cis-Diaminedichloroplatinum(II) complexes reversibly bound to water-soluble polyaspartamide carriers for chemotherapeutic applications. II: Platinum coordination to ethylenediamine ligands attached to poly(ethylene oxide)-grafted carrier polymers

In continuation of previous investigations aiming at the development of macromolecular metal complexes for biomedical use, this communication describes poly(alkylene oxide)-grafted polymeric platinum complexes. The platinum-containing macromolecules are obtained from presynthesized polyaspartamide carriers bearing poly(ethylene/propylene oxide) side chains and hydroxyethyl side groups as hydrosolubilizing units in addition to ethylenediamine side group terminals for metal coordination. Platination is brought about by treatment of the carriers with tetrachloroplatinate(II) ion in aqueous solution at 25–60°C. pH 4–6. The polymeric products, purified by dialysis in aqueous solution, are isolated by freeze-drying in yields of 60–80%. Platinum contents are in the range of 4–15%. The metal is bound to the carrier through chelation with the ethylenediamine ligands, forming square-planarcis-dichloroethylenediamine-platinum(II) complex species as side-chain terminals. Initially, the product polymers dissolve smoothly in water. Although on room-temperature storage in the solid state they gradually turn insoluble as a consequence of intermolecular solid-state interaction, solubility is retained on low-temperature storage and in frozen aqueous solutions.Presented in part at the Fifth International Symposium on Macromolecule-Metal Complexes. September 29–October 3, 1993. Bremen, Germany. For Part I of this Series, see Ref. 1.     

cis-Diaminedichloroplatinum(II) Complexes Reversibly Linked into the Main Chain of Water-Soluble Polyamides

As a follow-up study to previous work involving the platination of polyamide carriers through metal chelation by side group-incorporated ethylenediamine ligands, the present investigation is concerned with the synthesis of platinum-containing polymers in which the metal-coordinating ethylenediamine segments are components of the main chain. Two chloro groups in cis geometry are attached to each Pt atom as additional ligands, complementing a square-planar cis-diaminedichloroplatinum(II) complex system. The water-soluble polymeric carriers are synthesized by Michael-type addition polymerization, interfacial polymerization, and high-temperature solution polycondensation techniques and are crudely fractionated by stepwise aqueous dialysis, ultimately in tubing with a molecular mass cutoff of 25,000. Carrier platination is brought about by treatment with tetrachloroplatinate(II) anion in aqueous solution, care being taken to exercise strict control of reaction variables and workup conditions in an effort to restrict platination to the given ligands and avoid metal aquation or hydroxylation. The platinum conjugates, with Pt contents ranging from about 11 to 23% by mass, are completely soluble in aqueous media when freshly prepared, although long-term storage at room temperature in the solid state is conducive to gradual loss of solubility. The conjugates are of interest as carcinostatic agents.     

cis-Diaminedichloroplatinum(II) Complexes Reversibly Linked into the Main Chain of Water-Soluble Polyamides

As a follow-up study to previous work involving the platination of polyamide carriers through metal chelation by side group-incorporated ethylenediamine ligands, the present investigation is concerned with the synthesis of platinum-containing polymers in which the metal-coordinating ethylenediamine segments are components of the main chain. Two chloro groups in cis geometry are attached to each Pt atom as additional ligands, complementing a square-planar cis-diaminedichloroplatinum(II) complex system. The water-soluble polymeric carriers are synthesized by Michael-type addition polymerization, interfacial polymerization, and high-temperature solution polycondensation techniques and are crudely fractionated by stepwise aqueous dialysis, ultimately in tubing with a molecular mass cutoff of 25,000. Carrier platination is brought about by treatment with tetrachloroplatinate(II) anion in aqueous solution, care being taken to exercise strict control of reaction variables and workup conditions in an effort to restrict platination to the given ligands and avoid metal aquation or hydroxylation. The platinum conjugates, with Pt contents ranging from about 11 to 23% by mass, are completely soluble in aqueous media when freshly prepared, although long-term storage at room temperature in the solid state is conducive to gradual loss of solubility. The conjugates are of interest as carcinostatic agents.     

