductive polymeric nickel complexes of salen-type Schiff base ligands in the electrode layer. The structure and electrochemical behavior of the electrodes prepared by this method have been investigated. Polymeric metal complexes have been shown to successfully perform the functions of binding and conductive components and also reversibly store charge in the lithium iron phosphate cathodes, which could result in the improvement of the specific capacity of the cathode layer, as compared with the conventional electrodes.

Nickel(II)-pyridinedicarboxamide-co-polydimethylsiloxane complexes as elastic self-healing silicone materials with reversible coordination

The nickel(II)-pyridinedicarboxamide-co-polydimethylsiloxane complexes as elastic silicone rubbers were prepared. The structure of the Ni(II) coordination cross-links was fully characterized by X-ray crystallography, high-resolution mass spectrometry, IR and UV–vis spectroscopy of the low-molecular weight model complex. The nickel content in the polymer-metal complexes varied from 2.78 to 0.12 wt%. Mechanical properties of the polymer-metal complexes was controlled by the Ni(II) load variations, metal to ligand molar ratios of 1:(1–8), and by the polydimethylsiloxane unit length, Mn: 850–900, 5000 or 25000 g∙mol−1; an increase of the polysiloxane chain length and a decrease of Ni(II) load led to higher elasticity and lower hysteresis (3%). The elongation at break of the polymer-metal complexes was up to 1800% and the self-healing efficiency was up to 92.5% at room temperature (for the rubber with a polydimethylsiloxane unit Mn = 25000 g∙mol−1). The glass transition temperatures of the nickel(II)-pyridinedicarboxamide-co-polydimethylsiloxanes were from −123 °C to −112 °C, and the electroconductivity was 10−13–10−11 S∙cm−1.

Ferrocene fortified multifunctional hybrid polyurethane coatings: Synthesis, characterization and properties evaluation

The present work delineates the development of ferrocene (Fc) fortified, multifunctional, hybrid polyurethane coating films. Initially ferrocene containing polyol (Fc-PL) was successfully synthesized with the assistance of catalyst free azide-alkyne click chemistry and each step of the synthesis was confirmed by Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1H NMR), carbon-13 nuclear magnetic resonance (13C NMR), Ultraviolet-visible spectroscopy (UV/Vis) spectroscopy and Electrospray ionization mass (ESI-mass) spectrometry. Polyurethane coatings of varying concentrations of Fc-PL, polypropylene glycol (PPG), trimethylol propane (TMP) were prepared in such a way that to maintain Fc concentrations in 0, 5, 10, 15 weight percentages with respect to polyol mixture and mixed with polymeric diphenylmethane diisocyanate (PMDI) at a OH: NCO ratio of 1:1.05 and cured under atmospheric moisture to obtain corresponding polyurethane coatings and labeled as Fc-0, Fc-5, Fc-10, Fc-15. Successful incorporation of Fc into PU coatings was confirmed by energy-dispersive X-ray spectroscopy (EDS) analysis. Effect of ferrocene on thermal stability and thermo-mechanical properties was assessed by thermo-gravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA) respectively and TGA suggests that onset decomposition temperature, 30 % weight loss temperature, 50 % weight loss temperature and weight % remaining at 500°C increased as Fc wt% increases from 0 to 15 wt%, which implies that thermal stability enhanced with increasing the ferrocene concentration. DMTA demonstrated that mechanical properties i.e., storage modulus enhanced and glass transition temperature (Tg) declined with increasing the ferrocene concentration, on account of redistribution of intermolecular hydrogen bonds and metal-polymer complex formation. Ferrocene effect on corrosion resistant property, water contact angle and anti-fungal susceptibility was studied by electrochemical polarization analysis, contact angle measurements and disk diffusion test respectively. Electrochemical polarization analysis revealed that corrosion resistant property improved as the ferrocene content increases from Fc-0 to Fc-15. Ferrocene additionally imparted hydrophobicity to synthesized PU coatings. Fc-5 PU coating sample showed better hydrophobicity than other samples i.e, Fc-0, Fc-10 and Fc-15. These PU coatings are anti-fungal in nature due to the presence of hydrogen bonded triazole ring formed by click chemistry.

