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Diverse heteroleptic ytterbium(III) thiocyanate complexes by oxidation from bis(thiocyanato)ytterbium(II).

The new ytterbium(II) thiocyanate complex [Yb(NCS)2(thf)2] (1), synthesised by redox transmetallation between [Hg(SCN)2] and ytterbium metal in THF at room temperature, gave monomeric, eight coordinate [Yb-(NCS)2(dme)3] (2, dme = 1,2-dimethoxyethane) on crystallisation from DME, and is a powerful, synthetically useful reductant. Thus, oxidation of 1 with Hg(SCN)2, Hg(C6F5)2/HOdpp (HOdpp = 2,6-diphenylphenol), TlCp (Cp = C5H5 or CH3C5H4), Tl(Ph2pz) (Ph2pz = 3,5-diphenylpyrazolate) and CCl3CCl3 in THF yielded the ytterbium(II) complexes [Yb(NCS)3(thf)4] (3), [Yb-(NCS)2(Odpp)(thf)3](4), [Yb(NCS)2Cp-(thf)3] (Cp = C5H5 (5), CH3C5H4 (6)), [Yb(NCS)2(Ph2pz)(thf)4] (7) and [Yb(NCS)2Cl(thf)4] (8). In the solid state, complexes 4, 6 and 7 were shown by X-ray crystallography to be six, eight and eight coordinate monomers, respectively. Exclusively terminal, N-bound transoid thiocyanate bonding is observed with eta1-Odpp (4), eta5/-C5H4Me (6) and eta2-Ph2Pz (7) ligands attached approximately perpendicular to the N...N vector. The chloride complex 8 is not a molecular species, but consists of discrete, seven coordinate [YbCl2(thf)5] cations and [Yb(NCS)4(thf)3] anions. By contrast, oxidation of 1 with TlO2CPh gave a mixture of [[Yb(NCS)-(O2CPh)2(thf)2]2] (9) and 3 through rearrangement of an initially formed [Yb(NCS)2(O2CPh)] species. The X-ray structure of 9 indicates a dimeric complex with a (Yb(mu-O2CPh)4Yb] core that contains both bridging bidentate and bridging tridentate benzoate groups, and with a terminal N-bound thiocyanate and two THF ligands on each ytterbium. Reduction of Ph2CO with 1 in THF yielded the dinuclear complex [[Yb(NCS)2(thf)3]2(mu-OC(Ph)2C(Ph)2O)] (10), in which two octahedral Yb centres are bridged by a 1,1,2,2-tetraphenylethane-1,2-diolate ligand, derived from reductive coupling of the benzophenone reagent.

Journal Article↗

Ytterbium-DTPA. A potential intravascular contrast agent.

Ytterbium-DTPA was evaluated as a potential intravascular contrast agent. Ytterbium-DTPA was synthesized from ytterbium oxide and diethylene triamine penta-acetic acid (DTPA). CT scans of increasing concentrations of ytterbium and iodine showed that at 125 kVp, ytterbium was denser than an equal concentration of iodine. The LD50 of intravenous ytterbium-DTPA was 10 mM/kg (1.73 g ytterbium/kg) in rats. In enhanced CT scans and pulmonary angiography in dogs, ytterbium was visibly denser than iodine, and CT Hounsfield units showed greater enhancement of the aorta and inferior vena cava with ytterbium. The animals showed no sign of acute or delayed toxicity. Ytterbium-DTPA deserves further evaluation as a contrast agent for high kVp techniques.

Animals↗

Refined crystal structure of ytterbium-substituted carp parvalbumin 4.25 at 1.5 A, and its comparison with the native and cadmium-substituted structures.