cis-Diaminedichloroplatinum(II) complexes reversibly bound to water-soluble polyaspartamide carriers for chemotherapeutic applications. I. Platinum coordination to preformed,carrier-attached ethylenediamine ligands

Copolyaspartamides3–5, bearing the ethylenediamine (en) ligand as a repetitive side-chain component in addition to various hydrosolubilizing groups, are synthesized from polysuccinimide1 by a two-step aminolytic ring opening reaction. The completely water-soluble polyamides, possessing inherent viscosities of 5–20 ml g^?1, are used as polymeric carriers for the “anchoring” of the biomedically important diaminedichloroplatinum(II) coordination complex. Conjugate formation is brought about by treatment of the carriers with the tetrachloroplatinate(II) dianion in aqueous solution at pH 6.0 ± 0.5. The resulting, water-soluble conjugates3-Pt-5-Pt, purified by dialysis (12,000–14,000 molecular mass cutoff) and isolated in the solid state by freeze-drying from aqueous solution, possess platinum contents in the typical range of 15–25%. The metal is bound as acis-dichloro-en-Pt(II) complex to the polymer main chain via a short spacer segment incorporating a biofissionable amide link suitable forin vivo release of the complex. The conjugates are of interest as water-soluble macromolecular platinum coordination compounds for potential use in the chemotherapy of cancerous diseases.     

Studies on uptake behavior of Hg(II) and Pb(II) by amine modified glycidyl methacrylate–styrene–N,N′-methylenebisacrylamide terpolymer

The removal of mercury and lead ions from aqueous solutions investigated by ethylenediamine, diethylenetriamine and tetraethylenepentamine functionalized polymeric adsorbent. The adsorbent was prepared by amination of terpolymer synthesized from glycidylmethacrylate, styrene and N,N′-methylenebisacrylamide. In the single metal species system (only mercury or lead ions are present) poly(glycidylmethacrylate–ethylenediamine) (PGMA–EDA), poly(glycidylmethacrylate–diethylenetriamine) (PGMA–DETA), and poly(glycidylmethacrylate–tetraethylenepentamine) (PGMA–TEPA) were found to adsorb lead or mercury ions with a slightly higher adsorption uptake capacity for lead than mercury ions. Among the three functionalized polymers poly(glycidylmethacrylate–diethylenetriamine) (PGMA–DETA) shows faster and higher adsorption capacity than poly(glycidylmethacrylate–ethylenediamine) (PGMA–EDA), poly(glycidylmethacrylate–tetraethylenepentamine) (PGMA–TEPA). The natural pH of both the metal ions was found to be most suitable for uptake. The uptake of Hg(II) and Pb(II) ions was investigated by using batch technique. The maximum adsorption capacities of Pb ions were predicted to be 4.74, 4.76 and 4.73 mmol/g and the maximum Hg(II) ion uptakes were found to be 4.76, 4.80 and 4.21 mmol/g respectively for PGMA–EDA, PGMA–DETA and PGMA–TEPA resins at their natural pH. The uptakes of Hg(II) and Pb(II) ions on the resins were found to follow Langmuir adsorption isotherm and pseudosecond order kinetics.     

Water-Soluble Monoamineplatinum(II) Complexes Bound to Polyaspartamide Carriers by a Poly(ethylene Oxide) Spacer

In continuation of earlier work in this laboratory comprising the synthesis of water-soluble polyaspartamide-monoamineaquadichloroplatinum conjugates as potential antineoplastic agents, the presently described project is concerned with related conjugates in which the same type of monoamineplatinum complex unit is bound to polyaspartamide carriers via main chain-attached poly(ethylene oxide) (PEO) spacers introduced here in order to improve certain biomedical performance features. The conjugates are synthesized by aqueous-phase platination of amine terminals on the PEO side chains of the carriers, brought about by treatment with tetrachloroplatinate(II) anion under closely controlled conditions of time, temperature, and acidity, followed by dialysis. The target polymers, separated by freeze-drying, are completely water soluble upon isolation, yet undergo slow intermolecular interaction in the solid state with a gradual loss of solubility unless stored in (frozen) aqueous solution at –30°C.     

