WorldWideScience

Sample records for ndiii smiii gdiii

  1. Stability constants of La(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III) and Dy(III) complexes with N-(2-hydroxyphenyl) p-toluene sulphonamide

    Energy Technology Data Exchange (ETDEWEB)

    Chopra, S.C.; Mathur, K.C. (Jodhpur Univ. (India). Dept. of Chemistry)

    1981-01-01

    The dissociation constants of the ligand and stability constants of La(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III) and Dy(III) complexes with N-(2-hydroxyphenyl) p-toluene sulphonamide have been determined potentiometrically using Calvin-Bjerrum pH titration technique at 30 +- 1deg C and ..mu.. = 0.1 M (NaClO/sub 4/) in aqueous medium. The stability constants of these metal complexes are found to follow the order Dy > Tb > Gd > Sm > Nd > Pr > La.

  2. Co(II)4, Co(II)7, and a Series of Co(II)2Ln(III) (Ln(III) = Nd(III), Sm(III), Gd(III), Tb(III), Dy(III)) Coordination Clusters: Search for Single Molecule Magnets.

    Science.gov (United States)

    Modak, Ritwik; Sikdar, Yeasin; Thuijs, Annaliese E; Christou, George; Goswami, Sanchita

    2016-10-03

    We report herein the syntheses and investigation of the magnetic properties of a Co(II)4 compound, a series of trinuclear Co(II)2Ln(III) (Ln(III) = Nd(III), Sm(III), Gd(III), Tb(III), Dy(III)) complexes, and a Co(II)7 complex. The homometallic Co(II)4 core was obtained from the reaction of Ln(NO3)3·xH2O/Co(NO3)2·6H2O/H2vab/Et3N in a 0.5:0.5:1:2 ratio in methanol. Variation in synthetic conditions was necessary to get the desired Co(II)-Ln(III) complexes. The Co(II)-Ln(III) assembly was synthesized from Ln(NO3)3·xH2O/Co(OAc)2·4H2O/H2vab/NaOMe in a 0.4:0.5:1:1 ratio in methanol. The isostructural Co(II)2Ln(III) complexes have a core structure with the general formula [Co2Ln(Hvab)4(NO3)](NO3)2·MeOH·H2O, (where H2vab = 2-[(2-hydroxymethyl-phenylimino)-methyl]-6-methoxy-phenol) with simultaneous crystallization of Co(II)7 complex in each reaction. The magnetic investigation of these complexes reveals that both homometallic complexes and four Co(II)-Ln(III) complexes (except Co(II)-Nd(III)) display behavior characteristic of single molecule magnets.

  3. Extraction and separation of Nd(III), Sm(III), Dy(III), Fe(III), Ni(II), and Cs(I) from concentrated chloride solutions with N,N,N',N'-tetra(2-ethylhexyl) diglycolamide as new extractant

    Institute of Scientific and Technical Information of China (English)

    E.A. Mowafy; D. Mohamed

    2015-01-01

    The feasibility of using N,N,N',N'-tetra(2-ethylhexyl)diglycolamide (TEHDGA) in 75 vol.% n-dodecane-25 vol.% n-octanol as agents for the extraction and separation of Nd(III), Sm(III), Dy(III), Fe(III), Ni(II), and Cs(I) from concentrated chlo-ride solution was investigated. Different extraction behaviors were obtained towards rare earth elements (REE) studied and Fe(III), Ni(II) and Cs(I). Efficient separation of Nd(III), Sm(III) and Dy(III) from Fe(III), Ni(II), and Cs(I) was achieved by TEHDGA, depending on the HCl, HNO3 or H2SO4 concentration. A systematic investigation was carried out on the detailed extraction prop-erties of Nd(III), Sm(III), and Dy(III) with TEHDGA from chloride media. The IR spectra of the extracted species were investi-gated.

  4. Investigations into the synthesis and fluorescence properties of Eu(III), Tb(III), Sm(III) and Gd(III) complexes of a novel bis-beta-diketone-type ligand.

    Science.gov (United States)

    Luo, Yi-Ming; Chen, Zhe; Tang, Rui-Ren; Xiao, Lin-Xiang; Peng, Hong-Jian

    2008-02-01

    A novel bis-beta-diketon ligand, 1,1'-(2,6-bispyridyl)bis-3-phenyl-1,3-propane-dione (L), was designed and synthesized and its complexes with Eu(III), Tb(III), Sm(III) and Gd(III) ions were successfully prepared. The ligand and the corresponding metal complexes were characterized by elemental analysis, and infrared, mass and proton nuclear magnetic resonance spectroscopy. Analysis of the IR spectra suggested that each of the lanthanide metal ions coordinated to the ligand via the carbonyl oxygen atoms and the nitrogen atom of the pyridine ring. The fluorescence properties of these complexes in solid state were investigated and it was discovered that all of the lanthanide ions could be sensitized by the ligand (L) to some extent. In particular, the Tb(III) complex was an excellent green-emitter and would be a potential candidate material for applications in organic light-emitting devices (OLEDs) and medical diagnosis.

  5. Investigations into the synthesis and fluorescence properties of Eu(III), Tb(III), Sm(III) and Gd(III) complexes of a novel bis- β-diketone-type ligand

    Science.gov (United States)

    Luo, Yi-Ming; Chen, Zhe; Tang, Rui-Ren; Xiao, Lin-Xiang; Peng, Hong-Jian

    2008-02-01

    A novel bis- β-diketon ligand, 1,1'-(2,6-bispyridyl)bis-3-phenyl-1,3-propane-dione (L), was designed and synthesized and its complexes with Eu(III), Tb(III), Sm(III) and Gd(III) ions were successfully prepared. The ligand and the corresponding metal complexes were characterized by elemental analysis, and infrared, mass and proton nuclear magnetic resonance spectroscopy. Analysis of the IR spectra suggested that each of the lanthanide metal ions coordinated to the ligand via the carbonyl oxygen atoms and the nitrogen atom of the pyridine ring. The fluorescence properties of these complexes in solid state were investigated and it was discovered that all of the lanthanide ions could be sensitized by the ligand (L) to some extent. In particular, the Tb(III) complex was an excellent green-emitter and would be a potential candidate material for applications in organic light-emitting devices (OLEDs) and medical diagnosis.

  6. Extraction of Sm(IIIand Nd(III with N,N,N’,N’-tetrabutyl-3-oxy-diglycolamidefrom hydrochloric acid

    Directory of Open Access Journals (Sweden)

    Yang J.H.