The crystal structure of carp parvalbumin 4.25 containing a 1:1 molar ratio of ytterbium chloride to protein has been refined at 1.5 A resolution by restrained least-squares methods to a crystallographic R value of 0.199. The crystal structure confirms the NMR studies, which suggest that low concentrations of ytterbium cause an extensive displacement of calcium from the EF metal binding site. A comparison of the ytterbium-substituted model with the native and cadmium-substituted structure show no significant differences, except around the substituted EF metal-binding region. The displacement of calcium by ytterbium at the EF site has caused a movement in the polypeptide backbone of Ser-91 and Asp-92. This movement resulted in an increase in the number of oxygen ligands bound to ytterbium in the EF site from seven to eight.

Amino Acid Sequence↗

Homolysis of the Ln-N (Ln = Yb, Eu) bond. Synthesis, structural characterization and catalytic activity of ytterbium(II) and europium(II) complexes with methoxyethyl functionalized indenyl ligands.

The interaction of methoxyethyl functionalized indene compounds (C(9)H(6)-1-R-3-CH(2)CH(2)OMe, R =t-BuNHSiMe(2)(1), Me(3)Si (2), H (3)) with [(Me(3)Si)(2)N](3)Ln(mu-Cl)Li(THF)(3)(Ln=Yb (4), Eu (5)) produced a series of new ytterbium(II) and europium(II) complexes via tandem silylamine elimination/homolysis of the Ln-N (Ln=Yb, Eu) bond. Treatment of the lanthanide(III) amides [(Me(3)Si)(2)N](3)Ln(mu-Cl)Li(THF)(3)(Ln=Yb (4), Eu (5) with 2 equiv. of, 1,2 and 3, respectively, produced, after workup, the ytterbium(II) complexes [eta5:eta1-Me(2)Si(MeOCH(2)CH(2)C(9)H(5))(NHBu-t)](2)Yb(II) (6), (eta5:eta1-MeOCH(2)CH(2)C(9)H(5)SiMe(3))(2)Yb(II) (7), (eta5:eta1-MeOCH(2)CH(2)C(9)H(6))(2)Yb(II)(8) and the corresponding europium(II) complexes [eta5:eta1-Me(2)Si(MeOCH(2)CH(2)C(9)H(5))(NHBu-t)](2)Eu(II)(9), (eta5:eta1-MeOCH(2)CH(2)C(9)H(5)SiMe(3))(2)Eu(II)(10) and (eta5:eta1-MeOCH(2)CH(2)C(9)H(6))(2)Eu(II)(11) in moderate to good yield. In contrast, interaction of the corresponding indene compounds 1, 2 or 3 with the lanthanide amides [(Me(3)Si)(2)N](3)Ln (Ln = Yb, Eu) was not observed, while addition of 0.5 equiv. of anhydrous LiCl to the corresponding reaction mixture produced, after workup, the corresponding ytterbium(II) or europium(II) complexes. All the new compounds were fully characterized by spectroscopic and elemental analyses. The structures of complexes, and were determined by single-crystal X-ray analyses. The catalytic activity of all the ytterbium(II) and europium(II) complexes on MMA polymerization was examined. It was found that all the ytterbium(II) and europium(II) complexes can function as single-component MMA polymerization catalysts. The temperature, solvent and ligand effects on the catalytic activity were studied.

Journal Article↗

Proton nuclear magnetic resonance determination of the sequential ytterbium replacement of calcium in carp parvalbumin.

The substitution of the paramagnetic lanthanide ion ytterbium for the calcium ions bound to the CD and EF sites of carp parvalbumin results in a series of 1H NMR resonances which are shifted far outside the envelope of the 1H NMR spectrum of the diamagnetic form of the protein. Titration of Ca2+-saturated parvalbumin with ytterbium (YB3+) demonstrate that Yb3+ sequentially replaces the two bound calcium ions of the protein. Analysis of the 1H NMR data yields the relative affinities of the two sites (CD and EF) for ytterbium with respect to calcium. The dissociation constants for ytterbium are then calculated to be KYb3+CD equals (4-7) x 10(-10) M and KYb3+EF equals (2-6) x 10(-10) M from the known dissociation constants for calcium [Haiech, J., Derancourt, J., Pechere, J.-F., & Demaille, J. G. (1979) Biochemistry 18, 2752-2758]. The approximate equality of these constants is verified by Yb3+ titrations of apoparvalbumin.