Formation of Copper(II) Complexes with Low- and High-Methoxylated Pectins Modified with Salicylic and Anthranylic Acids

Low- and high-methoxylated pectins were synthesized and modified with anthranilic and salicylic acids to obtain effective polymeric ligands. On their basis, new copper(II) metal-polymer complexes were obtained, their composition was determined, stability constants and thermodynamic characteristics of the complex formation process were calculated. The efficiency of the metal binding to the polymer ligand depends mainly on the degree of pectin methoxylation, the acidity of the medium, the temperature of the process, and also on the structure of the pharmacologically active modifier acid. The thermal stability of polymeric copper(II) complexes increases with the introduction of an organic complexone into the polysaccharide and with a decrease in the degree of pectin methoxylation.

Synthesis of Water-Soluble Copolymers of N-vinylpyrrolidone with N-vinyldithiocarbamate as Multidentate Polymeric Chelation Systems and Their Complexes with Indium and Gallium.

Dithiocarbamate (DTC) derivatives of N-vinylpyrrolidone-N-vinylamine (VP–VA) copolymers were synthesized via reaction between the copolymers and carbon disulfide in alkaline medium; molecular masses of the products were 12 and 29 kDa; the VP:VDTC ratios were 94:6 and 83:17 mol.%. Complexation between the obtained DTC derivatives and metal ions (indium and gallium) was investigated. It was demonstrated that metal–DTC ligand complexes with 1:3 ratio between components were formed. Gallium metal–polymer complexes (MPC) were unstable in solution. Individual indium MPC were isolated and characterized by spectral and chromatographic methods. Unlike similar gallium MPC, they appeared to be stable in histidine challenge reaction.

Enhanced performance of terpolymer resin derived from resorcinol/formaldehyde/salicylic acid for antibacterial application

A terpolymer resin derived from Resorcinol, Formaldehyde and Salicylic acid was synthesized through condensation reaction. Transition metal ions namely Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) were incorporated into the resin forming polymer-metal complexes. Both the resin and the complexes were characterized by FTIR, UV–Vis., XRD, 1H NMR, TGA and SEM/EDX. Elemental analysis was carried out to determine the percentage of different elements present in the resin and its complexes. Conductivity measurement data showed higher conductivity of the metal complexes as compared to its precursor resin. The terpolymer resin and its metal complexes were tested against five strains of gram positive bacteria namely; S. aureus, S. mutans, S. pyrogenes, C. xerosis, C. diphtheria, and three strains of gram negative bacteria namely; E. coli, K. pneuomoniae and P. aeruginosa. All the metal complexes exhibited enhanced antibacterial properties as compared to its terpolymer resin. The Mn(II) and Co(II) demonstrated strong antibacterial activity.

Fabrication of Nanocomposites Complexed with Gold Nanoparticles on Polyaniline and Application to Their Nerve Regeneration.

Electrically conductive materials can stimulate stem cells through electric shock and thereby contribute to the regulation of cell proliferation and differentiation. Recently, polymer-metal complexes composed of polyaniline and gold nanoparticles have emerged as novel candidates for use in regenerative medicine. By mixing two different materials, such composites maximize the benefits while alleviating the disadvantages of using either material alone. Based on their excellent conductivity, these complexes can be applied to nerve regeneration using stem cells. In this study, we investigated a method for producing hybrid nanocomposites by complexing gold nanoparticles to polyaniline and tested the resultant composites in a model of nerve regeneration. We manipulated the shape, size, and electrical conductivity of the hybrid composites by compounding the component materials at various ratios. The most efficient nanocomposite was named conductive reinforced nanocomposites (CRNc's). When the CRNc was delivered directly to cells, no cytotoxicity was observed. After the intracellular delivery of the CRNc, the stem cells were electrically stimulated using an electroporator. As a result of performing mRNA-sequencing (Seq) analysis after electrical stimulation (ES) of the CRNc-internalized cells, it was confirmed that the CRNc-internalized cells have a pattern similar to that of the positive group-induced neuron cells. In particular, microtubule-associated protein 2 is more than twice that of the control group (negative control), and the nerve fiber protein is strongly expressed as in the positive control group. In addition, we verified that neural differentiation progressed by monitoring the growth of neurites from stem cells. Together, these findings show that the CRNc can be used to induce the formation of neuron-like cells by applying ES to stem cells.