    2013-01-01

    Full Text Available The extraction behavior of Sm(III and Nd(III with N,N,N’,N’-tetrabutyl-3-oxa-diglycolamide (TBDGA in 70% kerosene-30% n-octanol from hydrochloride acid wasstudied. The effect of hydrochloric acid concentration, extractant concentration,and temperature on the distribution of rare earth elementswas investigated. The extraction mechanism was established and the stoichiometry of the main extracted species was confirm to be SmCl3•2TBDGA and NdCl3•2TBDGA for Sm(III and Nd(III, respectively. The extraction distribution ratio decreases with an increase in temperature, which demonstrates that the extraction reaction is exothermic. The IR spectra of the loaded organic phase and free extractant were recorded and discussed.

  7. Me-3,2-HOPO Complexes of Near Infra-Red (NIR) Emitting Lanthanides: Efficient Sensitization of Yb(III) and Nd(III) in Aqueous Solution

    Energy Technology Data Exchange (ETDEWEB)

    Moore, Evan G.; Xu, Jide; Dodani, Sheel; Jocher, Christoph; D' Aleo, Anthony; Seitz, Michael; Raymond, Kenneth

    2009-11-10

    The synthesis, X-ray structure, solution stability, and photophysical properties of several trivalent lanthanide complexes of Yb(III) and Nd(III) using both tetradentate and octadentate ligand design strategies and incorporating the 1-methyl-3-hydroxy-pyridin-2-one (Me-3,2-HOPO) chelate group are reported. Both the Yb(III) and Nd(III) complexes have emission bands in the Near Infra-Red (NIR) region, and this luminescence is retained in aqueous solution ({Phi}{sub tot}{sup Yb} {approx} 0.09-0.22%). Furthermore, the complexes demonstrate very high stability (pYb {approx} 18.8-21.9) in aqueous solution, making them good candidates for further development as probes for NIR imaging. Analysis of the low temperature (77 K) photophysical measurements for a model Gd(III) complex were used to gain an insight into the electronic structure, and were found to agree well with corresponding TD-DFT calculations at the B3LYP/6-311G{sup ++}(d,p) level of theory for a simplified model monovalent sodium complex.

  8. Potentiometric studies on the complex formation of some Ln(III) ions with 4-nitrocatechol

    Energy Technology Data Exchange (ETDEWEB)

    Bhuyan, B.C.; Dubey, S.N. (Kurukshetra Univ. (India). Dept. of Chemistry)

    1981-07-01

    The interaction of La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III), Dy(III), Ho(III) and Y(III) with 4-nitrocatechol has been investigated potentiometrically in aqueous medium at 25deg and at ionic strengths of 0.05, 0.1, 0.15 and 0.2M (KNO/sub 3/). The proton-ligand formation constants and metal-ligand formation constants have been calculated using the Calvin-Bjerrum titration technique as modified by Irving and Rossotti. The thermodynamic formation constants have also been determined. The order of stabilities of the lanthanide complexes with the above ligand is found to be: La(III) < Ce(III) approximately Pr(III) < Nd(III) < Sm(III) < Gd(III) < Y(III) < Tb(III) < Dy(III) < Ho(III).

  9. Computer Simulation of Gd(III) Speciation in Human Interstitial Fluid

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The speciation and distribution of Gd(III) in human interstitial fluid was studied by computer simulation. Meantime artificial neural network was applied to the estimation of log β values of complexes. The results show that the precipitate species, GdPO4 and Gd2(CO3)3, are the predominant species. Among soluble species, the free Gd(III), [Gd(HSA)] , [Gd(Ox)] and then the ternary complexes of Gd(III) with citrate are main species and [Gd3(OH)4] becomes the predominant species at the Gd(III) total concentration of 2.2×10-2mol/L.

  10. Gd(III) functionalized gold nanorods for multimodal imaging applications.

    Science.gov (United States)

    Sun, Hongmei; Yuan, Qinghai; Zhang, Baohua; Ai, Kelong; Zhang, Pengguo; Lu, Lehui

    2011-05-01

    We demonstrate a novel noncovalent method for producing Gd(III)-functionalized gold nanorods as multimodal contrast agents for MRI and CT imaging. The ligand is connected to the surface of the gold nanorods by a noncovalent bond making the Gd(III) ions directly accessible to water molecules, and resulting in a longitudinal relaxivity as high as 21.3 mM(-1) s(-1). In addition, compared with spherical gold nanoparticles, gold nanorods have more binding sites for Gd(III) ions due to their large surface-to-volume ratio. Benefiting from the advantages of the new type of carry material and the novel fabrication approach, the multimodal imaging probes exhibit a high longitudinal relaxivity r(1) on the order of 1.1 × 10(7) mM(-1) s(-1) on a per-particle basis, which is 24 times higher than that of Gd(III)-ion-functionalized spherical gold nanoparticles. Furthermore, CT imaging shows that such nanoprobes could induce an efficient contrast enhancement when the gold concentration is at least equal to 1.31 mg ml(-1). These results demonstrate that the as-prepared Gd functionalized gold nanorods could provide a new and versatile platform for the development of multimodal imaging probes.

  11. Luminescence studies of Sm(III) and Cm(III) complexes in NaSCN/DHDECMP extraction systems

    CERN Document Server

    Chung, D Y; Kimura, T

    1999-01-01

    Laser-induced fluorescence (LIF) studies of Sm(III) and Cm(III) complexes in the NaSCN/DHDECMP solvent extraction system were carried out. Luminescence lifetimes were measured to determine the number of water molecules coordinated to Sm(III), Tb(III), Dy(III), and Cm(III) in the sodium thiocyanate solution and in the DHDECMP phase. The hydration number of Sm(III), Tb(III), Dy(III), and Cm(III) in the sodium thiocyanate solution decreased linearly with increasing sodium thiocyanate concentration. The hydration numbers of Sm(III), Dy(III), and Cm(III) in the DHDECMP phase decreased with increasing sodium thiocyanate concentration. The water molecules in the inner coordination sphere of Sm(III) and Dy(III) extracted into the DHDECMP were not completely removed at low sodium thiocyanate concentration but decreased with increasing sodium thiocyanate concentration. However, in the case of Cm(III) extracted into the DHDECMP phase from the sodium thiocyanate solution, there was no water in the inner coordination sphe...