Animals↗

Binding affinity and capacities for ytterbium(3+) and hafinum(4+) by chemical entities of plant tissue fragments.

The binding affinity of ytterbium (Yb3+) and hafinum (Hf4+) to ligands of chemical entities of fragments of bermudagrass tissues and their resistance to exchanging Yb with other ligands and to displacement by protons were investigated. Chemical entities of acid resistant NDF (ARNDF), 0.1 N acid detergent fiber (0.1 N ADF), and permanganate cellulose (CELL) were prepared from fragments of bermudagrass hay (Cynodon dactylon [L.] Pers.) obtained by grinding to pass a 2-mm sieve. 175Ytterbium and Yb, as YbCl3, were initially bound to each preparation by soaking for 12 h in pH 5.5 borate buffer to obtain Yb bound onto ligands having affinity constants for Yb equal to or greater than that for the weakly stable borate ligand, Yb > or = borate. The fraction of Yb > or = borate was measured and fragments then sequentially exposed to acetate, citrate, nitrotriacetate (NTA), and EDTA ions to allow exchange of Yb from Yb > or = borate with ligands having affinity constants for Yb equal to or greater than acetate (Yb > or = acetate), citrate (Yb > or = citrate), NTA (Yb > or = NTA), and EDTA (Yb > or = EDTA) ions. Binding of Yb > or = borate indicated the existence of two species of ligands: strong ligands binding essentially 100% of added Yb at levels of 1 to 1,300 ppm (0.1 N ADF) and at 1 to 7,000 ppm (ARNDF); and weaker ligands binding 4 and 8% of the Yb, respectively, at levels of added Yb greater than 1,300 ppm and 7,000 ppm. Ytterbium > or = acetate of ARNDF, but not 0.1 N ADF, was as resistant to exchange as Yb > or = citrate. Ytterbium > or = borate was exchanged extensively (85% or greater) with soluble ligands having affinity constants > or = NTA. Ytterbium resistance to proton displacement at pH of 1.5 increased with Yb > or = EDTA > Yb > or = NTA > Yb > or = citrate > Yb > or = acetate. Very efficient binding of Yb to CELL suggested that such chemical preparations are not representative of native cellulose. Hafnium (4+) was strongly bound to plant tissues rendering both Hf and Hf-bound DM insoluble at a pH of 1.5 and insoluble in a modified NDF solvent without EDTA. It is concluded that Yb specifically applied as Yb > or = acetate and Hf4+ are indelible markers for estimating sojourn time of undigested plant tissues at the normal pH of the rumen. Because of its resistance to proton displacement, Hf4+ would be an indelible marker for estimating sojourn time in more acidic postgastric segments of the gastrointestinal tract.

Animals↗

[Hygienic regulation of yttrium, terbium, ytterbium and lutetium fluorides in the air of the workplace].

The study (experiments on animals and on culture of rats' peritoneal macrophages) covered fluorides of rare-earth metals (REM) assigned to yttrium group--yttrium, terbium, ytterbium, lutetium. Fluorides of REM have low toxicity and cumulativity, induce no local irritation of skin and eyes. Fluorides of yttrium, terbium and lutetium, if administered into stomach, result in specific intoxication (fluorosis). Fluoride of ytterbium did not cause such intoxication. According to short-term tests of cytotoxicity, the foreseeable fibrogenic danger for ytterbium fluoride is moderate, for fluorides of yttrium, terbium and lutetium is mild. The authors recommend to control the level of yttrium, terbium and lutetium fluorides in the air of workplace through the MACs for the fluorides at 2.5 mg/cu m (maximal single concentration) and 0.5 mg/cu m (average shift concentration), the level of ytterbium fluoride as moderate fibrogenic dust at 6 mg/cu m.

