Figure - available from: Journal of Inorganic and Organometallic Polymers and Materials
This content is subject to copyright. Terms and conditions apply.
Source publication
The advances and problems associated with the synthesis, properties and structure of metal complexes based on chelating polymer ligands are presented and assessed. The polymeric metal chelates (PMCs) are divided into molecular, intracomplex, macrocyclic and polynuclear types, which in turn are grouped according to the nature of the donor atoms (N,N...
Similar publications
![Figure 1. Perspective view of [13]ane(phenN 2 )S 2 as represented by...](publication/341018048/figure/fig1/AS:885647489380352@1588166224246/Perspective-view-of-13anephenN-2-S-2-as-represented-by-30-probability-ellipsoids_Q320.jpg)
A new tetradentate mixed aza-thioether macrocyclic ligand 2,6-dithia[7](2,9)-1,10-phenanthrolinophane ([13]ane(phenN2)S2) was successfully synthesized. Reacting metal precursors [Fe(CH3CN)2(OTf)2], Ni(ClO4)2·6H2O, and Cu(ClO4)2·6H2O with one equivalent of [13]ane(phenN2)S2 afforded [Fe([13]ane(phenN2)S2)(OTf)2] (1), [Ni([13]ane(phenN2)S2)](ClO4)2 (...
Citations
... Chelating polymers have received much attention because of their intrinsic environmentally harmless and degradable properties. Various functional groups can be used as chelators, such as phosphorous acids, carboxylates, oximes, and 1,3-diketones [5][6][7]. Chelating polymers provide several applications in a wide range of fields [8], including the ...
Chelating hyperbranched polyester (CHPE) nanoparticles have become an attractive new material family for developing high-capacity nanoscale chelating agents with highly branched structures and many functional groups in the main chains and end groups that can be used to remove heavy metals from water. In this study, a hyperbranched polyester with a particle size of 180–643 nm was synthesized with A2+B3 interfacial polymerization, using dimethylmalonyl chloride as the difunctional monomer (A2) and 1,1,1-tris(4-hydroxyphenyl)ethane (THPE) as the trifunctional monomer (B3). FTIR and NMR were used to characterize the CHPE and confirm the structure. The CHPE nanoparticles were generally considered hydrophilic, with an observed swelling capacity of 160.70%. The thermal properties of the CHPE nanoparticles were studied by thermal gravimetric analysis (TGA) with 1% mass loss at temperatures above 185 °C. The XRD of the CHPE nanoparticles showed a semi-crystalline pattern, as evident from the presence of peaks at positions ~18° and 20°. The nature of the surface of the CHPE was examined using SEM. Batch equilibrium was used to investigate the removal properties of the CHPE nanoparticles towards Cd(II) ions as a function of temperature, contact time, and Cd(II) concentration. The Cd(II) ion thermodynamics, kinetics, and desorption data on the CHPE nanoparticles were also studied.
... To calculate thermodynamic factors such Gibbs free energy (∆G, kJ/mol), enthalpy change (∆H, kJ/mol), and entropy change (∆S, J/mol.K). These thermodynamic parameters were measured using the following formulae [74][75][76]: ...
To retain uranium and molybdenum ions from G.Gattar leach liquor (GI), North Eastern Desert, Egypt, a new fabricated chelating 3-mercapto-2-trioctyl phosphinimine propionic acid (MTPP), was functionalized. Specifications for MTPP chelating ligand were successfully completed by utilizing a variety of methods. Enhanced experimental factors controlling, namely; pH, shaking time, initial uranium and molybdenum conc., MTPP dosage, A/O phase ratio, temp. and stripping agents, have been achieved. At 25 °C, pH 2 for uranium and 3.5 for molybdenum, 30 min shaking for uranium and 40 for molybdenum and 4.08 × 10–3 mol/L, MTPP/kerosene has a maximum retention power of 135 and 173.5 mg/g for uranium and molybdenum respectively. From the stoichiometric calculations point of view, approximately 1 mol of MTPP can chelate 1 mol of uranium and 3 mol of MTPP can chelate 1 mol of molybdenum. According to kinetic aspects, pseudo-second order kinetic model well interpret the extraction of U⁶⁺ and Mo⁶⁺ by MTPP giving a retention power of 131.57 mg/g for uranium and 175.43 mg/g for molybdenum. The distribution isotherm (McCabe–Thiele), predicts three theoretical extraction stages necessary to extract nearly all the uranium and molybdenum ions at an A/O ratio of 1/2 for uranium and 1/1.7 for molybdenum ions respectively, while in stripping, four and three theoretical stripping stages are needed. Based on thermodynamic regards, the extraction process by MTPP was predicted as an exothermic with a -ΔH, spontaneous with a -ΔG, and advantageous extraction at low temperatures with a small –ΔS for uranium and molybdenum ions. Uranium and molybdenum ions may be stripped successfully from the loaded MTPP/kerosene by 2 M H2SO4 with 99% efficiency. The enhanced optimized variables were finally put to use to produce uranium and molybdenum concentrate (Na2U2O7, MoO3) with 65.23% uranium content and 87% purity and 60.37% molybdenum content and 90.53% purity.