Synthesis and Characterization of Cross Linked Acetoguanamine Polymer Complexes: Investigation of their Thermal and Magnetic Properties

In this study, 2,4-diamino-6-methyl-1,3,5-triazine (acetoguanamine) was used as the starting material. 2,4-diamino-6-methyl-1,3,5-triazine was boiled under reflux with glutaraldehyde and terephthaldehyde in acetonitrile. And, s-triazine-containing polymer ligands (IV and V) were obtained by these condensation reactions. These target s-triazin containing polymer ligands we obtained were analyzed by 1H-NMR, FT-IR and elemental analysis. Then, polymeric metal (Co2+, Ni2+ and Cu2+) complexes of the polymeric ligands (VI-XI) were obtained from the interaction with CoCl2 ∙ 6H2O, NiCl2 ∙ 6H2O and CuCl2 ∙ 2H2O at 60 ℃ in ethyl alcohol. The structures of these complexes were also illuminated and elucidated using FT-IR, elemental analysis and magnetic susceptibility analysis. The polymerization degrees of the polymeric ligands were determined by the molecular weight determination study with the viscometer.

УРУҒЧИЛИК ХЎЖАЛИКЛАРИ УЧУН БИОЛОГИК ФАОЛ ПОЛИМЕР ПРЕПАРАТИВ ФОРМАЛИ КУПРУМХИТ ОЛИШ ТЕХНОЛОГИЯСИ

A technological scheme for producing a biologically active polymer – chitosan, obtained from pupae, silkworms, and copper (II) has been developed. Optimal parameters of obtaining of 9–12% of coppercontained polymer metal complexes under the technological conditions at 22°C, pH=6, and the molar ratio Chit–NH2: Cu2+1:1 were identified. On the basis of this technology, a 20 l polymeric form of Copprierchit preparation has been developed. The fungicidal and stimulating properties of the ecologically safe preparation of Copprierchit were studied in laboratory conditions. The structure and composition of the obtained biopolymers were confirmed by UV spectroscopy and elemental analysis. The results show that the polymer composition has high biological activity with 1% polymer metal complex and 0.5% polyacrylamide.

A Novel PHEMA-Based Bismuth Oxide Composite with High Photocatalytic Activity

The Stober method was used to synthesize silicon sphere carriers with uniform size. The surface of the silicon sphere carrier was treated with 3-aminopropyltrimethoxysilane and 2-bromopropionyl bromide as atom transfer radical polymerization (ATRP) initiator and grafted with polyhydroxyethyl methacrylate (PHEMA) by ATRP. Bismuth nitrate was used as bismuth source to form polymer-metal complex with PHEMA. Sodium borohydride was used to reduce the bismuth ions in the composite material to metallic bismuth, and the metal bismuth on the surface of the composite material was oxidized in air atmosphere at 450 °C to obtain the inorganic–organic bismuth oxide composite. The morphology, elemental composition and photocatalytic degradation efficiency of Rhodamine B by bismuth oxide composite were characterized by various measurements. The TG and TEM results show that the composite material has good thermal stability, and Bi2O3 has very good dispersibility and stability in the prepared Bi2O3 composite. When the pH value is 4 with a catalyst dosage of 1.2 g/L, the degradation efficiency of Rhodamine B can reach 99.3% after 4 h of light irradiation, which is 24.2% higher than that of pure bismuth oxide. After 5 cycles, Bi2O3 composites still have a strong degradation effect with a degradation rate of 90.1% for Rhodamine B dye solution, which illuminates that the prepared Bi2O3 composite has good cyclic degradation performance.

Novel Polyester Amide Membranes Containing Biquinoline Units and Complex with Cu(I): Synthesis, Characterization, and Approbation for n-Heptane Isolation from Organic Mixtures.

The wide possibilities of designing a chemical structure and creating complexes with transition metals make polymers of heteroaromatic structure interesting objects, from both scientific and practical aspects. In this work, modern biquinoline-containing polymers, namely polyester amide (PEA) and its metal–polymer complex (PEA–Cu(I)), were synthesized and used to form dense flat membranes. A comparative study of their morphology, same physical properties (density, free volume, and contact angles), and thermomechanical characteristics was carried out. The transport properties of the modern membranes were studied during pervaporation, to solve a problem of n-heptane isolation from its binary mixtures with thiophene and methanol. It was shown that only the PEA membrane is selective for the separation of thiophene impurities from the mixture with n-heptane. In pervaporation of methanol/n-heptane mixture, the РЕА–Cu(I) membrane exhibits significantly higher pervaporation separation index, as compared with that of the РЕА membrane.