Studies of poly(8‐hydroxy‐4‐azoquinolinephenol‐formaldehyde) and its metal complexes

Poly(8‐hydroxy‐4‐azoquinolinephenol‐formaldehyde) resin (8H4AQPF) was prepared by condensing 8‐hydroxy 4‐azoquinoline phenol with formaldehyde (1 : 1 mol ratio) in the presence of oxalic acid. Polychelates were obtained when the DMF solution of poly(8H4AQPF) containing a few drops of ammonia was treated with the aqueous solution of Cu(II) and Ni(II) ions. The polymeric resin and polymer–metal complexes were characterized with elemental analysis and spectral studies. The elemental analysis of the polymer–metal complexes 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 polymer–metal complexes of the Cu(II) complexes were square planar and those of the Ni(II) complexes were octahedral. X‐ray diffraction studies revealed that the polymer metal complexes were crystalline. The thermal properties of the polymer and polymer–metal complexes were also examined. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1506–1510, 2006     

Cytotoxicity of Selected Water-Soluble Polymer–cis-Diaminedichloroplatinum(II) Conjugates Against the Human HeLa Cancer Cell Line

Several polymer-platinum conjugates comprising the square-planar cis-diaminedichloroplatinum(II) complex system of cisplatin-type anticancer drugs are screened for antiproliferative activity in cell culture tests. The water-soluble conjugates prepared in this study or taken from preceding investigations are obtained by platination of aliphatic polyamide carriers containing ethylenediamine segments as side-group or main-chain components. These segments, coordinating to the metal as cis-diamine chelating ligands, are bound to, or into, the carrier backbone through biofissionable amide links permitting drug release from the carrier. In vitro tests are performed against a HeLa human cervix carcinoma cell line. IC₅₀ data, expressed as the concentration of Pt in the conjugates (μg/ml), causing 50% inhibition of cell growth, show the highest activity, with IC₅₀=14 μg/ml, to be associated with a conjugate derived from a polyaspartamide carrier that contains the platinum complex as a side group in proximity to the main chain and, additionally, contains dimethylaminopropyl side groups as solubilizing functions. At the low end of the performance spectrum is a conjugate, with IC₅₀>120 μg/ml, possessing a similar backbone and metal-binding structure, yet comprising long poly(ethylene oxide) grafts. The latter apparently shield the complex-binding tether from enzymatic attack and thus prevent efficient intracellular release of the monomeric complex. Selected conjugates will be submitted for toxicological evaluation.     

Water-soluble oxidized starch in complexation of Fe(III), Cu(II), Ni(II) and Zn(II) ions

The structure of the bromate-oxidized wheat starch (OS) contains partly opened glucose units with carbonyl and carboxyl groups at C2-, C3- or C6-positions. OS with a variable degree of oxidation (DO) was studied in alkaline conditions as a water-soluble complexing agent for Fe(III), Cu(II), Ni(II) and Zn(II) ions, which are common in various wastewaters. Complexation was studied by inductively coupled plasma-optical emission spectrometry (ICP–OES) in a single metal ion or multi-metal ion solutions. The DO affected the efficiency of the complexation with metal ions. OS with the high DO (carboxyl and carbonyl DO of 0.72 and 0.23, respectively) complexed and held Fe(III) or Zn(II) ions in a soluble form effectively in 0.5 mM single ion alkaline solution with the molar ratio of 0.65:1 of oxidized starch-to-metal ion (OS-to-M). The OS-to-M molar ratio of 1.3:1 was required to form a soluble complex with Cu(II) or Ni(II) ions. These complexes were thermally stable at the temperature range of 20–60 °C. OS with the low DO (carboxyl and carbonyl DO 0.47 and 0.17, respectively) complexed Zn(II) ions highly, Cu(II) and Ni(II) ions poorly and Fe(III) ions only partly. In the multi-metal ion solution of OS the solubility of these metal ions improved with the increasing DO of starch, which followed the same tendency as was observed in the single metal ion systems. The increased molar ratio of OS-to-M improved the complexation and solubility of the metal ions in all multi-metal ion series. As the soluble multi-metal ion complexes were reanalyzed after 7 days, all solutions had kept the high complexation and solubility of metal ions (ca. 90%). Complexation by OS did not show a selective binding of the ions in the multi-metal ion solution. It was concluded that the flexible, opened ring structure units of OS prevented the selective binding to metal ions but made the complexes highly stable. Titrimetric studies of OS–Fe(III) complexation showed that each anhydroglucose unit of OS had more than one coordination site and as the content of OS increased, the free sites coordinated to Fe(III) ions and formed cross-linked starch structures.     

