Lanthanide binuclear macrocyclic complexes as synthetic enzymes for the cleavage of DNA

Lanthanide binuclear complexes can accelerate the cleavage of pUC19 plasmid DNA, yielding predominantly linear form. The saturation kinetics of the cleavage of pUC19 was studied. The observed rates with lanthanide binuclear complexes showed the expected increase with the catalyst concentration. The rate of cleavage is greater than that of lanthanide ions alone. (C) 1998 Elsevier Science B.V. All rights reserved.

Synthesis of the first mono(cyclopentadienyl)lanthanide Schiff base complex bearing C-2-symmetric tetradentate ligand: crystal structure of [(eta(5)-C5H5)Yb(mu-OC20H20N2O)](2)(mu-THF)(THF)

Reaction of YbCl3 with 3 equimolar CpNa (Cp = cyclopentadienide) in THF, followed by treatment with trans-(+/-)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine led to the isolation of first mono(cyclopentadienyl) lanthanide Schiff base complex, [(eta(5)-C5H5)Yb(mu-OC20H20N2O)](2) (mu-THF)(THF) (1). The molecular structure of 1 shows that it is a dimer in which the two [(eta(5)-C5H5)Yb(mu-OC20H20N2O)] units connecting via a bridging THF oxygen and two bridging oxygen atoms from Schiff base ligands. (C) 1998 Elsevier Science S.A.

Bright red electroluminescent devices based on a soluble lanthanide complex Eu(DBM)(3)(phen)

Electroluminescent devices with PVK film doped with Eu(DBM)(3)(phen) and PBD were fabricated. The device structure of glass substrate/indium-tin-oxide/PPV/PVK:Eu(DBM)(3)-(phen):PBD/Alq(3)/Al was employed. The emissive layer was formed by spin-casting method. A sharply red electroluminescence with a maximum luminance of 114.4 cd/m(2) was achieved at 42 V.

Synthesis and X-ray crystal structure of [(eta(5)-C5H5)Sm(mu-OC20H20N2O)](2)(mu-THF)(THF)(2): Mono(cyclopentadienyl)lanthanide complex bearing a C-2-symmetric tetradentate Schiff-base ligand

Cp2SmCl(THF) reacts with 0.5 equivalent disodium salts of trans-(+/-)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine give the title complex [(eta(5)-C5H5)Sm(mu-OC20H20N2O)](2)(mu-THF)(THF)(2) (1). X-ray crystal determination shows that the molecule is a dimer, in which two (eta(5)C(5)H(5))Sm(mu-OC20H20N2O) units are connected via a THF oxygen and two bridging oxygen atoms of Schiff base ligands. The average Sm-C distance is 2.78(7) Angstrom, while those of Sm-O (bridging THF oxygen) and Schiff base oxygens are 2.79(3) and 2.43(4) Angstrom; respectively. (C) 1998 Elsevier Science Ltd. All rights reserved.

Electrochemical studies of a lanthanide heteropoly tungstate/molybdate complex in polypyrrole film electrode and its electrocatalytic reduction of bromate

An electrode modified with a polybasic lanthanide heteropoly tungstate/molybdate complex K10H3[Nd(SiMo7W4O39)(2)] entrapped into polypyrrole (PPy) film, denoted as Nd(SiMo7W4)(2)-PPy, exhibits three couples of two-electron redox waves in pH 1-5 buffer solutions. The redox waves are surface-controlled at lower scan rates and diffusion-controlled at higher scan rates. The effects of pH on the electrochemical behavior of Nd(SiMo7W4)(2) in PPy film were investigated in detail and compared with that of Nd(SiMo7W4)(2) in aqueous solution. The various charge states of PPy during its redox process have peculiar effects on the relationship between pH and formal potentials of Nd(SiMo7W4)(2)-PPy at different acidities. The Nd(SiMo7W4)(2)-PPy cme can remarkably catalyze the electrochemical reduction of bromate with good stability. (C) 1997 Elsevier Science Ltd.

Syntheses of indenyl lanthanide derivatives and the molecular structures of [(C9H7)(2)PrCl(THF)](2) and [(C9H7)(3)La(THF)]

The reaction of anhydrous PrCl3 with Na(C9H7) in 1.2 mole ratio in THF gives [(C9H7)(2)PrCl(THF)](2)1. 1 crystallized in monoclinic system, space group P2(1)/c with a = 7.808(2), b = 17.796(6), c = 14.070(4) Angstrom, beta = 93.97(2)degrees, V= 1950.3(9) Angstrom(3), Dcalcd = 1.63 g/cm(3) and Z = 2. Each Pr ion is surrounded by two indenyl, two Cl and one THF in a roughly trigonal bipyramid arrangement with average Pr-C(ring) and Pr-Cl distances of 2.81 and 2.84 Angstrom. The reaction of LaCl3 with Na(C9H7) in 1:3 mole ratio gives (C9H7)(3)LaTHF 2, which crystallizes in the monoclinic space group P2(1)/a with unit cell constants a = 21.871(8), b = 10.585(3), c = 23.652(7) Angstrom,beta = 114.62(2)degrees, V = 4977.9 Angstrom(3) and Z = 8. (C) 1997 Elsevier Science S.A.