  12. Synthesis, characterization, cytotoxicity, DNA cleavage and antimicrobial activity of homodinuclear lanthanide complexes of phenylthioacetic acid

    Institute of Scientific and Technical Information of China (English)

    T. F. Abbs Fen Reji; A. Jeena Pearl; Bojaxa A. Rosy

    2013-01-01

    Lanthanide complexes of Eu(III), Gd(III), Nd(III), Sm(III), and Tb(III) with phenylthioacetic acid were synthesized and characterized by elemental analysis, mass, infrared radiation (IR), electronic spectra, molar conductance, thermogravimetric analysis (TGA), and powder X-ray diffraction (XRD). The results showed that the lanthanide complexes were homodinuclear in nature. The two lanthanide ions were bridged by eight oxygen atoms from four carboxylate groups. Thermal decomposition profiles were consis-tent with the proposed formulations. Powder XRD studies showed that all the complexes were amorphous in nature. Antimicrobial studies indicated that these complexes exhibited more activity than the ligand itself. The DNA cleavage activity of the ligand and its complexes were assayed on CT DNA using gel electrophoresis in the presence of H2O2. The result showed that the Eu(III) and Nd(III) complexes completely cleaved the DNA. The anticancer activities of the complexes were also studied towards human cervical cancer cell line (HeLa) and colon cancer cells (HCT116) and it was found that the Eu(III) and Nd(III) complexes were more active than the corresponding Gd(III), Sm(III), Tb(III) complexes and the free ligand on both the cancer cells.

  13. Trinuclear lanthanide complexes of a compartmental ligand N, N'-bis(2-pyridinyl)-2,6-pyridinedicarboxamide: A spectroscopic investigation

    Science.gov (United States)

    Gudasi, Kalagouda B.; Shenoy, Rashmi V.; Vadavi, Ramesh S.; Patil, Siddappa A.

    2006-11-01

    Trinuclear lanthanide complexes of the formula [Ln 3(PPDA)(NO 3) 6(H 2O) 2]·NO 3·2H 2O where Ln = La(III), Pr(III), Sm(III), Nd(III), Eu(III) Gd(III) Tb(III), Dy(III) and Y(III); H 2PPDA = N, N'-bis(2-pyridinyl)-2,6-pyridinedicarboxamide, have been isolated. The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibility measurements and spectral (IR, NMR, UV-vis, fluorescence, FAB and EPR) and thermal studies.

  14. Tricarboxylate-based Gd(III) coordination polymers exhibiting large magnetocaloric effects.

    Science.gov (United States)

    Liu, Sui-Jun; Cao, Chen; Xie, Chen-Chao; Zheng, Teng-Fei; Tong, Xiao-Lan; Liao, Jin-Sheng; Chen, Jing-Lin; Wen, He-Rui; Chang, Ze; Bu, Xian-He

    2016-05-31

    Two Gd(III) coordination polymers with the formula [Gd(cit)(H2O)]∞ () and [Gd(nta)(H2O)2]∞ () (H4cit = citric acid, H3nta = nitrilotriacetic acid) have been successfully prepared under hydrothermal conditions. Complex exhibits a three-dimensional (3D) structure based on carboxylate-bridged layers, while complex is a double-layer structure containing eight-coordinated Gd(III). Magnetic investigations reveal that weak antiferromagnetic couplings between adjacent Gd(III) ions in both and with different Weiss values result in large cryogenic magnetocaloric effects. It is notable that the maximum entropy changes (-ΔS) of and reach 31.3 J kg(-1) K(-1) and 32.2 J kg(-1) K(-1) at 2 K for a moderate field change (ΔH = 3 T), and a remarkable -ΔS (41.5 J kg(-1) K(-1) for and 42.0 J kg(-1) K(-1) for ) could be obtained for ΔH = 7 T.

  15. Complexation of gluconic acid with Nd(III) in acidic solutions: A thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Zhicheng [Washington State University, Pullman, WA 99164 (United States); Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States)], E-mail: lxzhang@wsu.edu; Bottenus, Brienne; Clark, Sue B. [Washington State University, Pullman, WA 99164 (United States); Tian Guoxin [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Zanonato, PierLuigi [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Dipartimento di Scienze Chimiche, Universita di Padova, via Marzolo 1, 35131 Padova (Italy); Rao Linfeng [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States)

    2007-10-11

    Thermodynamic properties of gluconic acid (HGH{sub 4}(aq)) complexation with Nd(III) have been studied in acidic solutions at 25 deg. C and 1.0 M NaClO{sub 4} by potentiometry, spectrophotometry and calorimetry. Three Nd(III)/gluconate complexes were identified in solutions of pC{sub H} 2.5-4.5. The formation constants and the complexation enthalpies are: log {beta}{sub 1} = 2.55 {+-} 0.05 and {delta}H{sub 1}{sup o}=-(8.22{+-}0.23)kJmol{sup -1} for Nd(GH{sub 4}){sup 2+}, log {beta}{sub 2} = 4.45 {+-} 0.05 and {delta}H{sub 2}{sup o}=-(15.3{+-}0.4)kJmol{sup -1} for Nd(GH{sub 4}){sub 2}{sup +}, and log {beta}{sub 3} = 5.60 {+-} 0.15 and {delta}H{sub 3}{sup o}=-(24.6{+-}0.6)kJmol{sup -1} for Nd(GH{sub 4}){sub 3}(aq). The thermodynamic parameters indicate that gluconic acid, like other {alpha}-hydroxycarboxylic acids, forms stronger complexes with Nd(III) than simple monocarboxylic acids, likely by the participation of the {alpha}-hydroxyl group during complexation. The same type of binding appears to occur with Ca{sup 2+} and NpO{sub 2}{sup +} as the 1:1 stability constants are linearly correlated with the effective cationic charges of the metal cations.

  16. Planar tetranuclear Dy(III) single-molecule magnet and its Sm(III), Gd(III), and Tb(III) analogues encapsulated by salen-type and β-diketonate ligands.

    Science.gov (United States)

    Yan, Peng-Fei; Lin, Po-Heng; Habib, Fatemah; Aharen, Tomoko; Murugesu, Muralee; Deng, Zhao-Peng; Li, Guang-Ming; Sun, Wen-Bin

    2011-08-01

    The syntheses, structures, and magnetic properties are reported for four new lanthanide clusters [Sm(4)(μ(3)-OH)(2)L(2)(acac)(6)]·4H(2)O (1), [Gd(4)(μ(3)-OH)(2)L(2)(acac)(6)]·4CH(3)CN (2), and [Ln(4)(μ(3)-OH)(2)L(2)(acac)(6)]·2H(2)L·2CH(3)CN (3, Ln = Tb; 4, Ln = Dy) supported by salen-type (H(2)L = N,N'-bis(salicylidene)-1,2-cyclohexanediamine) and β-diketonate (acac = acetylacetonate) ligands. The four clusters were confirmed to be essentially isomorphous by infrared spectroscopy and single-crystal X-ray diffraction. Their crystal structures reveal that the salen-type ligand provides a suitable tetradentate coordination pocket (N(2)O(2)) to encapsulate lanthanide(III) ions. Moreover, the planar Ln(4) core is bridged by two μ(3)-hydroxide, four phenoxide, and two ketonate oxygen atoms. Magnetic properties of all four compounds have been investigated using dc and ac susceptibility measurements. For 4, the static and dynamic data indicate that the Dy(4) complex exhibits slow relaxation of the magnetization below 5 K associated with single-molecule magnet behavior.