Removal of Cd(II), Hg(II), and Pb(II) ions from aqueous solution using p(HEMA/chitosan) membranes

An interpenetration network (IPN) was synthesized from 2‐hydroxyethyl methacrylate (HEMA) and chitosan, p(HEMA/chitosan) via UV‐initiated photo‐polymerization. The selectivity to different heavy metal ions viz Cd(II), Pb(II), and Hg(II) to the IPN membrane has been investigated from aqueous solution using bare pHEMA membrane as a control system. Removal efficiency of metal ions from aqueous solution using the IPN membranes increased with increasing chitosan content and initial metal ions concentrations, and the equilibrium time was reached within 60 min. Adsorption of all the tested heavy metal ions on the IPN membranes was found to be pH dependent and maximum adsorption was obtained at pH 5.0. The maximum adsorption capacities of the IPN membrane for Cd(II), Pb(II), and Hg(II) were 0.063, 0.179, and 0.197 mmol/g membrane, respectively. The adsorption of the Cd(II), Hg(II), and Pb(II) metal ions on the bare pHEMA membrane was not significant. When the heavy metal ions were in competition, the amounts of adsorbed metal ions were found to be 0.035 mmol/g for Cd(II), 0.074 mmol/g for Hg(II), and 0.153 mmol/g for Pb(II), the IPN membrane is significantly selective for Pb(II) ions. The stability constants of IPN membrane–metal ions complexes were calculated by the method of Ruzic. The results obtained from the kinetics and isotherm studies showed that the experimental data for the removal of heavy metal ions were well described with the second‐order kinetic equations and the Langmuir isotherm model. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Design and syntheses of blue luminescent Cu(II) and Zn(II) polymeric complexes with 2-(2′-pyridyl)benzimidazole derivative ligand

The polymeric complexes of 4,4′-bis[2-(2′-pyridyl)benzimidazolyl]biphenyl (Bmbp) with Cu(II) (1), Zn(II) (2) and 1,3,5-tris[2-(2′-pyridyl)benzimidazolyl]benzene (Tmb) with Cu(II) (3), Zn(II) (4) were successfully synthesized and characterized by IR spectroscopy, elemental analysis, thermal analysis and conductivity measurements. The results indicate that the stoichiometry of these metal complexes is metal: Bmbp (or Tmb) = 1:1 for 1 and 2 (2:1 for 3 and 4). Ligands coordinated with metal ions to get a five-membered chelate ring and formed polymeric complexes with metal ion. Their luminescence properties were also studied by UV–vis and fluorescence spectra. At room temperature, complexes 1–4 emit blue luminescence from 419 to 483 nm in the solid state and purple/blue luminescence from 385 to 437 nm in DMF solution. Thermal properties measurement and analysis shows that they have good thermal stabilities.     

Poly(ethylene Oxide)-Modified Polyaspartamide–Ferrocene Conjugates

In continuation of earlier investigations of polymer–ferrocene conjugates for biomedical applications, this article deals with conjugates prepared by N-acylation of linear, amine-functionalized polyaspartamide carriers with 4-ferrocenylbutanoic acid. Acylation is brought about both by mediation of HBTU coupling agent and by the N-hydroxysuccinimide active ester method. The polymeric carriers contain oligo- or poly(ethylene oxide) side chains introduced here for enhancement of water solubility. The longer side chains, in addition, are to impart such biomedically important properties as increased resistance to uptake by the reticuloendothelial system and to protein binding, extended circulation life time, and lowered immunogenicity. The conjugates comprise from 10 to 25 mol% ferrocenylated subunits, corresponding to ca. 2–5% Fe by mass. Freshly prepared and isolated in the solid state, they dissolve smoothly in aqueous media, with upper concentration limits (>0.2g/ml) dictated solely by their viscosity behavior. The conjugates are of interest in biomedical applications.     