... Metal salts, in contrast to metal powder, are assumed to be easily distributed into lignin, since there are significant amounts of O-, S-and/or N-based functional groups in lignin structures. The strategy to uniformly disperse metal ions into huge 3D lignin molecules is to chelate metal ions to functional groups and form M-O, M-S, or M-N bonds when mixing lignin and metal salts in an appropriate way [3,20]. In many cases, metal-biomass mixtures are often made by incipient wetness method [21], where metal-salt solution is added to a dry biomass material and the metal salt solution is absorbed into the inner pores of the biomass through capillary action. ...
Chemical coprecipitation technique is proven to be a beneficial method to prepare uniformly mixed catalyst metal and Kraft lignin precursors. Coprecipitation is a simple, yet very complex process which is highly sensitive to the reaction conditions, particularly temperature. In an exothermic coprecipitation process, the reaction rate can become uncontrollable over certain temperatures which could lead to a thermal runaway reaction. In this work, metal-lignin nanocomposites were synthesized by coprecipitation of metal (M) salts and Kraft lignin. Kraft lignin and metal salts were dissolved in organic solvents and DI water, respectively, to make lignin solution/suspension and metal salt aqueous solution. The aqueous solutions of metal salts were then added to the lignin solutions/suspensions and mixed well, resulting in chelation of transition metal ions to the functional groups of lignin chains and co-precipitation of metal-lignin composites from the solvents. To develop a safe process for producing M-lignin composites in a large volume, potential reactions, exothermic or endothermic processes, hazards gases, and volatiles were evaluated during the coprecipitation process. The effects of transition metal type, solvent selection, concentration of metal salts, and initial solution temperature on the interactions between metal ions and Kraft lignin, metal uniformity in the lignin matrix, and morphology of the metal-lignin composites were investigated during the coprecipitation process. Cu, Mo, Ni, and Fe were investigated as the transition metals for the metal-lignin composites. Fenton or Fenton-like reactions were discovered to occur during the Fe- and Cu-lignin coprecipitation process and tremendous heat evolved, which lead to the overshoot of the reaction system temperature in a very short time (i.e. a few seconds). Significant amounts of CO2 and toxic NO2 gasses were released during the coprecipitation process when Fenton or Fenton-like reactions occurred. No interaction or a very weak interaction occurred between lignin and Mo(VI) ions when mixing both solutions. Ni ions were coordinated strongly to oxygen-containing functional groups in lignin, but no Fenton or Fenton-like reaction was detected during Ni-lignin coprecipitation. Fenton reaction or Fenton-like reaction occurred when tetrahydrofuran (THF) and acetone were used to dissolve Kraft lignin, and the reaction became highly fierce and unmanageable with increasing of iron content in the composite. The reaction initialization time was shortened with increase of initial solution temperature and thermal runaway reaction might occur if the initial mixing temperature reached 60 °C or above.
... Our group began studying the conjugated thermolysis of MCMs 30 years ago under the guidance of Professor A.D. Pomogailo, who was the Head of the Laboratory of metallopolymers at the Institute of Problems of Chemical Physics of the Russian Academy of Sciences [66]. Over the years, many of our research papers were published in the Journal of Inorganic and Organometallic Polymers [62,[67][68][69][70][71][72], and its special issue (6,2016) was dedicated to Professor A.D. Pomogailo (guest editor G.I. Dzhardimalieva). This review focuses on the main advances in the field of conjugated thermolysis of MCMs and the production of core-shell nanostructured advanced materials. ...
A detailed analysis of recent advances in the use of metal-containing monomers as precursors for the preparation of core–shell nanostructured advanced materials by the method of conjugated thermolysis was carried out. This method consists in the simultaneous course of the processes of thermal polymerization of monomers and the formation of metal-containing nanoparticles during thermal transformation. The general scheme of conjugated thermolysis includes three successive stages: dehydration (desolvation), polymerization and thermolysis of the resulting metallopolymers. Particular attention was paid to the composition of solid-phase products of conjugated thermolysis. Kinetic schemes and reactions of thermal transformation of metal-containing monomers were analyzed. The use of the obtained nanocomposites as magnetic materials, sensors, catalysts and tribological materials was generalized. Problems and prospects of using conjugated thermolysis for the production of advanced nanomaterials were outlined.
... Our group has been devoted in the syntheses of Type II metallopolymers, aiming to energy transfer systems, magnetic and thermochromic properties [32,[34][35][36][37]. Concerning thermochromic properties the major interest resides in the solid state properties, due to the potential application as nanothermometers. Various reports came out [23,38], including ours [32] describing metallopolymers with dual emissions sensitive to temperature variations, but the majority of them is related either to solution properties or with dispersions in a doping matrix [39][40][41]. ...