  17. Dodecanuclear [Cu(II)6Gd(III)6] nanoclusters as magnetic refrigerants.

    Science.gov (United States)

    Dinca, Alina S; Ghirri, Alberto; Madalan, Augustin M; Affronte, Marco; Andruh, Marius

    2012-04-02

    A novel dodecanuclear complex, [{(HL)(L)(DMF)Cu(II)Gd(III)(DMF)(H(2)O)}(6)]·6DMF (1; DMF = N,N-dimethylformamide), has been obtained using the ligand resulting from the condensation of 3-formylsalicylic acid with hydroxylamine (H(3)L). The exchange interaction between the phenoxo-bridged Cu(II) and Gd(III) ions is weak ferromagnetic (J = +1.01 cm(-1)). The combination of a high-spin ground state with small anisotropy leads to a significant magnetocaloric effect [-ΔS(m)(0-7 T) = 23.5 J K g(-1) K(-1) at ∼2 K].

  18. Generic tags for Mn(ii) and Gd(iii) spin labels for distance measurements in proteins.

    Science.gov (United States)

    Yang, Yin; Gong, Yan-Jun; Litvinov, Aleksei; Liu, Hong-Kai; Yang, Feng; Su, Xun-Cheng; Goldfarb, Daniella

    2017-09-28

    High-affinity chelating tags for Gd(iii) and Mn(ii) ions that provide valuable high-resolution distance restraints for biomolecules were used as spin labels for double electron-electron resonance (DEER) measurements. The availability of a generic tag that can bind both metal ions and provide a narrow and predictable distance distribution for both ions is attractive owing to their different EPR-related characteristics. Herein we introduced two paramagnetic tags, 4PSPyMTA and 4PSPyNPDA, which are conjugated to cysteine residues through a stable thioether bond, forming a short and, depending on the metal ion coordination mode, a rigid tether with the protein. These tags exhibit high affinity for both Mn(ii) and Gd(iii) ions. The DEER performance of the 4PSPyMTA and 4PSPyNPDA tags, in complex with Gd(iii) or Mn(ii), was evaluated for three double cysteine mutants of ubiquitin, and the Gd(iii)-Gd(iii) and Mn(ii)-Mn(ii) distance distributions they generated were compared. All three Gd(iii) complexes of the ubiquitin-PyMTA and ubiquitin-PyNPDA conjugates produced similar and expected distance distributions. In contrast, significant variations in the maxima and widths of the distance distributions were observed for the Mn(ii) analogs. Furthermore, whereas PyNPDA-Gd(iii) and PyNPDA-Mn(ii) delivered similar distance distributions, appreciable differences were observed for two mutants with PyMTA, with the Mn(ii) analog exhibiting a broader distance distribution and shorter distances. ELDOR (electron-electron double resonance)-detected NMR measurements revealed some distribution in the Mn(ii) coordination environment for the protein conjugates of both tags but not for the free tags. The broader distance distributions generated by 4PSPyMTA-Mn(ii), as compared with Gd(iii), were attributed to the distributed location of the Mn(ii) ion within the PyMTA chelate owing to its smaller size and lower coordination number that leave the pyridine nitrogen uncoordinated. Accordingly, in

  19. Incorporation of trinuclear lanthanide(III) hydroxo bridged clusters in macrocyclic frameworks.

    Science.gov (United States)

    Kobyłka, Michał J; Ślepokura, Katarzyna; Acebrón Rodicio, Maria; Paluch, Marta; Lisowski, Jerzy

    2013-11-18

    A cluster of lanthanide(III) or yttrium(III) ions, Ln3(μ3-OH)2, (Ln(III) = Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Yb(III), or Y(III)) can be bound in the center of a chiral macrocyclic amines H3L1(R), H3L1(S), and H3L2(S) obtained in a reduction of a 3 + 3 condensation product of (1R,2R)- or (1S,2S)-1,2-diaminocyclohexane and 2,6-diformyl-4-methylphenol or 2,6-diformyl-4-tertbutylphenol. X-ray crystal structures of the Nd(III), Sm(III), Gd(III), Dy(III), and Y(III) complexes reveal trinuclear complexes with Ln(III) ions bridged by the phenolate oxygen atoms of the macrocycle as well as by μ3-hydroxo bridges. In the case of the Nd(III) ion, another complex form can be obtained, whose X-ray crystal structure reveals two trinuclear macrocyclic units additionally bridged by hydroxide anions, corresponding to a [Ln3(μ3-OH)]2(μ2-OH)2 cluster encapsulated by two macrocycles. The formation of trinuclear complexes is confirmed additionally by (1)H NMR, electrospray ionization mass spectrometry (ESI MS), and elemental analyses. Titrations of free macrocycles with Sm(III) or Y(III) salts and KOH also indicate that a trinuclear complex is formed in solution. On the other hand, analogous titrations with La(III) salt indicate that this kind of complex is not formed even with the excess of La(III) salt. The magnetic data for the trinuclear Gd(III) indicate weak antiferromagnetic coupling (J = -0.17 cm(-1)) between the Gd(III) ions. For the trinuclear Dy(III) and Tb(III) complexes the χ(M)T vs T plots indicate a more complicated dependence, resulting from the combination of thermal depopulation of mJ sublevels, magnetic anisotropy, and possibly weak antiferromagnetic and ferromagnetic interactions.

  20. Spontaneous resolution upon crystallization of chiral La(III) and Gd(III) MOFs from achiral dihydroxymalonate.

    Science.gov (United States)

    Gil-Hernández, Beatriz; Höppe, Henning A; Vieth, Jana K; Sanchiz, Joaquin; Janiak, Christoph

    2010-11-21

    The achiral chelating and bridging dihydroxymalonato (mesoxalato) ligand is a new enantiopurity enforcer in extended structures by yielding the Λ/Δ-metal configured homochiral MOFs 2D-[Ln(2)(μ-mesoxalato)(3)(H(2)O)(6)] (Ln = La(III), Gd(III)) through self-resolution during crystal growth.

  1. Spectral study of the complexation of Nd(III) with glutathione reduced (GSH) in the presence and absence of Zn(II) in aquated organic solvents

    Indian Academy of Sciences (India)

    Th David Singh; Ch Sumitra; N Rajmuhon Singh; M Indira Devi

    2004-11-01

    Studies on the difference in energy parameters and comparative absorption spectrophotometry involving 4-4 transitions on Nd(III) and glutathione reduced (GSH) in the absence and presence of Zn(II) have been carried out in aquated organic solvents (50 : 50) like methanol, dioxane, acetonitrile and dimethylformamide. Variations in the spectral energy parameters - Slater-Condon () factor, Lande spin-orbit coupling constant (4), nephelauxetic ratio (), bonding parameter (1/2) and percent covalency () - are calculated and correlated with binding of Nd(III) with GSH in presence and absence of Zn(II).