Air Pollutants, Occupational↗

Effects of ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) derivatives on penetration of ytterbium-169 and cerium-144 into the rat offspring.

Effects of ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) derivatives on penetration of ytterbium-169 and cerium-144 into the rat offspring. Acta Physiol. Pol., 1976, 27 (2): 175-181. Penetration of radioactive ytterbium-169 and cerium-144 into fetuses was determined at the end of pregnancy and penetration into the organism of suckling rats was studied during feeding with the milk of exposed mothers when EDTA or DTPA derivatives were being administered. Injection of ytterbium-169 as a complex with EDTA or DTPA or injection of Na2Ca EDTA or Na3Ca DTPA 1h after administration of cerium-144 to mothers reduced penetration of both radionuclides into offsprings in relation to the animals receiving no complex compounds. It was observed that the action of DTPA was stronger than that of EDTA. Passage of ytterbium with milk and across the placenta was greater than the passage of cerium.

Animals↗

(+)-(18-Crown-6)-2,3,11,12-tetracarboxylic acid and its Ytterbium(III) complex as chiral NMR discriminating agents

The compound (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid (I) and its ytterbium(III) complex are evaluated as chiral NMR discriminating agents. The crown ether is a useful chiral discriminating agent for protonated amino acid esters, amines, and amino alcohols. The crown can also be used with neutral primary amines since amines are protonated through a neutralization reaction with a carboxylic acid moiety of the crown. Enantiodiscrimination with the crown is observed in methanol and acetonitrile. Addition of ytterbium(III) nitrate to crown-substrate mixtures causes upfield shifts in the NMR spectrum of the substrate and often enhances the enantiomeric discrimination. Evidence indicates that the ytterbium(III) bonds to the carboxylic acid moieties of the crown, but enhancements in enantiomeric discrimination result from either the different association constants of the enantiomers with the crown or diastereomeric nature of the resulting crown-substrate complexes. The ytterbium complex with the crown is suitable for use in methanol but precipitates in acetonitrile.

Journal Article↗

Pentaaza macrocyclic ytterbium(III) complex and solvent controlled supramolecular self-assembly of its dimeric mu-eta 2:eta 2 peroxo-bridged derivatives.

The unprecedented template action of ytterbium ion in the synthesis of pentaaza macrocyclic Schiff bases is exemplified by isolation and definitive identification of the seven-coordinate pentagonal bipyramidal complex with the formula of [YbLCl(2)]ClO(4) (1), where L is 2,14-dimethyl-3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca-1(19),2,13,15,17-pentaene, providing the first example of crystallographically characterized pentaaza macrocyclic ytterbium complex. For the first time the spectrum of the (2)F(7/2) --> (2)F(5/2) transition has been obtained for a molecular complex of ytterbium with organic ligands in which all ligand-field components of the ground and excited state are well displayed at room temperature. This complex is capable of forming a dimeric peroxo Yb(2)(mu-eta(2):eta(2)-O(2))L(2)(4+) (2) derivative containing the biologically significant planar side-on doubly bidentate coordination mode of the peroxide. Inclusion of the appropriate solvent molecule into the crystal structure generates supramolecular architectures (2a-d) in which the solvent controlled self-assembly is observed. Spectral properties of these complexes were found to be very important and promising in the area of ytterbium physicochemistry.

Journal Article↗

Synthesis, structure and oxidation of new ytterbium(II) bis(phenolate) compounds and their catalytic activity towards epsilon-caprolactone.