Aiming the development of a nanothermometer, a new Type II metallopolymer consisting of a fluorene derivative polymer complexed with europium ions is introduced, as a material with good solubility in common organic solvents and easy film formation. The structural and photophysical properties are discussed focusing on the observed ratiometric thermochromism behavior in solid state. For comparison purposes, the same structure without the complexed ions (LaPPS75) and a model compound simulating the complexed sites (LaPPS75 M) were used. The ratiometric luminescent temperature shows an operational range between 260 and 380 K with a maximum relative thermal sensitivity of 3.29% K⁻¹ at 380 K.
... Fe 2+ was bound by FOs and EDTA in a dose-dependent manner, and chelation of Fe 2+ in samples was significantly (P < 0.05) weaker than EDTA in the concentration range of 0.2 to 5.0 mg/ml. It was found that metal ion was chelated with ligand through carbonyl oxygen to form a stable chelate [53]. The FOs could to chelate combine with metal ions based on the phenoxy group, but chelating ability was affected by its charge density due to introduction of para oligosaccharides in FOs. ...
In this study, four main components of feruloylated oligosaccharides (FOs),FOs-1, FOs-2, FOs-3 and FOs-4,were isolated from wheat bran by use of Amberlite XAD-2 and Sephadex LH-20. Structural characterization of FOs was determined by use of high performance liquid chromatography (HPLC), gas chromatography (GC) and fourier transform-infrared spectroscopy (FT-IR). Antioxidant properties were investigated in vitro. Average degrees of polymerization (DP) of the four components (FOs-1, FOs-2, FOs-3 and FOs-4) were approximately 10.6, 7.7, 6.1 and 3.4, respectively. In addition, DP were consistent with molar ratios of arabinose and xylose in 1:9.46, 1:5.30, 1:2.91 and 1:0.19, respectively. The presence of β-glycosidic linkage was confirmed at 896 cm − 1 by use of FT-IR. In vitro antioxidant studies demonstrated that FOs-1, FOs-2, FOs-3 and FOs-4 possessed significant antioxidant activities in the dose-dependent manner. In addition, the degree of polymerization affected antioxidant capacity. These results have improved our understanding of the relationship between FOs with different structural types and their antioxidant activities.
... The methods of binding metal compounds to a polymer are very diverse and include different types of interactions [181,182]. ...
This review summarizes the latest advances in the preparation of metal-polymer nanocomposites by chemical reduction of metal ions in polymer matrices that are classified according to their functions as stabilizing agents, templates and reducing agents. Particular attention is paid to various factors affecting the size and morphology of particles, the composition and structure of metal-polymer nanocomposites. Problems and prospects of development of metal-polymer nanocomposites obtained by chemical reduction of metal ions are considered.
... Our group began studying the conjugated thermolysis of MCMs 30 years ago under the guidance of Professor A.D. Pomogailo, who was the Head of the Laboratory of metallopolymers at the Institute of Problems of Chemical Physics of the Russian Academy of Sciences [66]. Over the years, many of our research papers were published in the Journal of Inorganic and Organometallic Polymers [62,[67][68][69][70][71][72], and its special issue (6,2016) was dedicated to Professor A.D. Pomogailo (guest editor G.I. Dzhardimalieva). This review focuses on the main advances in the field of conjugated thermolysis of MCMs and the production of core-shell nanostructured advanced materials. ...
A common drawback of practically all methods for obtaining metal–polymer nanocomposite materials with “core–shell” structure is the multistage of process, on the one hand, and the formation of polydispersed systems with a wide distribution of particle size, on the other hand. Traditional approaches are rather laborious and include the stage of formation of macromolecular complexes, metal ions reduction reaction to form nano-sized particles, separation of the phase of chemically unbound components.
The present work describes the grafting of a polymer-metal chelate (PMC) from mesoporous silica (SBA-15) via the Surface Initiated-Atom Transfer Radical Polymerization (SI-ATRP). SBA-15 was silylated by 2-bromo-2-methyl-N-(3-(trimethoxysilyl)propanamide (BTPAm) to give the surface-anchored ATRP initiator. The monomer, N-(4-(5-(pyridin-2-yl)-1,3,4-oxadiazol-2-yl)phenyl)acrylamide (POPA), was polymerized from the SBA-15 surface via the ATRP approach to give poly(POPA)-g-SBA-15. The grafted chelating polymer ligand (CPL) was treated with an ethanolic solution of PdCl2 to afford the SBA-15 grafted PMC, poly(POPA)-g-SBA-15-Pd(II). The grafted PMC was characterized by FT-IR, CP/MAS 13C NMR, thermo-gravimetric analysis (TGA), and Brunauer–Emmett–Teller (BET) analysis. X‐Ray photoelectron spectroscopy (XPS) corroborated that the major palladium species have the (+2) oxidation state. The catalytic activity of the grafted PMC was examined in the Heck reaction between haloarenes and olefins after establishing the optimal reaction conditions. Interestingly, chloroarenes exhibited enhanced activities than bromoarenes. Their activity was comparable to iodoarenes. The excellent recyclability of the catalyst was shown by negligible deactivation over six runs.
