Synthesis and characterization of antibacterial polychelates of urea–formaldehyde resin with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) metal ions

We studied the reaction between urea and formaldehyde with the purpose of preparing new polychelates of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) metal ions. These compounds were characterized by elemental analysis, IR spectroscopy, ¹H‐NMR, electronic spectroscopy, thermogravimetric analysis (TGA), and molar conductance measurements. The percentage of metal in all of the polychelates was found to be consistent with 1:1.5 (metal/ligand) stoichiometry. The thermal behaviors of these coordination polymers were studied by TGA in a nitrogen atmosphere up to 750°C. The TGA results reveal that the complexes had higher thermal‐resistance properties compared to the common urea–formaldehyde resin. The molar conductivity and magnetic susceptibility measurements of the synthesized polychelates confirmed the geometry of the complexes. The antibacterial activity of the polychelates was also investigated with agar diffusion methods. The antibacterial activity of these polychelates was found to be reasonably good compared with standard drugs, namely, ciprofloxacin, ampicillin, and kanamycin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 928–936, 2006     

Polychelates of poly[N-(4-carboxy-3-hydroxyphenyl)maleimide]

The reactions of the bidentate polymeric chelating ligand poly[N-(4-carboxy-3-hydroxyphenyl)maleimide] with Co(II), Ni(II), Cu(II), Zn(II) and UO₂(II) metal ions were investigated. Analytical, magnetic, spectral and thermal studies were used to characterize these polychelates. All these polychelates are stable, intensely coloured solids and insoluble in common organic solvents.     

New polymeric Schiff base and its metal complexes

A novel polymeric Schiff base was synthesized by the reaction of a Schiff base from 2,4‐dihydroxy benzaldehyde and aniline with acryloyl chloride and was polymerized in methyl ethyl ketone at 70°C with benzoyl peroxide as a free‐radical initiator. Polychelates were obtained in an alkaline solution of poly(2‐hydroxy‐4‐acryloyloxy‐N‐phenylbenzylidine) with aqueous solutions of metal ions such as Cu(II), Ni(II), Co(II), Ca(II), Cd(II), Mn(II), and Zn(II). The polymeric Schiff base and polychelates were characterized with elemental analysis and spectral studies. The elemental analysis of the polychelates suggested that the metal‐to‐ligand ratio was 1:2. The IR spectral data of the polychelates indicated that the metals were coordinated through the nitrogen and oxygen of the phenolic ? OH group. Diffuse reflectance spectra, electron paramagnetic resonance, and magnetic moment studies revealed that the polychelates of the Cu(II) complex were square‐planar, those of the Ni(II), Mn(II), and Co(II) complexes were octahedral, and those of the Ca(II), Cd(II), and Zn(II) complexes were tetrahedral. X‐ray diffraction studies revealed that the polychelates were highly crystalline. The thermal properties of the Schiff base and polychelates were also examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 494–500, 2004     

Mechano-chemische Komplexbildung durch Schwingmahlung von Poly(ε-caprolactam) mit Eisenchlorid in an- oder Abwesenheit von Äthylendiamin

Mechano-chemical syntheses of polychelates by vibratory milling using poly(ε-caprolactam) as parent polymer was studied. As ligands were utilized either distruction fragments of poly(ε-caprolactam) or their polycondensation products with ethylenediamine. As complexing centers were used Fe³⁺ ions from FeCl₃·6H₂O. Some properties of the polychelates are described.     

Polymer–metal complexes: Synthesis and characterization of poly(4-acetyl-3-hydroxyphenylacrylate) and its metal chelates

4-Acetyl-3-hydroxyphenylacrylate (AHAH) was synthesized and polymerized in 2-butanone using benzoyl peroxide as initiator. Poly(4-acetyl-3-hydroxyphenyl-acrylate) (PAHAH) was characterized by infrared and nuclear magnetic resonance techniques. The molecular weight of the polymer was determined by gel permeation chromatography. Cu(II) and Ni(II) chelates of PAHAH were synthesized. The diffuse reflectance spectra and magnetic moments of the polychelates show distorted planar and octahedral structures for poly[Ni(AHA)₂] and poly[Cu(AHA)₂(OH₂)₂] complexes, respectively. The thermal properties of the polychelates are also discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 177–182, 1998     

