Biologically active polymers. IV. Synthesis and antimicrobial activity of polymers containing 8‐hydroxyquinoline moiety

Polymers containing 8‐hydroxyquinoline moiety were prepared. Modifications of the base polymer of glycidyl methacrylate were carried out in order to introduce chloromethyl groups, either by the hydrolysis of the poly(glycidyl methacrylate) and the chloroacetylation of the hydrolyzed polymer by the reaction with chloroacetyl chloride or by aminating the poly(glycidyl methacrylate) either with ethylenediamine or with hexamethylenediamine, followed by reacting the aminated polymers with chloroacetyl chloride. The polymers containing 8‐hydroxyquinoline moiety were prepared by reacting the chloromethyl groups containing polymers with potassium salt of 8‐hydroxy quinoline. The antimicrobial activity of the polymers obtained was examined against gram‐negative bacteria (Escherichia coli) and gram‐positive bacteria (Bacillus subtilus) as well as the fungus Trichophyton rubrum. Generally, all three polymers proved effective against the tested microorganisms, but growth inhibitory effects varied from one another. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1364–1374, 2001     

Synthesis and photovoltaic properties of main chain polymeric metal complexes containing 8‐hydroxyquinoline metal complexes conjugating alkyl fluorene or alkoxy benzene by CN bridge for dye‐sensitized solar cells

Four main chain polymeric metal complexes ( P1–P4 ) based on 8‐hydroxyquinoline metal complexes have been synthesized by the Heck coupling and characterized by gel‐permeation chromatography, Fourier transform infrared spectroscopy, proton‐nuclear magnetic resonance, thermogravimetric analysis, ultraviolet–visible absorption, photoluminescence spectroscopy, elemental analysis, and cyclic voltammetry. The applications of these polymers as dye sensitizers in dye‐sensitized solar cells (DSSCs) are also studied. The study results show that the solar cells have good device performance with power conversion efficiency of P1–P4 up to 2.17, 2.04, 2.45, and 2.18%, respectively. The highest power conversion efficiency of DSSCs is up to 2.45%, for P3 consisting of alkoxy benzene unit and Cd–metal complex under the illumination of air mass 1.5 G, 100 mW cm⁻². POLYM. COMPOS., 34:1629–1639, 2013. © 2013 Society of Plastics Engineers     

Synthesis and properties of a novel (main‐chain)– (side‐chain) polymeric peroxide

A novel (main‐chain)‐(side‐chain) vinyl polyperoxide, poly(dipentene peroxide) (PDP), an alternating copolymer of dipentene (DP) and oxygen, has been synthesized by thermal oxidative polymerization of DP. The PDP was characterized by ¹H NMR, ¹³C NMR, FTIR, DSC, TGA, and EI‐MS studies. The overall activation energies of the degradation from Kissinger's method were 28 and 33 kcal/mol, respectively, for the endocyclic and acyclic peroxide units. The side‐chain peroxy groups were found to be thermally more stable than the main chain. Above 45°C the rate of polymerization increases sharply at a particular instant showing an “autoacceleration” with the formation of knee point. The kinetics of autoacceleration has been studied at various temperatures (45–70°C) and pressures (50–250 psi). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1549–1555, 2001     

Studies on poly(8‐hydroxy‐4‐azoquinolinephenylmethacrylate) and its metal complexes

8‐Hydroxy‐4‐azoquinolinephenylmethacrylate (8H4AQPMA) was prepared and polymerized in ethyl methyl ketone (EMK) at 65°C using benzoyl peroxide as free radical initiator. Poly(8‐hydroxy‐4‐azoquinolinephenylmethacrylate) poly(8H4AQPMA) 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) complexes of poly(8H4AQPMA) were prepared. Elemental analysis of polychelates suggests that the metal‐ligand ratio is about 1 : 2. The polychelates were further characterized by infrared spectra, X‐ray diffraction, spectral studies, and magnetic moments. Thermal analyses of the polymer and polychelates were carried out in air. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1516–1522, 2006     