  2. Structural and thermodynamic study of the complexes of Nd(III) with N,N,N',N'-tetramethyl-3-oxa-glutaramide and the acid analogues.

    Science.gov (United States)

    Tian, Guoxin; Teat, Simon J; Rao, Linfeng

    2014-09-15

    The thermodynamics of Nd(III) complexes with N,N,N',N'-tetramethyl-3-oxa-glutaramide (TMOGA, L(I)), N,N-dimethyl-3-oxa-glutaramic acid (DMOGA, HL(II)), and oxydiacetic acid (ODA, H2L(III)) in aqueous solutions was studied. Stability constants, enthalpies, and entropies of complexation were determined by spectrophotometry, potentiometry, and calorimetry. The stability constants of corresponding Nd(III) complexes decrease in the following order: Nd(III)/L(III) > Nd(III)/L(II) > Nd(III)/L(I). For all complexes, the enthalpies of complexation are negative and the entropies of complexation are positive, indicating that the complexation is driven by both enthalpy and entropy. Furthermore, from L(III) to L(II), and to L(I), the enthalpy of complexation becomes more exothermic and the entropy of complexation less positive, suggesting that the substitution of a carboxylate group with an amide group on the ligands enhances the enthalpy-driven force but weakens the entropy-driven force of the complexation with Nd(III). Crystal structures of three 1:3 Nd(III) complexes, Nd(L(I))3(ClO4)3 (I), Nd(L(I))3(NO3)3(H2O)2 (II), and Nd(L(II))3(H2O)7.5 (III), were determined by single-crystal X-ray diffraction and compared with the structure of a 1:3 Nd(III)/L(III) complex in the literature, Na3NdL(III)3(NaClO4)2(H2O)6 (IV). In all four structures, the ligands are tridentate and Nd(III) is nine-coordinated with similar distorted tricapped trigonal prism geometry by three ether oxygen atoms capped on the three faces of the prism, and six oxygen atoms from the ketone group or carboxyl group at the corners. The absorption spectra of Nd(III) in solutions showed very similar patterns as Nd(III) formed successive 1:1, 1:2, and 1:3 complexes with L(I), L(II), and L(III), respectively, implying that the Nd(III) complexes with the three ligands have similar coordination geometries in aqueous solutions, as observed in the solids.

  3. Complexation of Am(III) and Nd(III) by 1,10-Phenanthroline-2,9-Dicarboxylic Acid

    Energy Technology Data Exchange (ETDEWEB)

    Ogden, Mark D.; Sinkov, Sergey I.; Nilsson, Mikael; Lumetta, Gregg J.; Hancock, Robert D.; Nash, Ken L.

    2013-01-01

    The complexant 1,10-phenanthroline-2,9-dicarboxylic acid (PDA) is a planar tetradentate ligand that is more preorganized for metal complexation than its unconstrained analogue ethylendiiminodiacetic acid (EDDA). Furthermore, the backbone nitrogen atoms of PDA are aromatic, hence are softer than the aliphatic amines of EDDA. It has been hypothesized that PDA will selectively bond to trivalent actinides over lanthanides. In this report, the results of spectrophotometric studies of the complexation of Nd(III) and Am(III) by PDA are reported. Because the complexes are moderately stable, it was necessary to conduct these titrations using competitive equilibrium methods, competitive cation omplexing between PDA and diethylenetriaminepentaacetic acid, and competition between ligand protonation and complex formation. Stability constants and ligand protonation constants were determined at 0.1 mol/L ionic strength and at 0.5 mol/L ionic strength nitrate media at 21 ± 1 C. The stability constants are lower than those predicted from first principles and speciation calculations indicate that Am(III) selectivity over Nd(III) is less than that exhibited by 1,10-phenanthroline.

  4. Complexation of Nd(III) with tetraborate ion and its effect on actinide (III) solubility in WIPP brine

    Energy Technology Data Exchange (ETDEWEB)

    Borkowski, Marian [Los Alamos National Laboratory; Richmann, Michael K [Los Alamos National Laboratory; Reed, Donald T [Los Alamos National Laboratory; Yongliang, Xiong [SNL

    2010-01-01

    The potential importance of tetraborate complexation on lanthanide(III) and actinide(III) solubility is recognized in the literature but a systematic study of f-element complexation has not been performed. In neodymium solubility studies in WIPP brines, the carbonate complexation effect is not observed since tetraborate ions form a moderately strong complex with neodymium(III). The existence of these tetraborate complexes was established for low and high ionic strength solutions. Changes in neodymium(III) concentrations in undersaturation experiments were used to determine the neodymium with tetraborate stability constants as a function of NaCl ionic strength. As very low Nd(III) concentrations have to be measured, it was necessary to use an extraction pre-concentration step combined with ICP-MS analysis to extend the detection limit by a factor of 50. The determined Nd(III) with borate stability constants at infinite dilution and 25 C are equal to log {beta}{sub 1} = 4.55 {+-} 0.06 using the SIT approach, equal to log {beta}{sub 1} = 4.99 {+-} 0.30 using the Pitzer approach, with an apparent log {beta}{sub 1} = 4.06 {+-} 0.15 (in molal units) at I = 5.6 m NaCl. Pitzer ion-interaction parameters for neodymium with tetraborate and SIT interaction coefficients were also determined and reported.

  5. Complexation of Nd(III) with tetraborate ion and its effect on actinide(III) solubility in WIPP brine

    Energy Technology Data Exchange (ETDEWEB)

    Borkowski, M.; Richmann, M.; Reed, D.T. [Earth and Environmental Sciences Div., Los Alamos National Lab., Carlsbad Operations, NM (United States); Xiong, Y. [Sandia National Labs., Carlsbad Program Group, Carlsbad, NM (United States)

    2010-07-01

    The potential importance of tetraborate complexation on lanthanide(III) and actinide(III) solubility is recognized in the literature but a systematic study of f-element complexation has not been performed. In neodymium solubility studies in WIPP brines, the carbonate complexation effect is not observed since tetraborate ions form a moderately strong complex with neodymium(III). The existence of these tetraborate complexes was established for low and high ionic strength solutions. Changes in neodymium(III) concentrations in undersaturation experiments were used to determine the neodymium with tetraborate stability constants as a function of NaCl ionic strength. As very low Nd(III) concentrations have to be measured, it was necessary to use an extraction pre-concentration step combined with ICP-MS analysis to extend the detection limit by a factor of 50. The determined Nd(III) with borate stability constants at infinite dilution and 25 C are equal to log {beta}{sub 1} = 4.55 {+-} 0.06 using the SIT approach, equal to log {beta}{sub 1} = 4.99 {+-} 0.30 using the Pitzer approach, with an apparent log {beta}{sub 1} = 4.06 {+-} 0.15 (in molal units) at I = 5.6 m NaCl. Pitzer ion-interaction parameters for neodymium with tetraborate and SIT interaction coefficients were also determined and reported. (orig.)