Thermal,catalytic, antimicrobial,and chelating aspects of phenolic resin and its polychelates with f‐block elements

The polymeric ligand (resin) was synthesized by condensation of 2‐hydroxy‐4‐ethoxybenzophenone with ethane diol in the presence of polyphosphoric acid as a catalyst at 145°C for 10 h. The synthesized resin was used to study its ion exchange efficiency and to synthesize its polychelates with 4f‐block elements. The resin and its polychelates were characterized on the basis of elemental analyses, electronic spectra, magnetic susceptibilities, IR, NMR, and thermogravimetric analyses. The molecular weight was determined using number–average molecular weight (M_n ) by a vapor pressure osmometry (VPO) method. Ion‐exchange studies at various concentrations of different electrolytes, pH, and rate have been carried out for f‐block elements. Antimicrobial activity of all polychelates and catalytic activity of selected polychelates in organic synthesis have been studied. It is observed that resin can be used as an ion‐exchanger and polychelates are found to be an efficient catalysts and antimicrobial agents. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthetic,spectroscopic, magnetic,thermal, and antimicrobial approach towards new biocidal coordination polymers

O‐aminophenol was reacted with glutraldehyde to obtain Schiff base, which was then reacted with formaldehyde in slight acidic medium to generate phenolic groups. Now the substituted Schiff base was reacted with the transition metal acetates of Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) to get polymeric metal complexes. Their structures have been elucidated on the basis of elemental analyses, ¹H NMR spectra, ¹³C NMR spectra, magnetic measurements, thermogravimetric analyses, electronic spectra, and infrared spectra. The results are in accordance with an octahedral environment around the central metal ion. The polychelates of Mn(II), Co(II), Ni(II), and Cu(II) are paramagnetic while Zn(II) polychelate was found to be diamagnetic. The synthesized Schiff base acted as a uninegative bidentate ligand and bonding occurs through the hydroxyl oxygen and nitrogen atoms. The thermal behavior of these coordinating polymers was studied by TGA in nitrogen atmosphere up to the temperature range of 800°C. All the synthesized polychelates were also screened for their biocidal activity against Escherichia coli, Staphylococcus aureus, Bacillus subtilis (bacteria), Candida albicans, and Muller species (yeast) by using agar well diffusion method. All the metal polychelates show promising antimicrobial activities. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci 124:3971–3979, 2012     

Thermal Aspects of Coordination Polymeric Chain Assemblies of Some Transition Metal Ions with 8-Hydroxy Quinoline

The novel chelating (QMCM) has been synthesized through copolymerization of 8-hydroxyquinoline and 4,4′-methylene bisphenol monomers in the presence of a base as a catalyst. The novel developed copolymer ligand (H₂L) has been used to prepare a series of five polymeric chelates (ML) using transition metal ions. The chemical structure of polychelates on the basis of elemental and IR characterization suggests that the uninegative bidentate ligand (H₂L) coordinates to metal ions through an oxygen atom of the phenolic hydroxyl group by replacing the hydrogen atom and nitrogen of the quinoline ring. The studies of magnetic moments and electronic spectra reveal that all polychelates with octahedral geometry are paramagnetic in nature, except that of Zn(II) chelate, which is diamagnetic. The thermogravimetric analysis of parent ligand and its metal chelates have shown remarkable difference in mode of thermal decomposition and their thermal stabilities. The kinetic parameter and energy of activation (E _a) of thermal decomposition has also been estimated by the Broido method.     