Allylic hydrocarbon polymers complexed with Fe(II)(salen) as a ultrahigh oxygen-scavenging and active packaging film

Abstract Macromolecular metal complexes provide a molecular-based synergy function of organic polymers and combined metal complexes. A new category of macromolecular complexes includes catalytically active metal complexes immobilized by organic polymers containing reactive substrate moieties in their repeating units. Here, we describe the extremely efficient oxidation of allylic hydrocarbon polymers with the attached iron complex catalyst, as well as the efficient oxygen-consumption or oxygen-scavenging function of the matrix polymer film. The less toxic N,N´-di(salicylaldehyde)ethylenediiminatoiron(II) complex was combined with or fixed onto a series of allylic hydrocarbon polymers as both the oxidative substrate and the film matrix, i.e. poly(1,2-butadiene), polynorbornene, poly(5-vinyl-2-norbornene), poly(2,5-norboenadiene), poly(dicyclopentadiene), and poly(5-ethylidene-2-norbornene). Ultra-high oxygen-scavenging capacity up to 300 mL (oxygen gas at STP)/g(film) was achieved, based on the oxidative consumption of the allylic bond (particularly of poly(5-ethylidene-2-norbornene)), which was more than three times that of the previously reported highest oxygen-scavenging polymers. These oxygen-scavenging films are based on the high reactivity of polymer-metal complexes that provides an innovative development in the area of active packaging polymer films that facilitate cost-effective performance, safety, and sustainability.

Sustainable approach: Utilizing modified waste Styrofoam as an eco-friendly catalyst for dual treatment of wastewater

Styrofoam waste (WPS) was used to prepare a grafted polymer named WPS-g-MA that was applied as an adsorbent for Ni2+ and Cd2+. The obtained polymer–metal complexes (WPS-g-MA…M, where M = Ni or Cd) were then utilized separately as a photocatalyst to enhance the degradation of methylene blue (MB) dye. The chemical structure of the WPS-g-MA and WPS-g-MA…M was confirmed by their relative functional bands that appear at FTIR chart. Energy-dispersive X-ray (EDX) spectroscopy confirmed the formation of WPS-g-MA (the presence of oxygen) and WPS-g-MA…M (the presence of Ni/Cd). The surface morphology of the polymers was investigated by scanning electron microscope (SEM) measurements. The adsorption of Ni and Cd ions onto the WPS-g-MA surface depended on the pH of the metal ions solution as well as the WPS-g-MA dosage. The adsorption performance of WPS-g-MA was calculated and found to be 70% and 80% for Ni and Cd ions, respectively, at pH = 7. The WPS-g-MA...M was used as a heterogeneous catalyst to activate peroxymonosulfates (PMSs) for the production of the sulfate radicals (the most effective and non-selective catalyst for the oxidation of organic compounds). The WPS-g-MA...M caused enhancement of the catalytic activity of PMS (27%) for MB degradation to 100% after 120 min.

Ionization and Complexing Properties of Hyperbranched Polyester Poly[3-(2-aminoethyl)amino)]propionate

Syntheses of a polydentate ligand based on the second-generation hyperbranched polyester containing 3-(2-aminoethyl)amino]propionate groups and its metal complex with copper(II) ions have been elaborated. In view of the IR, electronic absorption, and EPR spectroscopy data, it has been suggested that the coordination sites in the metal-polymer complex are paramagnetic sites with the CuN4Solv2 or CuN2O2Solv2 composition (Solv = H2O, DMSO).

Получение медьсодержащих полимерных комплексов на основе хитозана, перспективных для сельскохозяйственных применений

It is well-known, due to the geological features in a number of regions of the Russian Federation, there may be a shortage of certain microelements and other important “nutrients” in animal diets. The main approach to solve this problem is to use special feed additives. At present, preparations based on organic sources, for example, metal-polymer complexes, are considered a promising alternative. The purpose of this study is to develop an improved method for preparation of the copper-containing polysaccharide complexes and to study their most important parameters. Using CuCl2 as an example, it was shown that the formation of chitosan hydrogels is possible without the usage of potentially hazardous cross-linking agents (for example, glutaraldehyde) or polyvalent anions (for example, SO4 2–), which provide non-covalent cross-linking of chitosan due to electrostatic interactions with NH3 + in its composition. It was found that, upon frontal «gelation» of a 2% chitosan solution (MM 400±100 kDa) in acetic acid (1 vol%), the formation of stable metal gels is observed provided that the content of CuCl2 and ethanol in the precipitant solution is more than 40 mg/ml or more than 24 vol.%, respectively (Vchitosan = Vprecipitant). The obtained complexes are stable in aqueous-alcoholic solutions and swell in water up to destruction (pH 5,5). After additional treatment with an aqueous 1,5% ammonia solution, complexes practically do not swell in solutions with ≥ pH 5,5 (at least τ = 6 days) and dissolve at pH ≤ 4,2. Thus, the use of these complexes is able to provide the release of Cu2 + not in the rumen (pH 6,3–7,2), but in the abomasum (pH ~ 3), which can increase the bioavailability of copper. The development of an improved method for obtaining metal-polysaccharide complexes in a gel form that does not contain «ballast» (in terms of nutritional value and physiology of farm animals) anions (for example, SO4 2–) opens up new opportunities for the development of highly effective feed additives for animal husbandry.