Two ytterbium(II) bis(phenolate) complexes, [LRYb] where R=NMe2 and OMe have been synthesized and characterized, with being structurally defined to be a dimeric species with an unsymmetrical coordination of the bis(phenolate) ligand which is preserved in solution. Both and have been oxidized by a variety of oxidants (AgX, ROH) to form heteroleptic ytterbium(III) bis(phenolate) complexes: [(LNMe2)YbPF6], [(LNMe2)YbOSO2CF3(thf)], [(LNMe2)YbOBut], [(LNMe2)YbOPh], [(LOMe)YbOPh]. Compound has been structurally characterized as having a quasi-octahedral environment around ytterbium, with significant inter species hydrogen bonding between CHx and triflate fluorine atoms. Ligand exchange between Yb(N(SiMe3)2)3(thf)2 and H2LR yielded [(LNMe2)YbN(SiMe3)2] and [(LOMe)YbN(SiMe3)2], while metathesis from YbI2(thf)2 and K2LOMe reproducibly afforded the surprising oxidized product [(LOMe)2YbK(dme)2], which was structurally characterized as having a distorted octahedral environment around the ytterbium(III) centre. Compounds were used to polymerize epsilon-caprolactone at room temperature in toluene, with only compounds and exhibiting significant catalytic activities. The polycaprolactone formed in these reactions was generally of high molecular weight and polydispersities<1.90 in all but one case.

Journal Article↗

A 13C-n.m.r. study of the binding of ytterbium(III) to chondroitin sulphate and chondroitin.

13C-N.m.r. spectra of chondroitin 4- and 6-sulphates, chondroitin, beta-D-glucuronate, and beta-D-glucose 6-sulphate were measured in the presence of ytterbium(III) in deuterium oxide. The structure of the ytterbium-polysaccharide compounds in solution was found to be similar to that reported for calcium chondroitin 4-sulphate in a stretched film. In the glucuronate complex, Yb(III) coordinates to the carboxylate group. For beta-D-glucose 6-sulphate, the ytterbium-induced shifts are too small to allow the structure to be determined.

Carbon Isotopes↗

Lanthanide-sensitized lanthanide luminescence: terbium-sensitized ytterbium luminescence in a trinuclear complex.

A heterotrinuclear lanthanide complex has been prepared which contains two terbium ions in DO3A-derived binding sites and a single ytterbium ion in a DTPA-like site. The luminescence properties of the system have been investigated, showing that the terbium remains in a seven-coordinate binding site throughout the synthesis, while the ytterbium occupies the eight-coordinate site. Pumping the 488 nm absorption band of the terbium ion results in energy transfer to ytterbium with emission at 980 nm.

Chelating Agents↗

[CT contrast administration of iodine, gadolinium and ytterbium. In-vitro studies and animal experiments].

The absorption of the elements iodine, gadolinium and ytterbium in various dilutions was studied in relation to CT. Regression analysis and specific CT density measurements showed that absorption decreases from gadolinium to ytterbium and iodine. These results were confirmed by experiments using ten dogs. Boli of 0.5 molar gadolinium used for angio-CT without table movement showed the largest increase in density in the aorta and liver with an average of 190HU and 21HU respectively compared with iodine which gave 157HU and 12HU respectively. The animal experimental studies suggest that gadolinium and ytterbium are suitable contrast media for dynamic CT investigations.

Absorption↗

Identification of the calcium binding site and a novel ytterbium site in blood coagulation factor XIII by x-ray crystallography.

The presence or absence of calcium determines the activation, activity, oligomerization, and stability of blood coagulation factor XIII. To explore these observed effects, we have determined the x-ray crystal structure of recombinant factor XIII A2 in the presence of calcium, strontium, and ytterbium. The main calcium binding site within each monomer involves the main chain oxygen atom of Ala-457, and also the side chains from residues Asn-436, Asp-438, Glu-485, and Glu-490. Calcium and strontium bind in the same location, while ytterbium binds several angstroms removed. A novel ytterbium binding site is also found at the dimer two-fold axis, near residues Asp-270 and Glu-272, and this site may be related to the reported inhibition by lanthanide metals (Achyuthan, K. E., Mary, A., and Greenberg, C. S. (1989) Biochem. J. 257, 331-338). The overall structure of ion-bound factor XIII is very similar to the previously determined crystal structures of factor XIII zymogen, likely due to the constraints of this monoclinic crystal form. We have merged the three independent sets of water molecules in the structures to determine which water molecules are conserved and possibly structurally significant.