Block copolymer micelles as carriers of transition metal ions Y(III) and Cu(II) and gelation thereof

Poly(ethylene oxide)-block-poly(2-(diethylamino)ethyl methacrylate) (PEO-b-PDEAEMA) diblock copolymer was synthesized by anionic polymerization, whose molecular structure was characterized by ¹H NMR and size exclusion chromatography (SEC). The diblock copolymer self-assembled into micelles in nonacid aqueous solution with PEO and PDEAEMA as corona and core respectively. By virtue of the coordinating property of PDEAEMA block to metal ions, the resultant micelles were then used as carriers to load metal ions Y(III) and Cu(II) in the micellar core. The morphology and stability of the metal loaded micelles were characterized by dynamic light scattering (DLS), atomic force microscopy (AFM) and transmission electron microscopy (TEM). The metal loading amounts were determined by elemental analyses, UV spectrometry and titrimetric analysis. In addition, the Y(III) loaded micelles were demonstrated to complex with α-cyclodextrins and form supramolecular hydrogels in-situ. The metal loaded micelles and the resultant supramolecular hydrogels will have potential application for cancer internal radiotherapy.     

cis-Diaminedichloroplatinum(II) complexes reversibly bound to water-soluble polyaspartamide carriers for chemotherapeutic applications. I. Platinum coordination to preformed, carrier-attached ethylenediamine ligands

Copolyaspartamides3–5, bearing the ethylenediamine (en) ligand as a repetitive side-chain component in addition to various hydrosolubilizing groups, are synthesized from polysuccinimide1 by a two-step aminolytic ring opening reaction. The completely water-soluble polyamides, possessing inherent viscosities of 5–20 ml g^–1, are used as polymeric carriers for the anchoring of the biomedically important diaminedichloroplatinum(II) coordination complex. Conjugate formation is brought about by treatment of the carriers with the tetrachloroplatinate(II) dianion in aqueous solution at pH 6.0 ± 0.5. The resulting, water-soluble conjugates3-Pt-5-Pt, purified by dialysis (12,000–14,000 molecular mass cutoff) and isolated in the solid state by freeze-drying from aqueous solution, possess platinum contents in the typical range of 15–25%. The metal is bound as acis-dichloro-en-Pt(II) complex to the polymer main chain via a short spacer segment incorporating a biofissionable amide link suitable forin vivo release of the complex. The conjugates are of interest as water-soluble macromolecular platinum coordination compounds for potential use in the chemotherapy of cancerous diseases.Presented in part at the XXVII International Conference on Coordination Chemistry, Broadbeach, Australia, 2–7 July 1989, abstract T6.     

Synthesis,characterization, and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid)–metal complexes

The metal‐ion complexation behavior and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid) were investigated. The polymeric ligand was prepared by solution polymerization. The metal‐ion complexation was studied with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions. The metal uptake followed the order: Cu(II) > Cr(III) > Mn(II) > Co(II) > Fe(III) > Zn(II) > Ni(II). The polymeric ligand and the metal complexes were characterized by various spectral methods. The catalytic activity of the metal complexes were investigated toward the hydrolysis of p‐nitrophenyl acetate (NPA). The Co(II) complexes exhibited high catalytic activity. The kinetics of catalysis was first order. The hydrolysis was controlled by pH, time, amount of catalyst, and temperature. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 272–279, 2004     

New polymeric structures designed for the removal of Cu(II) ions from aqueous solutions

New polymeric structures obtained by chemical transformations of maleic anhydride/dicyclopentadiene copolymer with triethylenetetraamine, p‐aminobenzoic acid, and p‐aminophenylacetic acid were used for the removal Cu(II) ions from aqueous solutions. The experimental values prove the importance of the chelator nature and of the macromolecular chain geometry for the retention efficiency. The retention efficiency (η_r), the retention capacity (Q _e ), and the distribution coefficient of the metal ion into the polymer matrix (K _d ) are realized by evaluation of residual Cu(II) ions in the effluent waters, by atomic adsorption. Also are discussed the influence of pH, the thermal stability of the polymer, and their polymer–metal complex, as well as the particular aspects regarding the contact procedure and the batch time. Based on the polymers and polymer–metal complexes characterization a potential retention mechanism is proposed. All polymer supports as well theirs metal–complexes are characterized by ATD and FTIR measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1397–1405, 2007     

