Novel poly(aryl ether ketone)s containing various pendant groups .2. Gas-transport properties

The gas transport of hydrogen, oxygen, nitrogen, carbon dioxide, and methane gases in a series of poly(aryl ether ketone)s was examined. These polymer membranes have a wide range of permeability coefficients and permselectivity coefficients, showing excellent gas-transport properties. The enhanced interchain interaction in the polymers due to intermolecular hydrogen bonds and ionic bonds results in a considerable increase in permselectivity but a decrease in permeability. On the contrary, the polymers with bulky arkyl substituents show significantly increased permeability. The causes of this trend are interpreted in terms of the free volume, interchain distance, and glass transition temperature together with the respective contribution of gas solubility and diffusivity to the overall permeability. Of interest is the observation that the ionomer IMPEK-K+, which simultaneously contains bulky isopropyl substituents and pendant carboxylate groups, exhibits over twice higher CO2 permeability and 15% higher CO2/CH4 permselectivity than those of bisphenol-A p'olysulfone (PSF). The possibility of using the new synthesized poly(aryl ether ketone)s in gas separation membrane application is also discussed. (C) 1997 John Wiley & Sons, Inc.

Synthesis and Aqueous Solution Properties of Hydrophobically Modified Anionic Acrylamide Copolymers

In this investigation, hydrophobically modified polyacrylamide with low amounts of anionic long-chain alkyl was synthesized by the free radical polymerization in deionized water. This water-soluble copolymerization method is more convenient compared with the traditional micellar copolymerization methods. The copolymers were characterized using Fourier transform infrared, H-1 NMR, and the molecular weight and polydispersity were determined using gel permeation chromatography. The solution behavior of the copolymers was studied as a function of composition, pH, and added electrolytes. As NaCl was added to solutions of AM/C(11)AM copolymers or pH was lowered, the shielding or elimination of electrostatic repulsions between carboxylate groups of the C(11)AM unit lead to coil shrinkage.

Poly[[diaqua-mu-4,4 '-bipyridine-dinitratodi-mu-L-tyrosinato-dicopper(II)]: a chiral two-dimensional coordination polymer

The title compound, [Cu-2(C9H10NO3)(2)(NO3)(2)(C10H8N2)-(H2O)(2)](n), contains Cu-II atoms and L-tyrosinate (L-tyr) and 4,4'-bipyridine (4,4'-bipy) ligands in a 2:2:1 ratio. Each Cu atom is coordinated by one amino N atom and two carboxylate O atoms from two L-tyr ligands, one N atom from a 4,4'-bipy ligand, a monodentate nitrate ion and a water molecule in an elongated octahedral geometry. Adjacent Cu atoms are bridged by the bidentate carboxylate groups into a chain. These chains are further linked by the bridging 4,4'-bipy ligands, forming an undulated chiral two-dimensional sheet. O-H center dot center dot center dot O and N-H center dot center dot center dot O hydrogen bonds connect the sheets in the [100] direction. This study offers useful information for the engineering of chiral coordination polymers with amino acids and 4,4'-bipy ligands by considering the ratios of the metal ion and organic components.

K-2[MoO3(C2O4)].H2O

In the title compound, catena-poly[dipotassium [[(oxalato-O,O')dioxomolybdate]-mu-oxo]monohydrate], oxalate acts as a bidentate ligand coordinating to each Mo atom through the two deprotonated carboxylate groups. The coordination polyhedron of molybdenum is distorted octahedral and there are infinite chains in the structure. Principal dimensions are: Mo-O(terminal) 1.560 (3) and 1.739 (3) Angstrom, Mo-O(bridging) 2.046 (4) and 2.410 (4) Angstrom, and Mo-O(carboxylate) 1.949 (3) and 2.113 (3) Angstrom.