  6. Sorption of environmentally relevant radionuclides (U(VI), Np(V)) and lanthanides (Nd(III)) on feldspar and mica

    Energy Technology Data Exchange (ETDEWEB)

    Richter, Constanze

    2015-11-05

    A safe storage of radioactive waste in repositories is an important task to protect humans and the environment from radio- and chemotoxicity. Long-term safety assessments predict the behavior of potential environmental contaminants like the actinides plutonium, uranium, or neptunium, in the near and far field of repositories. For such safety assessments, it is necessary to know the migration behavior of the contaminants in the environment, which is mainly dependent on the aquatic speciation, the solubility product of relevant solid phases, and the retardation due to sorption on surrounding minerals. Thus, an investigation of sorption processes of contaminants onto different minerals as well as the derivation of mineral specific surface complexation model (SCM) parameters is of great importance. Feldspar and mica are widely distributed in nature. They occur as components of granite, which is considered as a potential host rock for a repository in Germany, and in numerous other rocks, and thus also in the far field of nearly all repositories. However, their sorption behavior with actinides has only been scarcely investigated until now. In order to better characterize these systems and subsequently to integrate these minerals into the long-term safety assessments, this work focuses on the investigation of the sorption behavior of U(VI), Np(V), and Nd(III) as analogue for An(III) onto the minerals orthoclase and muscovite, representing feldspars and mica, respectively. All investigations were performed under conditions relevant to the far field of a repository. In addition to the extensive characterization of the minerals, batch sorption experiments, spectroscopic investigations, and surface complexation modeling were performed to elucidate the uptake and speciation of actinides on the mineral surfaces. In addition, the influence of microorganisms naturally occurring on the mineral surfaces and the effect of Ca{sup 2+} on U(VI) uptake on the minerals was studied. The

  7. Synthesis, crystal structure, interaction with BSA and antibacterial activity of La(III) and Sm(III) complexes with enrofloxacin.

    Science.gov (United States)

    Wang, Yan-Jun; Hu, Rui-Ding; Jiang, Dong-Hua; Zhang, Ping-Hua; Lin, Qiu-Yue; Wang, Yun-Yun

    2011-03-01

    Two new La(III) and Sm(III) complexes with enrofloxacin (HER, 1-cyclopropyl-7-(4-ethyl-1-piperazinyl)-6-fluoro-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, C(19)H(21)FN(3)O(3)), [La(2)(ER)(6)(H(2)O)(2)]·14H(2)O(1) and [Sm(2)(ER)(6)(H(2)O)(2)]·14H(2)O(2) have been synthesized and characterized by elemental analysis, FT-IR, TG-DTG and X-ray single crystal diffraction. Both of the complexes are triclinic system with space group Pī. The structure of the complexes show that each rare earth atom in both complexes was nine-coordinated. Two of the enrofloxacin ions acted as tridentate chelate and bridging ligands, while the others as bidentate chelate ligands. The binding reaction between the complexes and bovine serum albumin (BSA) was studied by UV-vis absorption spectra and fluorescence spectroscopy. The results indicated that the two complexes had a quite strong ability to quench the fluorescence from BSA and the binding reaction was mainly a static quenching process. The binding constants K ( A )/(L·mol(-1)) were 1.46 × 10(5)(1) and 8.59 × 10(6)(2) and one binding site was formed. The synchronous spectroscopy suggested that tryptophan residues were placed in BSA. It was also found that the two complexes exhibited greater antimicrobial activity than enrofloxacin at given concentrations.

  8. Aggregation-induced white-light emission from the triple-stranded dinuclear Sm(iii) complex.

    Science.gov (United States)

    Leng, Jiaqi; Li, Hongfeng; Chen, Peng; Sun, Wenbin; Gao, Ting; Yan, Pengfei

    2014-08-28

    A novel bis-β-diketone ligand, 4,4'-bis(4,4,4-trifluoro-1,3-dioxobutyl)(phenoxy)-1,1'-binaphthalene (BTPB), is designed for synthesis of a white light emissive lanthanide complex. The ligand bears two benzoyl β-diketonate sites linked by a 1,1'-binaphthoxy spacer. Reaction of the doubly negatively charged bis-bidentate ligand with lanthanide ions forms triple-stranded dinuclear complexes Sm2(BTPB)3(H2O)4 () and Gd2(BTPB)3(H2O)4 (), which have been fully characterized by various spectroscopic techniques. UV-Vis absorption and emission spectroscopic techniques are used to investigate photophysical properties of the ligand and its complexes in THF and CHCl3. In some cases aggregation of the ligand results in the appearance of a new luminescence band at about 510 nm in addition to the monomer fluorescence. In complex , partial energy transfer from BTPB results in Sm(iii)-based red light emission in addition to the BTPB-based blue/green emission. With the variation of the excited wavelength and concentration of the solution, complex shows a tunable white light emission with the balance of three primary colors. This is an unusual case of observation of white light emission from a single molecule Sm(iii) complex.

  9. Facile and highly efficient removal of trace Gd(III) by adsorption of colloidal graphene oxide suspensions sealed in dialysis bag

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Weifan, E-mail: dragon0791@sohu.com [School of Materials Science and Engineering, Nanchang University, Nanchang 330031 (China); Research Center of Rare Earths and Micro/Nano Functional Materials, Nanchang University, Nanchang 330031 (China); Wang, Linlin; Zhuo, Mingpeng; Liu, Yue; Wang, Yiping [School of Materials Science and Engineering, Nanchang University, Nanchang 330031 (China); Li, Yongxiu [Research Center of Rare Earths and Micro/Nano Functional Materials, Nanchang University, Nanchang 330031 (China)