Synthesis and metal uptake studies on poly(8‐hydroxy‐5‐azoquinolinephenylacrylate‐formaldehyde) resin and its metal complexes

8‐hydroxy‐5‐azoquinolinephenylacrylate‐formaldehyde (8H5AQPA‐F) macromonomer was prepared from acryloylchloride, with condensation products of 8‐hydroxy‐5‐azoquinolinephenol‐formaldehyde, and polymerized in DMF at 70°C using benzoyl peroxide as free radical initiator. Poly(8H5AQPA‐F) was characterized by infrared and nuclear magnetic resonance spectroscopic techniques. Polychelates were obtained in alkaline solution of polymeric ligand, with the aqueous solution of Cu(II) and Ni(II). Elemental analysis of polychelates suggests that the metal to ligand ratio is about 1:2. The polymer metal complexes were also characterized by IR, XRD, magnetic moments, and thermal analysis. The effects of pH and electrolyte on the metal uptake behavior of the resin were also studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 797–802, 2007     

双-8-羟基喹啉高分子配合物的合成与应用

用8-羟基喹啉在有相转移催化剂存在的碱性条件下,与氯仿作用合成5-甲酰基-8-羟基喹啉,然后将5-甲酰基-8-羟基喹啉分别与对苯二胺、联苯二胺,4,4＇-二氨基二苯砜反应,得到三种双-8-羟基喹啉-席夫碱配体,然后与金属离子配位,得到了一类新型的双-8-羟基喹啉-席夫碱-金属高分子配合物,再结合双-8-羟基喹啉-席夫碱配体与其它离子的显色反应,进行对比分析.利用红外光谱、紫外光谱对配体和配合物的结构进行表征,利用荧光光谱研究了高分子配合物的光致发光性能.     

Syntheses and magnetic properties of novel bithiazole‐containing polymeric complexes

Three novel bithiazole‐containing polymers were synthesized from 2,2′‐diamino‐4, 4′‐bithiazole (DABT) condensed with bismaleimide, bis(methyloxycarbonyl ethyl)tin dichloride (BETD), and 4,4′‐diphenylmethane diisocyanate (DPDI), respectively. A new series of polymeric complexes were prepared from Fe²⁺ and the three polymers. These polymers and their complexes were characterized through FTIR, ¹H‐NMR, and related techniques. The chemical compositions of the complexes were determined by XPS. The presence of the exchange interaction between the unpaired electrons was investigated by ESR spectroscopy. The magnetic behavior of these complexes was measured as a function of the magnetic field strength (0–40 kOe) at 5 K and as a function of temperature (5–300 K) at a magnetic field strength of 30 kOe. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1353–1359, 2001     

Thermal and electrical properties of copoly(1,3,4‐oxadiazole‐ethers) containing fluorene groups

A series of aromatic copolyethers containing 1,3,4‐oxadiazole rings and fluorene groups was prepared by nucleophilic substitution polymerization technique of 9,9‐bis(4‐hydroxyphenyl)fluorene, 1 , or of different amounts of 1 and an aromatic bisphenol, such as 4,4′‐isopropylidenediphenol or phenolphthalein, with 2,5‐bis(p‐fluorophenyl)‐1,3,4‐oxadiazole. The polymers were easily soluble in polar solvents like N‐methylpyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, and chloroform and can be cast from solutions into thin flexible films. They showed high thermal stability, with decomposition temperature being above 425°C. The polymers exhibited a glass‐transition temperature in the range of 195–295°C, with a reasonable interval between glass‐transition and decomposition temperature. Electrical insulating properties of some polymer films were evaluated on the basis of dielectric constant and dielectric loss and their variation with frequency and temperature. The values of the dielectric constant at 10 kHz and 20°C were in the range of 3.16–3.25. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Main chain polymeric metal complexes based on linkage fluorenevinylene or phenylenevinylene with thienyl(8‐hydro xyquinoline)–cadmium (II) complexes as dye sensitizer for dye‐sensitized solar cells