Structural characterization and luminescence studies of new lanthanide(III) complexes with nicotinic and isonicotinic acid N-oxides

Four new polymeric lanthanide(III) complexes of nicotinic acid N-oxide and isonicotinic acid N-oxide have been synthesized and structurally determined. In the isomorphous compounds [(Ln(L-1)(3) (H2O)(2))(n)]. 4nH(2)O(HL1 = nicotinic acid N-oxide; Ln = Eu, 1; Ln = Er, 2) the lanthanide(III) ions form infinite double chains along the b direction through the coordination of bridging carboxylate and N-oxide groups. The chains are cross-linked through hydrogen bonds between aqua ligands and uncoordinated N-oxide groups and between aqua ligands and lattice water molecules, to form a three-dimensional network. [(Eu(L-2)(2)-(H2O)(4))(n)](NO3)(n). nH(2)O (HL2 = isonicotinic acid N-oxide, 3) has a polymeric structure in which the europium (III) ions are connected into infinite chains by pairs of syn-syn carboxylate groups. Adjacent chains are interlinked by hydrogen bonds between aqua ligands and N-oxide groups to form a layer parallel to the (100) plane, and such layers are connected by hydrogen bonds between nitrate anions and aqua ligands, and between oxide groups and lattice water molecules, into a three-dimensional network. In [(Er-2(L-2)(4)(H2O)(10))](NO3)(2). H2O, 4, dinuclear units are inter-linked into a three-dimensional network through hydrogen bonding between aqua ligands and N-oxide groups of both bidentate bridging and unidentate L-2 ligands. Factors affecting the formation of coordination chains and dinuclear units are discussed. Luminescence properties of 1 and 3 have also been studied. (C) 1998 Elsevier Science Ltd. All rights reserved.

Synthesis and structural characterization of a novel polymeric praseodymium(III) complex with a new flexible double betaine

A novel polymeric Pr(III) complex with a new double betaine, namely [{Pr(L-1)(1.5)(H2O)(2)}(n)] [ClOli4]3(n). nH(2)O (1) (L-1= 1,4-diazoniobicyclo[2,2,2]octane- 1,4-dipropionate), has been synthesized and characterized by X-ray analysis. In the title complex, the Pr(III) atom is nine-coordinated by seven oxygen atoms from five L-1 ligands and two aqua ligands. Each pair of adjacent praseodymium(III) atoms is linked by a pair of mu(3) chelating and bridging carboxylate groups, thus forming an infinite metal metal chain running parallel to the a direction, and such chains are cross-linked by flexible backbones of L-1 ligands into a three-dimensional network with the perchlorate anions and lattice water molecules accommodated in the interstitial space. The title complex crystallizes in the monoclinic space group P2(1)/n with a = 8.085(2), b = 14.316(3), c = 29.775(6) Angstrom, beta = 103.04(3)degrees and Z = 4.

Synthesis, crystal structure and magnetic properties of a series of polymeric lanthanoid-copper complexes [Ln(2)Cu(3){O(CH2-CO2)(2)}(6)].nH(2)O (Ln=La, Nd, n=9; Ln=Er, n=6)

The reaction of diglycolic acid, O(CH2CO2H)(2), with Cu(NO3)(2) . H2O and lanthanoid nitrate hydrate produces a series of novel Ln-Cu mixed metal complexes, [Ln(2)CU(3){O(CH2CO2)(2)}(6)]. nH(2)O (Ln = La, Nd, n = 9; Ln = Er, n = 6), which have been characterized by elemental analysis, i.r. spectroscopy, magnetic measurements and X-ray crystallography. The Ln(3+) and Cu2+ ions are connected by the carboxylate groups of the ligands, resulting in the formation of a complicated network.

C-13 NMR study on the aqueous structure of lanthanide citrate complexes

The aqueous complexation of lanthanide complexes of citrate in pH 7.4 solutions has been studied by using lanthanide-induced shift and relaxation times measurement methods. These results indicate that citrate coordinate via 3-hydroxyl and 3-carboxylate groups with lanthanide ions and form 1:2 (Ln/cit) isostructural complexes through lanthanide series. We suggest a new coordination geometry which is different from that described in literature.

LANTHANIDE-INDUCED SHIFT AND RELAXATION RATE STUDIES OF THE AQUEOUS COMPLEXATION OF CITRATE

The aqueous complexation of lanthanide ions with citrate in pH 7.4 solution has been investigated with use of the lanthanide-induced shift and paramagnetic relaxation rate enhancement methods. The results show that citrate coordinates via hydroxyl and central carboxylate groups with lanthanide ions and forms 1:2 (Ln/cit) isostructural complexes through the lanthanide series. A new possible coordination geometry deduced from our experimental data is suggested and discussed.