Binding Sites↗

Ytterbium-169: calculated physical properties of a new radiation source for brachytherapy.

Seeds containing radioactive Ytterbium-169 (169Yb) have recently been manufactured for possible application to brachytherapy. Ytterbium-169 emits photons with an average energy of 93 keV (excluding energies less than 10 keV), and decays with a half-life of 32 days. Analytic and Monte Carlo computations have been used to predict physical quantities useful in treatment planning and radiation protection. Analytic calculations based on the primary photon spectrum of 169Yb (excluding energies less than 10 keV) yield an air-kerma rate constant of 0.0427 cGy cm2 h-1 MBq-1, and an exposure rate constant of 1.80 R cm2 mCi-1 h-1 for this radionuclide. Calculated fmed factors are 0.922 cGy/R for soft tissue and 2.12 cGy/R for bone. The first half-value layer in lead is 0.2 mm; the first tenth-value layer is 1.6 mm. Using Monte Carlo simulations, the relative dose distributions around 169Yb seeds (Amersham, prototypes 4 and 5) are provided, and are then compared with those around an 125I seed (3M model 6702). The 169Yb seeds produce more isotropic dose distributions, and for permanent implants, can deliver it at a greater initial dose rate. A value of 1.19 cm-2 was also calculated for the specific dose constant D0, a value which is applicable to both seed types. Radiation protection is not as easily achieved for permanent implants with 169Yb because of the higher energy emissions (vs 125I). However, for temporary implants, Ytterbium-169 may prove to be a useful substitute for 192Ir or 137Cs because of its relatively lower energy emissions. It is concluded that 169Yb merits further investigation, including dosimetry, radiobiological, and clinical studies.

Brachytherapy↗

The potential of ytterbium 169 in brachytherapy: a brief physical and radiobiological assessment.

Ytterbium 169 (half-life 32 days; mean gamma emission 93 keV, after excluding photons of energy less than 10 keV) is a radionuclide with interesting potential for brachytherapy applications. Although not yet commercially available, its possible application as a clinical radionuclide is currently being considered by Amersham International. This article presents an assessment of some properties of the nuclide that may be clinically relevant. Use is made of some new ideas that allow quantification of the likely dose homogeneity that can be obtained in a brachytherapy distribution, and in this context ytterbium 169 is shown to be superior to some currently available brachytherapy nuclides. The assessment also uses recent extensions to the linear-quadratic model to consider the likely radiobiological implications associated with the use of the nuclide. From this it is suggested that the main potential for ytterbium 169 would be as a source that may be re-used for a number of short-term applications, rather than as a permanently implantable nuclide.

Adipose Tissue↗

Determination of cadmium in spring water by graphite-furnace atomic absorption spectrometry after coprecipitation with ytterbium hydroxide.

A coprecipitation method with ytterbium hydroxide was studied for the determination of cadmium in water samples by graphite-furnace atomic absorption spectrometry. Up to 40 ng of cadmium in water samples was quantitatively coprecipitated with ytterbium hydroxide at pH 8.0-11.2. The concentration factor was 100 fold. The coprecipitated cadmium was sensitively determined without any influence of ytterbium and the calibration curve was linear from 0.1 to 4 ng/mL of cadmium. The detection limit (signal/noise = 2) was 2.9 pg/mL in 100 mL of the initial sample solution. Twenty-nine diverse ions tested did not interfere with the determination in at least a 10000-fold mass ratio to cadmium. The proposed method was successfully applied to the determination of cadmium in spring water.

Cadmium↗