Metal ion interaction of water‐soluble copolymers containing carboxylic acid groups in aqueous phase by membrane filtration technique

This article reports the synthesis of poly(N‐maleoylglycine‐co‐itaconic acid) by radical copolymerization under different feed mole ratios and its properties to remove various metal ions, such as Cu(II), Cr(III), Co(II), Zn(II), Ni(II), Pb(II), Cd(II), and Fe(III), in aqueous phase with the liquid‐phase polymer‐based retention(LPR) technique. The interactions of inorganic ions with the hydrophilic water‐soluble polymer were determined as a function of pH and filtration factor. Metal ion retention was found to strongly depend on the pH. Metal ion retention increased as pH and MG content units in the macromolecular backbone increased. The copolymers were characterized by elemental analysis, FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. Additionally, intrinsic viscosity, molecular weight, and polydispersity have been determined for the copolymers. Copolymer and polymer–metal complex thermal behavior was studied using differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques under nitrogen atmosphere. The thermal decomposition temperatures (TDT) were influenced by the copolymer composition. The copolymers present lower TDT than the polymer–metal complex with the same copolymer composition. All copolymers present a single T_g, indicating the formation of random copolymers. A slight deviation of the T_g for the copolymers and its complexes can be observed. The copolymer T_g is higher than the T_g value for the polymer–metal complexes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Studies on various divalent metal complexes of poly(2-hydroxy-4-acryloyloxybenzophenone) in aqueous medium

2-Hydroxy-4-acryloyloxybenzophenone (2H4ABP) prepared by reacting acryloyl chloride with 2,4-dihydroxybenzophenone, was polymerized in 2-butanone at 65°C using benzoyl peroxide as initiator. Polychelates were obtained in the alkaline solution of poly(2H4ABP) with aqueous solutions of metal ions such as Ni(II), Mn(II), Co(II), Ca(II), Cd(II) and Zn(II). The polymer and polychelates were characterized by elemental analyses and spectral studies. Elemental analyses of the polychelates suggest that the metal-to-ligand ratio is 1: 2. The IR spectral data of the polychelates indicate that the metals were coordinated through the oxygen of the keto group and oxygen of the phenolic −OH group. The diffuse reflectance spectra, EPR and magnetic moments studies reveal that the polychelates of Cu(II) complex are square planar, and Ni(II), Mn(II) and Co(II) complexes are octahedral, while Ca(II), Cd(II) and Zn(II) complexes are tetrahedral. X-ray diffraction studies revealed that the polychelates are highly crystalline. The thermal and electrical properties of polymer and polymer–metal complexes are discussed. © 1998 SCI.     

Antimicrobial Polychelates: Synthesis and Characterization of Transition Metal Chelated Barbituric Acid–Formaldehyde Resin

A monomeric Schiff base was prepared by the condensation reaction of salicylaldehyde and semicarbazide, which further react with formaldehyde and barbituric acid-formed polymeric Schiff base. Its metal polychelates were then formed with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II). All the synthesized compounds were characterized by elemental analysis, magnetic moment, FTIR, ¹HNMR, and electronic spectroscopies. The elemental analysis data show the formation of 1:1 [M: L] metal polychelates. Thermogravimetric analysis was carried out to find the thermal behavior of all the synthesized polymeric compounds and thermal data revealed that all the metal polychelates are more thermally stable than their parent polymeric Schiff base. All the synthesized polymeric compounds were screened for antimicrobial activity against some clinically important microorganisms, such as Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis, Staphylococcus aureus, Staphylococcus typhi, Candida albicans, Microsporum canis, and Aspergillus niger. In vitro antimicrobial activity was determined by the Agar Well Diffusion method and the result shows that all the metal polychelates exhibited better antimicrobial activity than their parent polymeric Schiff base.     

Synthesis,characterization, and thermal and antimicrobial studies of newly developed transition metal–polychelates derived from polymeric Schiff base

Monomeric Schiff base derived from salicylaldehyde and 1,3‐diaminopropane was subjected to polycondensation reaction with formaldehyde and piperazine in basic medium. The resin was found to form polychelates readily with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) metal ions. The materials were characterized by elemental analysis, spectral studies (IR, ¹H‐NMR, ¹³C‐NMR, and UV–visible), magnetic moment measurements, and thermal analysis. The electronic spectra and magnetic moment measurements of the synthesized polychelates confirmed the geometry of the central metal ion. Metal–resin bonds were registered in the IR spectra of the polychelates. The thermogravimetric analysis data indicated that the polychelates were more stable than the corresponding polymeric Schiff base. All the synthesized metal–polychelates showed excellent antibacterial activities against the selected bacteria. The antimicrobial activities were determined by using the shaking flask method, where 25 mg/mL concentrations of each compound were tested against 10⁵ CFU/mL bacteria solutions. The number of viable bacteria was calculated by using the spread‐plate method, where 100 μL of the incubated antimicrobial agent in bacteria solutions were spread on agar plates, and the number of bacteria was counted after 24 h of incubation period at 37°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis, characterization and solution properties of a double-hydrophilic multiblock copolymer with sulfonic groups