    2014-08-30

    Graphical abstract: Schematic diagram of Gd(III) adsorption and desorption on GO nanosheets in colloidal suspensions sealed by dialysis membrane. - Highlights: • Loading GO suspensions into dialysis bag for sorption of Gd(III) avoids re-pollution. • GO shows higher adsorption capacity for Gd(III) than any other currently reported. • Effects of pH, ionic strength and temperature on GO sorption for Gd(III) were studied. • Gd(III)-saturated GO has high desorption rate in nitric acid aqueous solution. • The thermodynamics and kinetics models of Gd(III) sorption on GO were studied. - Abstract: A facile, highly efficient and second-pollution-free strategy to remove trace Gd(III) from aqueous solutions by adsorption of colloidal graphene oxide (GO) suspensions in dialysis bag has been developed. The effects of pH, ionic strength and temperature on Gd(III) adsorption, and the pH-dependent desorption were investigated. The maximum adsorption capacity of Gd(III)on GO at pH = 5.9 ± 0.1 and T = 303 K was 286.86 mg g{sup −1}, higher than any other currently reported. The Gd(III)-saturated GO suspension could resume colloidal state in 0.1 M HNO{sub 3} with desorption rate of 85.00% in the fifth adsorption–desorption cycle. Gd(III) adsorption rate on GO was dependent more on pH and ionic strength than on temperature. The abundant oxygen-containing functional groups such as carboxyl and hydroxyl played a vital role on adsorption. The thermodynamics and kinetics investigations revealed that the adsorption of Gd(III) on GO was an endothermic, spontaneous and monolayer absorption process, which well fitted the pseudo-second-order model. GO could be a promising adsorbent applied in the enrichment and removal of lanthanides from aqueous solutions. More significantly, the combination of colloidal GO suspension with dialysis membrane facilely solves the re-pollution of the treated solutions due to the great difficulties in separation and recovery of GO.

  10. Near infrared (NIR) lanthanide emissive Langmuir-Blodgett monolayers formed using Nd(III) directed self-assembly synthesis of chiral amphiphilic ligands.

    Science.gov (United States)

    Barry, Dawn E; Kitchen, Jonathan A; Albrecht, Martin; Faulkner, Stephen; Gunnlaugsson, Thorfinnur

    2013-09-10

    The incorporation of chiral amphiphilic lanthanide-directed self-assembled Nd(III) complexes (Nd.13 and Nd.23) into stable Langmuir monolayers, and the subsequent Langmuir-Blodgett film formation of these, is described. The photophysical properties of the enantiomeric pair of ligands 1 and 2 in the presence of Nd(CF3SO3)3 were also investigated in CH3CN solutions using UV-vis, fluorescence, and lanthanide luminescence spectroscopies. Analysis of the resulting self-assembly processes revealed that two main species were formed in solution,1:1 and 1:3 Nd:L self-assembly complexes, with the latter being the dominant species upon the addition of 0.33 equivalents of Nd(III). Excited state lifetime measurements of Nd.13 and Nd.23 in CH3OH and CD3OD and CH3CN were also evaluated. The formation of the self-assembly in solution was also monitored by observing the changes in the circular dichroism (CD) spectra; and large differences were observed between the 1:3 and other stoichiometries in the spectra, allowing for correlation to be made with that seen in the emission studies of these systems. Surface pressure-area and surface pressure-time isotherms evidenced the formation of stable Langmuir monolayers of Nd.13 and Nd.23 at an air-water interface, and the deposition of these monolayers onto a quartz solid substrate (Langmuir-Blodgett films) gave rise to immobilized chiral monomolecular films which exhibited Nd(III) NIR luminescence upon excitation of the ligand chromophore, demonstrating efficient energy transfer to the Nd(III) excided state (sensitized) with concomitant emission centered at 800 and 1334 nm.

  11. Investigation of properties of rare earth complexes with dibromo--methyl-methylsulfonazo by spectral correction technique

    Indian Academy of Sciences (India)

    Hong-Wen Gao; Fa-Shui Hong; Qing-Song Ye

    2000-12-01

    The reactions were sensitive between seven rare earth (RE) metals Nd(III), La(III), Ce(III), Pr(III), Sm(III), Eu(III) and Gd(III) and dibromo--methylmethylsulfonazo (DBMMSA) in acidic solution. The spectral correction method has been applied in the determination of properties of RE complexes instead of ordinary spectrophotometry. Composition ratios, real molar absorptivities ( ) and stepwise stability constants () of each of the RE complexes were determined easily because the method eliminated the absorption influence of excess of ligand on complex. Results showed that the cumulative values of the complexes were between 3 91 × 1014 and 2 34 × 1028 and the real (not apparent) absorptivity between 8 85 × 104 and 2 12 × 105 l mol-1cm-1 at 640 nm.

  12. Complexes of light lanthanides with 2,3-dimethoxybenzoic acid

    Directory of Open Access Journals (Sweden)

    AGNIESZKA WALKÓW-DZIEWULSKA

    2001-08-01

    Full Text Available The complexes of light lanthanides with 2,3-dimethoxybenzoic acid of the formula: Ln(C9H9O43, where Ln = La(III, Ce(III, Pr(III, Nd(III, Sm(III, Eu(III and Gd(III have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric studies, as well as X-ray and magnetic measurements. The complexes have colours typical for Ln3+ ions (La, Ce, Eu, Gd–white, Sm–cream, Pr–green, Nd–violet. The carboxylate group in these complexes is a bidentate, chelating ligand or a tridentate chelating and bridging one. They are crystalline compounds characterized by low symmetry. On heating in air to 1173 K, the 2,3-dimethoxybenzoates of the light lanthanides decompose in various ways. The complexes of Ce(III, Pr(III, Sm(III, Eu(III and Gd(III decompose directly to oxides of the respective metals while those of La(III and Nd(III via the intermediate formation of La2O2CO3 and Nd2O2CO3. The solubilities of the 2,3-dimethoxybenzoates of the light lanthanides in water at 293 K are in the orders of 10-3 – 10-2 mol dm-3. The magnetic moments were determined in the range 4.2–298 K and the complexes are found to obey the Curie-Weiss law.

  13. Systematic theoretical investigation of the zero-field splitting in Gd(III) complexes: Wave function and density functional approaches

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Shehryar, E-mail: sherkhan@fysik.su.se; Odelius, Michael, E-mail: odelius@fysik.su.se [Department of Physics, Stockholm University, AlbaNova University Center, S-106 91 Stockholm (Sweden); Kubica-Misztal, Aleksandra [Institute of Physics, Jagiellonian University, ul. Reymonta 4, PL-30-059 Krakow (Poland); Kruk, Danuta [Faculty of Mathematics and Computer Science, University of Warmia and Mazury in Olsztyn, Sloneczna 54, Olsztyn PL-10710 (Poland); Kowalewski, Jozef [Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, S-106 91 Stockholm (Sweden)

    2015-01-21

    The zero-field splitting (ZFS) of the electronic ground state in paramagnetic ions is a sensitive probe of the variations in the electronic and molecular structure with an impact on fields ranging from fundamental physical chemistry to medical applications. A detailed analysis of the ZFS in a series of symmetric Gd(III) complexes is presented in order to establish the applicability and accuracy of computational methods using multiconfigurational complete-active-space self-consistent field wave functions and of density functional theory calculations. The various computational schemes are then applied to larger complexes Gd(III)DOTA(H{sub 2}O){sup −}, Gd(III)DTPA(H{sub 2}O){sup 2−}, and Gd(III)(H{sub 2}O){sub 8}{sup 3+} in order to analyze how the theoretical results compare to experimentally derived parameters. In contrast to approximations based on density functional theory, the multiconfigurational methods produce results for the ZFS of Gd(III) complexes on the correct order of magnitude.