Dye‐sensitized solar cells (DSSCs) have attracted interest from chemists in recent years because of their unique advantages: low cost, simple preparation technologies, and high efficiency. Three main chain polymeric metal complexes F, P1, and P2 connected with thienyl(8‐hydroxyquinoline)–Cadmium (II) complexes have been synthesized by Heck coupling and characterized by Gel Permeation Chromatography, Fourier transform infrared, 1H NMR, thermogravimetric analysis, TGA, UV‐vis, cyclic voltammetry, photoluminescence (PL) emission spectra, and the application of dye sensitizers in DSSCs has been studied. The DSSCs exhibited good performance with a power conversion efficiency of up to 1.77%, under simulated air mass 1.5 G solar irradiation. They possess good stabilities, indicating the polymeric metal complexes are suitable for the fabrication processes of optoelectronic devices. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis,characterization, and catalytic study of polymeric metal complexes derived from divalent transition metal ions with 2,4‐dihydroxy benzophenone and 2,4‐dihydroxy acetophenone

The polymeric metal complexes of poly (3‐hydroxy‐4‐((Z)‐1‐(phenylimino)ethyl)phenyl‐3‐methylbut‐2‐enoate) designated as [poly(3H4‐1PEPMB)] and poly (3‐hydroxy‐4‐((Z)‐phenyl(phenylimino)methyl)phenyl‐3‐methylbut‐2‐enoate designated as [poly(3H4‐PPMPMB)] containing Cu(II), Ni(II), Co(II), Cd(II), Mn(II), Ca(II), and Zn(II) ions were synthesized. The ploymer ligands and metal complexes were charcterized by Fourier transform infrared, nuclear magnetic resonance (NMR), thermogravimetric analysis, differential scanning calorimeter (DSC), and X‐ray diffraction (XRD) techniques. The XRD study of the complexes revealed highly crystalline nature of polychelates. The polymeric complexes were active for the oxidation of aldehyde group. The oxidation activity of Cu (II) complex of poly (3H4‐1PEPMB) was studied for the oxidation of benzaldehyde and its derivaties to corresponding carboxylic acids. The oxidation products were confirmed by GC‐MS analysis. The oxidation of aldehydes was quantitative with 100% selectivity for benzioc acid. Thermal analysis of complexes indicated reasonably good thermal stability. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and magnetic properties of novel poly(N‐2‐thiazolyl(meth)acrylamide)‐Fe(II) complexes

N‐2‐thiazolyl(meth)acrylamides were polymerized by a radical route to obtain polymers in good yields. The polymers, with a pendent heterocyclic group, are soluble in common organic solvents, which allow the corresponding metal complexes with higher loads to be prepared easily. FTIR, ¹H NMR, and energy‐dispersive X‐Ray spectroscopy (EDX) were applied to characterize these materials. The magnetic behavior of poly(N‐2‐thiazolyl(meth)acrylamide)‐Fe(II) complexes was examined as a function of applied magnetic field at 4 K and as a function of temperature (4 ～ 300 K) at an applied magnetic field of 1 ～ 3 kOe, exhibiting the characteristics of a ferromagnet. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 83–87, 2005     

Synthesis and properties of metal complexes of radiation grafted carboxyl containing copolymers

Metal complexes of copolymers based on polyacrylic acid radiation grafted onto films of low density polyethene were prepared by complex‐forming with solutions of salts of FeCl₃.6H₂O, CuCl₂.2H₂O, CoCl₂.6H₂O, NiCl₂.6H₂O, VOSO₄.5H₂O, Na₂MoO₄.2H₂O, Na₂WO₄.2H₂O, and NH₄VO₃. The introduction of metal ions was found to depend mainly on the degree of grafting of acrylic acid and was from 0.5 to 5.0 mass%. These complexes were characterized by IR, UV spectroscopy, and EPR. The moisture content of the materials obtained changed linearly with the degree of grafting of acrylic acid and was from 9.0 to 80.0%. The introduction of the MoO₂²⁺ and WO₂²⁺ towards carboxylic groups lead to increasing the thermal stability of the metal complexes of the copolymers compared to the initial grafted films. The modified acrylate copolymers were studied in reactions of catalytic oxidation of cyclohexene. The activities of the complexes obtained towards cyclohexene epoxidation can be arranged in the following order: PAA–MoO₂²⁺ > PAA–VO²⁺ > PAA–VO > PAA–WO₂²⁺, while for the reaction of cyclohexene hydroxylation the order was—PAA–Co²⁺ > PAA–Cu²⁺ > PAA–Fe³⁺ > PAA–Ni²⁺. The contents of cyclohexene oxide and 2‐cyclohexene‐1‐ol reached 38.5% and 7.5%, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1658–1665, 2006     