SYNTHESIS AND VIBRATIONAL SPECTRUM STUDIES OF RARE EARTH COMPLEXES WITH CYCLOHEXANE CARBOXYLIC ACID

The solid state complexes of trivalent lanthanid, yttrium and scandium with cyclohexane carboxylic acid have been isolated and characterized by IR and Raman spectroscopy. It was found that there are only chelated carboxylate groups in the scandium complex and that there are the chelated, bridged and chelate-bridged carboxylate groups in other rare earth complexes. The former is a mononuclear complex and the latter is a polynuclear polymer. The RE—O coordinate bonds possess the characters of convalent ionic ...

Catena-Poly[[[tetra-mu(2)-aqua-heptaaqua-(mu(2)-benzene-1,3,5-tricarboxylato)-mu(3)-hydroxido-trinickel(II)sodium]-mu(4)-benzene-1,3,5-tricarboxylato]sesqui-hydrate]

The title coordination polymer, {[Ni3Na(OH)(C9H3O6)(2)( H2O)(11)] center dot 1.5H(2)O}(n), is built up from three independent Ni-II ions and one Na-I cation bridged by benzene-2,4,6-tricarboxylate ( BTC) ligands and water molecules. Three Ni-II ions are bridged by three bidentate carboxylate groups of three BTC ligands, two aqua ligands and one OH- unit, to form a trinuclear metal cluster. The Na-I cation is bonded to the Ni-II cluster by two bridging water molecules. One of the three BTC ligands bridges neighbouring clusters into one-dimensional chains, which are further connected through a complex hydrogen-bonding scheme, forming a three-dimensional suprastructure. The title complex is isomorphous with the previously reported Co-II complex.

Effect of hydroxyl groups on nonradiative decay of Er3+: I-4(13/2)-> I-4(15/2) transition in zinc tellurite glasses

A series of zinc tellurite glasses of 75TeO(2)-20ZnO-(5-x)La2O3-xEr(2)O(3) (x=0.02, 0.05, and 0.1 mol%) with the different hydroxl groups were prepared by the conventional melt-quenching method. Infrared spectra were measured in order to estimate the exact content of OH- groups in samples. The observed increase of the fluorescence lifetime with the oxygen bubbling time has been related to the reduction in the OH- content concentration as evidenced by IR transmission spectra. Various nonradiative decay rates from I-4(13/2) of Er3+ with. the change of OH content were determined from the fluorescence lifetime and radiative decay rates were calculated on the basis of Judd-Ofelt theory. (c) 2005 Elsevier B.V. All rights reserved.

The effect of OH- groups on the spectroscopic properties of erbium-doped tellurite glasses

A series of five different concentration erbium-doped tellurite glasses with various hydroxl groups were prepared. Infrared spectra of glasses were measured. In order to estimate the exact content of OH- groups in samples, various absorption coefficients of the OH- vibration band were analyzed under the different oxygen bubbling times. The absorption spectra of the glasses were measured, and the Judd-Ofelt intensity parameters Omega(i) of samples with the different erbium ions concentration and OH- contents were calculated on the basis of the Judd-Ofelt theory. The peak stimulated emission cross-section of (I13/2 ->I15/2)-I-4-I-4 transition of the samples was finally calculated by using the McCumber theory. The fluorescence spectra of Er3+:I-4(13/2)->I-4(15/2) transition and the lifetime of Er3+:I-4(13/2) level of the samples were measured. The effects of OH- groups on the spectroscopic properties of Er3+ doped samples with the different concentrations were discussed. The results showed that the OH- groups had great influences on the Er3+ lifetime and the fluorescence peak intensity. The OH- group is a main influence factor of fluorescence quenching when the doping concentration of Er2O3 is smaller than 1.0 mol%, but higher after this concentration, the energy transfer of Er3+ ions turns into the main function of the fluorescence quenching. And basically, there is no influence on the other spectroscopic properties (FWHM, absorption spectra, peak stimulated emission cross section, etc.).

The influence of OH groups on laser performance in phosphate glasses

Because of the influence of OH groups in phosphate glasses on the radiation of rare-earth ions, the laser performance is degraded. The laser efficiency and the small signal gain experiment of several phosphate glass samples have been done, the concentration of OH groups in glasses was calculated from the measured absorption coefficient at 3.47 μm. It is shown that the concentration of OH groups in phosphate glasses can seriously influence the laser output characteristics, and the OH groups have worse influence on the laser amplifier than laser oscillator.