PSSMA修饰磁性氧化石墨烯对Pb2+、Cu2+ 的吸附性能

以氧化石墨烯(GO)、FeCl_3·6H_2O及聚(4-苯乙烯磺酸-共聚-马来酸)钠盐(PSSMA)为主要原料,通过简便一步溶剂热法制备了阴离子聚电解质修饰磁性氧化石墨烯(MGO@PSSMA),并将其用于水溶液中重金属Pb~(2+)、Cu~(2+)的吸附去除。采用FTIR、SEM、TEM、VSM和DLS对制备的MGO@PSSMA进行了表征。考察了溶液pH、吸附时间、溶液初始质量浓度对Pb~(2+)、Cu~(2+)在MGO@PSSMA及未经PSSMA修饰磁性氧化石墨烯(MGO)上吸附的影响。探讨了吸附等温过程、吸附动力学及吸附作用机理。结果表明:MGO表面引入PSSMA可有效增加其对Pb~(2+)、Cu~(2+)的吸附量。在pH=5,溶液初始质量浓度为300 mg/L时,MGO@PSSMA对Pb~(2+)和Cu~(2+)的实际吸附量达141.1和104.8 mg/g。当溶液初始质量浓度为150 mg/L时,MGO@PSSMA对Pb~(2+)和Cu~(2+)的吸附平衡时间分别为2和1.5 min。MGO@PSSMA对Pb~(2+)、Cu~(2+)的吸附动力学及吸附等温数据分别符合准二级吸附动力学模型和Langmuir吸附等温模型。使用乙二胺四乙酸(EDTA)和HCl可实现MGO@PSSMA的有效再生;通过外加磁场作用可实现MGO@PSSMA的回收再利用。     

Cellulose acetate–poly(ether sulfone) blend ultrafiltration membranes. II. Application studies

Ultrafiltration membranes are largely applied as macromolecular solutes and heavy‐metal‐ion separation from aqueous streams. Cellulose acetate and poly(ether sulfone) blend ultrafiltration membranes were prepared by the precipitation phase‐inversion technique in 100/0, 95/5, 85/15, and 75/25% polymer blend compositions in the absence and presence of a polymeric additive, poly(ethylene glycol) 600, at different additive concentrations and were used for the rejection of proteins trypsin, pepsin, egg albumin, and bovine serum albumin; a maximum of 94% rejection was achieved. The toxic heavy metal ions copper, nickel, and cadmium from dilute aqueous solutions were subjected to rejection by the blend membranes by complexation of the ions with the water‐soluble polymeric ligand, polyethyleneimine (PEI). Permeate flux studies of proteins and metal ions were performed simultaneously with the rejection experiments. The atomic absorption spectra results reveal maximum rejection for copper complex and a minimum rejection of about 60% for the cadmium complex. The rejection and permeate flux of the blend membranes were compared with those of pure cellulose acetate membranes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3659–3665, 2004     

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     

Reactive polymers,XXXIV. Complexes of Ag(I) and Ag(II) with ligands bound to solid support

The sorption of Ag(I) ions on sorbents containing ethylenediamine (en) and iminodiacetate (ida) groups was investigated. The basic backbone consisted on macroporous glass coatd on its inner surface with poly(glycidylmethacrylate) (glass-GMA), copolymer glycidylmethacrylate-ethylenedimethacrylate (GMA-EDMA), and GMA-EDMA encapsulated in poly(-2-hydroxyethylmethacrylate). The rate of sorption of Cu(II) in sorbents modified with en decreased in the same order. For the sorption of Ag(II), a sorbent was synthesized by a reaction of GMA-EDMA with 3-aminopyridine, and the reaction with the ion was carried out in an oxidizing solution. The types of complexes formed in the sorption were determined spectroscopically in all cases.