Photoluminescence studies of copolymer metal complexes with 8-hydroxyquinoline, hexamethylenediamine and formaldehyde

This current research article provides the information on the synthesis of 8-HQHMDAF resinous copolymer and co-polymeric metal complexes prepared from it. 8-HQHMDAF resinous copolymer was incorporated withformaldehydethroughrefluxed-condensationof8-hydroxyquinolineand1, 6-diamino hexane in fixed molar ratio for 5 hrs using two molar acidic catalyst that is hydrochloride. Reaction maintained at 124 ± 2 0C constant temperatures. The newly developed copolymer 8-HQHMDAF resin functioned as ligands to form co-ordination polymer complex in a molar ratio of 2:1 with three transition metal ions Cu2+, Ni2+ and Zn2+. The reaction conducted for 3hrs with an efficient reflux maintained at 60 °C temp. Elemental composition of 8-HQHMDAF-M copolymeric metal complexes was analyzed by elemental analysis method. FT-IR and 1H NMR Spectroscopic technique describe the structure of 8-HQHMDAF-M complex. The photoluminescence properties of newly synthesized copolymer metal complex samples were recorded on RF-501 (PC) S CE (LVD) MODEL PL spectrometer is used to records the photoluminescence spectra of synthesized copolymer metal complexes of three transition metal ion. Aim of the whole current study is the development new polymeric metal complexes to investigate its photo luminescent property and significant contributions from active researchers in the field.

Chemical modification utilizing a terminal structure exposed on the specific surface of polymer-metal complex nanocrystals

It has been difficult to selectively modify the surface of molecular crystals by chemical reactions because they usually have no reaction points on their surfaces. In this paper, focusing on the unique nanocrystal surface of the polymer metal complex (PMC) [{Cu2(μ-Br)2(PPh3)2}(μ-bpy)]n having an exposed reactive terminal chain, we successfully modified the surface of PMC nanocrystals (NCs) through an alkylation reaction. Interestingly, after the alkylation reaction, the luminescence spectrum of PMC NCs blue-shifted, and the luminescence quantum yield increased. PMC NCs with a large specific surface area showed optically peculiar or characteristic properties compared with the corresponding bulk crystals. PMC NCs have high potential as a new class of luminescent materials due to their surface effect.

Water-Soluble Metal—Polymer Gallium Complexes Based on Imino Derivatives of an N-Vinylpyrrolidone/N-Vinylamine Copolymer

Imino derivatives of salicylic aldehyde and a N-vinylpyrrolidone/N-vinylamine containing 15 mol % N-vinyl salicylidenimine were synthesized. Water-soluble metal—polymer complexes with a gallium content of 5 mol % were obtained by the interaction of imino derivatives with gallium(III) chloride. The structure and composition of the metal—polymer complex are confirmed by electron, vibrational, atomic emission spectroscopy with inductively coupled plasma, and by nuclear magnetic resonance spectroscopy.

Tunable Electronic Memory Performances Based on Poly(Triphenylamine) and Its Metal Complex via a SuFEx Click Reaction.

A triphenylamine derivative decorated with an azobenzene group (TDA) was synthesized via a SuFEx click reaction and its polymer, poly(triphenylamine) (PTDA), was polymerized through a redox polymerization. More interestingly, its polymeric metal complex, PTDA-Fe, can be simply obtained via one-pot reaction between TDA and FeCl3 owing to TDA showing a strong affinity to the FeIII ion. The sandwich memory device based on PTDA nanofilms as active layers exhibited a binary memory performance. However, the memory device based on its polymeric metal complex exhibited a unique ternary memory behavior. The different memory performances should come from the different conductive mechanism. The mechanism of such ternary memory devices is illustrated based on both the theoretical calculation and experiments. Our work provides new insights into the preparation of novel materials for multilevel memory devices.