The double-hydrophilic multiblock copolymers poly(ethylene glycol)-b-poly((2-acrylamido-2-methyl propanesulfonic sodium) (PEG-b-PAMPSNa) with different PEG and PAMPSNa ratio have been synthesized. The copolymers were characterized by FTIR, ¹H-NMR, elemental analysis, thermogravimetric analysis (TGA) and Gel permeation chromatography coupled with multi-angle light scattering laser light scattering (GPC-MALLS). According to the results, it was seen that the compositions had obvious influences to the characteristics of the copolymers. With more PEG content in the copolymers, the molecular weights and thermal stability increased, and the copolymers chain structures were more flexible. The solution properties of the copolymers were studied by dynamic light scattering (DLS), which also have great relationship with the copolymers compositions. And PEG-b-PAMPSNa was used as a crystal growth modifier to control the crystallization of BaSO₄ in its aqueous solution. The morphologies and sizes of BaSO₄ crystals can be well controlled by the copolymer. With the increasing concentration, the copolymer assembled in water and interacted with inorganic particles on the crystal faces, which is concerned with the controlling of crystal growth in solution.     

Polymer-metal complexes: Synthesis, characterization, and properties of poly(maleic acid) metal complexes with Cu(II), Co(II), Ni(II), and Zn(II)

SUMMARY Polymer metal complexes of poly(maleic acid) and Cu(II), Co(II), Ni(II), and Zn(II) were synthesized. Elemental analysis, as well as magnetic, spectral and thermal properties, in addition to electrical conductivities of the chelates were investigated, and possible structures have been assigned to the polychelates. Semi-empirical calculations at the PM3 level were carried out on the geometrical arrangement of the polychelates. Received: 19 November 1999/Revised version: 22 March 2000/Accepted: 31 March 2000     

Thermal properties of poly(maleic anhydride‐alt‐acrylic acid) in the presence of certain metal chlorides

Polychelates were synthesized by the addition of aqueous solutions of copper(II), cadmium(II), and nickel(II) chlorides to aqueous solutions of poly(maleic anhydride‐alt‐acrylic acid) [poly(MA‐alt‐AA)] in different pH media. The thermal properties of poly(MA‐alt‐AA) and its metal complexes were investigated with thermogravimetry and differential scanning calorimetry (DSC) measurements. The polychelates showed higher thermal stability than poly(MA‐alt‐AA). The thermogravimetry of the polymer–metal complexes revealed variations of the thermal stability by complexation with metal ions. The relative thermal stabilities of the systems under investigation were as follows: poly(MA‐alt‐AA)–Cd(II) > poly(MA‐alt‐AA)–Cu(II) > poly(MA‐alt‐AA)–Ni(II) > poly(MA‐alt‐AA). The effects of pH on the complexation and gravimetric analysis of the polychelates were also studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3926–3930, 2006     

Synthesis and characterization of poly(1,3‐thiazol‐2‐yl‐carbomoyl) methyl methacrylate: Its metal complexes and antimicrobial activity studies

Poly(1,3‐thiazol‐2‐yl‐carbomoyl) methyl methacrylate [poly(TCMMA)] is prepared in dimethyl sulfoxide using 2,2′‐azobisisobutyronitrile as an initiator at 60°C. Poly(TCMMA) is characterized by IR and ¹H‐NMR spectroscopic techniques. Cadmium(II), copper(II), and nickel(II) chelates of poly(TCMMA) were synthesized. An elemental analysis of the polychelates suggests a metal/ligand ratio of 1:2. The polychelates are further characterized by IR and magnetic susceptibility measurements. The thermal properties of the polymer and metal chelates are also discussed. The molecular weights of the poly(TCMMA) are determined by the gel permeation chromatography technique. The antimicrobial activities of the polymer and metal chelates are tested against Staphylococcus aureus COWAN I (bacteria), Escherichia coli ATCC 25922 (bacteria), Listeria monocytogenes SCOTTA (bacteria), Bacillus subtilis LMG (bacteria), Enterobacter aeroginosa CCM 2531 (bacteria), Klebsiela pneumania FMCS (bacteria), Candida albicans CCM 314 (Mayo yeast), and Saccharamyces cerevisiae UGA 102 (Mayo yeast). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3244–3251, 2003     