Enhanced performance in organic light‐emitting diodes with copolymers containing both tris(8‐hydroxyquinoline) aluminum and 8‐hydroxyquinoline lithium groups

We synthesized novel copolymers containing both tris(8‐hydroxyquinoline) aluminum (Alq₃) and 8‐hydroxyquinoline lithium (Liq) groups as emitting layers for use in conventional two‐layer organic light‐emitting diodes. The network structure and thermal stability of these materials is described. The optical and electroluminescent properties of the copolymers were also studied. The performance optimization of the devices with the copolymers through the variation of the ratio of Alq₃ to Liq is described. A mechanism responsible for the improved electron injection is put forward. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4404–4410, 2006     

Poly(2‐acrylamido glycolic acid‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid): Synthesis,characterization, and retention properties for environmentally impacting metal ions

Poly(2‐acrylamido glycolic acid‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) [P(AGA‐co‐APSA)] was synthesized by radical polymerization in an aqueous solution. The water‐soluble polymer, containing secondary amide, hydroxyl, carboxylic, and sulfonic acid groups, was investigated, in view of their metal‐ion‐binding properties, as a polychelatogen with the liquid‐phase polymer‐based retention technique under different experimental conditions. The investigated metal ions were Ag⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺, and Cr³⁺, and these were studied at pHs 3, 5, and 7. P(AGA‐co‐APSA) showed efficient retention of all metal ions at the pHs studied, with a minimum of 60% for Co(II) at pH 3 and a maximum close to 100% at pH 7 for all metal ions. The maximum retention capacity (n metal ion/n polymer) ranged from 0.22 for Cd²⁺ to 0.34 for Ag⁺. The antibacterial activity of Ag⁺, Cu²⁺, Zn²⁺, and Cd²⁺ polymer–metal complexes was studied, and P(AGA‐co‐APSA)–Cd²⁺ presented selective antibacterial activity for Staphylococcus aureus with a minimum inhibitory concentration of 2 μg/mL. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and applications of 3,6-carbazole-based conjugated side-chain copolymers containing complexes of 1,10-phenanthroline with Zn(II), Cd(II) and Ni(II) for dye-sensitized solar cells

Three novel donor-acceptor polymeric metal complexes based on polycarbazole containing complexes of 1,10-phenanthroline with Zn(II), Cd(II) and Ni(II) have been synthesized by the Ullmann reaction and characterized by gel permeation chromatography, FT-IR, UV-visible absorption and photoluminescence spectroscopy, cyclic voltammetry and elemental analysis. The application of these organometallic polymers in fabricated dye-sensitized solar cells has been studied. The solar cells exhibited good device performance with a power conversion efficiency of up to 0.44%, under simulated air mass 1.5 G solar irradiation.     

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     

Synthesis and magnetic properties of novel complexes of poly(N‐2‐thiazolylmethacrylamide) with Nd(III), Pr(III), and Sm(III)

N‐2‐Thiazolylmethacrylamide (NTMA) was polymerized by a radical route to obtain the polymer in good yields. The complexes of PolyNTMA with three rare earth ions Nd(III), Pr(III), and Sm(III) were prepared for the first time. FTIR and ¹H NMR were applied to characterize these materials. The magnetic behavior of PolyNTMA–metal complexes was examined as a function of applied magnetic field at 4 K and as a function of temperature (4–300 K) at an applied magnetic field of 30 kOe. It was found that Pr(III) complex exhibits an antiferromagnetic property, while Nd(III) and Sm(III) complexes exhibit a special magnetic property different from the typical magnet. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1289–1293, 2006