Studies on the coordination of lanthanide with L-hydroxyproline and DL-citrulline

The stability constants of binary and ternary complexes of lanthanide with L-hydroxyproline and DL-citrulline were obtained by using potentiometric titration under the physiological condition(37 degrees C, 0.15 mol/L NaCl). The coordination of lanthanide with the two ligands was discussed.

Stereospecific polymerization of styrene using a homogeneous lanthanide catalyst

Stereospecific polymerization of styrene was catalyzed by homogeneous neodymium phosphonate [Nd(P-507)(3)]-H2O-Al(i-Bu)(3) catalytic system. The polymer was separated into isotactic polystyrene and atactic polystyrene by extracting the latter with boiling 2-butanone. The conversion of styrene and the yield of isotactic polystyrene (IY) were influenced by the [H2O]/[Al(i-Bu)(3)] mole ratio and the solvent polarity. The reaction is first order with respect to monomer at 70 degrees C.

Lanthanide ions for the hydrolysis of 5'-mononucleotides and 3'-mononucleotides

Cleavage of adenosine-5'-monophosphate (5'-AMP), guanosine-5'-monophosphate (5'-GMP), adenosine-3'-monophosphate (3'-AMP) and guanosine-3'-monophosphate (3'-GMP) by lanthanides was investigated by NMR and the method of measuring the liberated phosphates. Rapid cleavage of both 5'-mononucleotides and 3'-mononucleotides by Ce-III and Ce-IV under air at pH 9 and 37 degrees C was observed. Other lanthanides showed less efficiency for hydrolyzing 5'-mononucleotides but 3'-mononucleotides were catalyzed by a range of lanthanide ions. The mechanism for hydrolyzing 3'-mononucleotides by lanthanides was:investigated. The notable difference in reactivity between Ce-III and the other lanthanide ions under air was further studied showing that the cleavage is enhanced with increasing molar fraction of Ce-IV. The fast cleavage of mononucleotides by Ce-III under air at pH 9 is ascribed to the resultant Ce-IV in the reaction mixture. (C) 1997 Elsevier Science Ltd.

Lanthanide metal complexes for the hydrolysis of adenosine-5'-monophosphate and deoxyadenosine-5'-monophosphate

The hydrolysis of adenosine-5'-monophosphate and deoxyadenosine-5'-monophosphate has been studied with lanthanide(III) metal complexes of 2-carboxyethylgermanium sesquioxide (Ge-132) by NMR and HPLC and by measuring the liberated inorganic phosphates.

Hydrothermal synthesis and lanthanide doping of complex fluorides, LiYF4, KYF4 and BaBeF4 under mild conditions

The complex fluorides LiYF4, KYF4, BaBeF4 and AYF(4)Eu(x) (A = Li, K) are hydrothermally synthesized at 140-240 degrees C and characterized by powder X-ray diffraction, thermogravimetric analysis, IR spectroscopy, scanning electron microscopy and luminescence measurements.

Lanthanide metal complexes for the hydrolysis of ribonucleoside 3',5'-cyclic phosphate and deoxyribonucleoside 3',5'-cyclic phosphate

Ytterbium(III) and praseodymium(III) complexes of 2-carboxyethylgermanium sesquioxide (Ge-132) can hydrolyze the phosphodiester linkage of 3',5'-cyclic adenosine monophosphate (cAMP) and 3',5'-cyclic deoxyadenosine monophosphate (dcAMP). Both cAMP and dcAMP are hydrolyzed with high selectivity, yielding predominantly 3'-monophosphates. The selectivity and activity for hydrolyzing cAMP and dcAMP by lanthanide metal(III) complexes and lanthanide metal ions are compared.

Lutetium: A special lanthanide prefers dimer in fullerene cages

Endohedral dilutetium fullerenes, Lu-2@C-2n(2n = 76 similar to 112), have been extracted from the soot prepared by are-burning method for the first time and different from other lanthanide encapsulated fullerenes, there is no signal corresponding to Lu@C-82 even in mass spectrum of the high-temperature, high-pressure extract.