Coordination polymers,VII. Polymeric metallated organic pigments of the schiff base derived from 4,4′-(4,4′-biphenylylene bisazo)di(salicylaldehyde) and p-toluidine

Chelate polymers of Cr(III), Fe(III), Fe(II), Co(II), Ni(II), and Cu(II) with the schiff base of 4,4′-(4,4′-biphenylylene bisazo)di(salicylaldehyde) with p-toluidine have been prepared. All the polychelates are dark coloured and insoluble in common organic solvents. The octahedral structures of the polychelates were suggested on the basis of electronic spectra and magnetic susceptibility measurements in conjunction with infra-red measurements. All polychelates are non-electrolytes. The thermal stability of all the polychelates was determined from their thermogravimetric analyses.     

Polychelates of poly(acrylic acid-co-acrylamide)with Cu(II), Co(II), and Ni(II) Synthesis and properties

SUMMARY Polychelates were obtained by addition of an aqueous solution of the poly(acrylic acid-co-acrylamide) to an aqueous solution of Cu(II), Co(II), and Ni(II). All the polychelates were insoluble in water and in common organic solvents. The polychelates were characterized by elemental analysis, FT-IR spectroscopy thermogravimetry, and showed tetrahedral arrangement for Co(II) and Ni(II). Magnetic and conductivity studies for all the polychelates were also carried out. The poly(acrylic acid-co-acrylamide) behaved as semiconductor. Received: 25 July 1997/Revised version: 1 December 1997/Accepted: 5 December 1997     

Effect of crosslinked structure on SO2 gas sorption properties in amino‐functional copolymers

SO₂ gas sorption properties were examined for poly(styrene‐co‐chloromethyl styrene) functionalized with N,N‐dimethyl‐1,3‐propanediamine (DMPDA). The DMPDA‐functional copolymers were prepared under various reaction conditions. Two types of SO₂ sorption behaviors were observed for these DMPDA‐functional copolymers: SO₂ sorption capacity was very high irrespective of slow sorption/desorption rates (type I), and the sorption/desorption rates were very fast while SO₂ sorption capacity was small (type II). Fourier transform infrared analysis and dielectric loss measurement revealed that the type II sorption behavior was obtained for the highly crosslinked DMPDA‐functional copolymers. The degree of crosslinking was affected by both the solvent used to react DMPDA with the copolymer and the percent conversion of the chloromethyl styrene group. It was confirmed that DMPDA‐functional copolymers having a highly crosslinked structure are suitable materials in quartz crystal microbalance (QCM)‐type polymeric SO₂ gas sensors. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2982–2987, 2003     

Synthesis,characterization and antimicrobial activity of transition metal chelated thiourea‐formaldehyde resin

A polymeric ligand (thiourea‐formaldehyde resin ‐ TUFR) bearing nitrogen and sulfur donor groups was synthesized by the polycondensation of thiourea and formaldehyde in acidic medium and its polychelates were prepared in alcoholic solution of metal ions such as Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). The TUFR polymeric ligand and its TUFR‐M(II) polychelates were characterized with micro‐analytical analysis and spectral studies. The FTIR spectra of polychelates indicated that the metal ions were coordinated through the sulfur of the thionyl (C?S) groups and formed a covalent bond with the nitrogen of the NH groups. Electronic spectra, electronic spin resonance (ESR) spectra and magnetic moments revealed that the polychelates of Mn(II), Co(II) and Ni(II) were octahedral; however, Cu(II) and Zn(II) polychelates were square‐planar and tetrahedral, respectively. The thermogravimetric analysis data indicated that the polychelates were more stable than the corresponding ligand. The antimicrobial activities of all the compounds against several bacteria and fungi were also investigated by using the agar well diffusion method. Copyright © 2006 Society of Chemical Industry