  14. Synthesis and in vitro microbial evaluation of La(III), Ce(III), Sm(III) and Y(III) metal complexes of vitamin B6 drug

    Science.gov (United States)

    Refat, Moamen S.; Al-Azab, Fathi M.; Al-Maydama, Hussein M. A.; Amin, Ragab R.; Jamil, Yasmin M. S.

    2014-06-01

    Metal complexes of pyridoxine mono hydrochloride (vitamin B6) are prepared using La(III), Ce(III), Sm(III) and Y(III). The resulting complexes are investigated. Some physical properties, conductivity, analytical data and the composition of the four pyridoxine complexes are discussed. The elemental analysis shows that the formed complexes of La(III), Ce(III), Sm(III) and Y(III) with pyridoxine are of 1:2 (metal:PN) molar ratio. All the synthesized complexes are brown in color and possess high melting points. These complexes are partially soluble in hot methanol, dimethylsulfoxide and dimethylformamide and insoluble in water and some other organic solvents. Elemental analysis data, spectroscopic (IR, UV-vis. and florescence), effective magnetic moment in Bohr magnetons and the proton NMR suggest the structures. However, definite particle size is determined by invoking the X-ray powder diffraction and scanning electron microscopy data. The results obtained suggested that pyridoxine reacted with metal ions as a bidentate ligand through its phenolate oxygen and the oxygen of the adjacent group at the 4‧-position. The molar conductance measurements proved that the pyridoxine complexes are electrolytic in nature. The kinetic and thermodynamic parameters such as: Ea, ΔH*, ΔS* and ΔG* were estimated from the DTG curves. The antibacterial evaluation of the pyridoxine and their complexes were also performed against some gram positive, negative bacteria as well as fungi.

  15. Synthesis, spectroscopic and antimicrobial studies of La(III), Ce(III), Sm(III) and Y(III) Metformin HCl chelates

    Science.gov (United States)

    Refat, Moamen S.; Al-Azab, Fathi M.; Al-Maydama, Hussein M. A.; Amin, Ragab R.; Jamil, Yasmin M. S.; Kobeasy, Mohamed I.

    2015-05-01

    Metal complexes of Metformin hydrochloride were prepared using La(III), Ce(III), Sm(III) and Y(III). The resulting complexes were discussed and synthesized to serve as potential insulin-mimetic. Some physical properties and analytical data of the four complexes were checked. The elemental analysis shows that La(III), Ce(III) Sm(III) and Y(III) formed complexes with Metformin in 1:3 (metal:MF) molar ratio. All the synthesized complexes are white and possess high melting points. These complexes are soluble in dimethylsulfoxide and dimethylformamide, partially soluble in hot methanol and insoluble in water and some other organic solvents. From the spectroscopic (infrared, UV-vis and florescence), effective magnetic moment and elemental analyses data, the formula structures are suggested. The results obtained suggested that Metformin reacted with metal ions as a bidentate ligand through its two imino groups. The molar conductance measurements proved that the Metformin complexes are slightly electrolytic in nature. The kinetic thermodynamic parameters such as: E∗, ΔH∗, ΔS∗ and ΔG∗ were estimated from the DTG curves. The antibacterial evaluations of the Metformin and their complexes were also performed against some gram positive, negative bacteria as well as fungi.

  16. Multifunctional Mesoporous Silica Nanospheres with Cleavable Gd(III) Chelates as MRI Contrast Agents: Synthesis, Characterization, Target-Specificity, and Renal Clearance

    Science.gov (United States)

    Vivero-Escoto, Juan L.; Taylor-Pashow, Kathryn M. L.; Huxford, Rachel C.; Rocca, Joseph Della; Okoruwa, Christie; An, Hongyu; Lin, Weili

    2013-01-01

    Mesoporous silica nanospheres (MSNs) are a promising material for magnetic resonance imaging (MRI) contrast agents. In this paper multifunctional MSNs with cleavable Gd(III) chelates are synthesized and characterized, and their applicability as MRI contrast agents is demonstrated both in vitro and in vivo. The MSNs contain Gd(III) chelates that are covalently linked via a redox-responsive disulfide moiety. The MSNs are further functionalized with polyethylene glycol (PEG) and an anisamide ligand to improve their biocompatibility and target specificity. The effectiveness of MSNs as an MRI imaging contrast agent and their targeting ability are successfully demonstrated in vitro using human colon adenocarcinoma and pancreatic cancer cells. Finally, the capability of this platform as an in vivo MRI contrast agent is tested using a 3T scanner. The Gd(III) chelate was quickly cleaved by the blood pool thiols and eliminated through the renal excretion pathway. Further tuning of the Gd(III) chelate release kinetics is needed before the MSN system can be used as target-specific MRI contrast agents in vivo. PMID:22069305

  17. Synthesis, thermal and spectroscopic behaviors of metal-drug complexes: La(III), Ce(III), Sm(III) and Y(III) amoxicillin trihydrate antibiotic drug complexes

    Science.gov (United States)

    Refat, Moamen S.; Al-Maydama, Hussein M. A.; Al-Azab, Fathi M.; Amin, Ragab R.; Jamil, Yasmin M. S.

    2014-07-01

    The metal complexes of Amoxicillin trihydrate with La(III), Ce(III), Sm(III) and Y(III) are synthesized with 1:1 (metal:Amox) molar ratio. The suggested formula structures of the complexes are based on the results of the elemental analyses, molar conductivity, (infrared, UV-visible and fluorescence) spectra, effective magnetic moment in Bohr magnetons, as well as the thermal analysis (TG), and characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The results obtained suggested that Amoxicillin reacted with metal ions as tridentate ligands, coordinating the metal ion through its amino, imino, and β-lactamic carbonyl. The kinetic thermodynamic parameters such as: Ea, ΔH*, ΔS* and ΔG* were estimated from the DTG curves.

  18. Synthesis, thermal and spectroscopic behaviors of metal-drug complexes: La(III), Ce(III), Sm(III) and Y(III) amoxicillin trihydrate antibiotic drug complexes.

    Science.gov (United States)

    Refat, Moamen S; Al-Maydama, Hussein M A; Al-Azab, Fathi M; Amin, Ragab R; Jamil, Yasmin M S

    2014-07-15

    The metal complexes of Amoxicillin trihydrate with La(III), Ce(III), Sm(III) and Y(III) are synthesized with 1:1 (metal:Amox) molar ratio. The suggested formula structures of the complexes are based on the results of the elemental analyses, molar conductivity, (infrared, UV-visible and fluorescence) spectra, effective magnetic moment in Bohr magnetons, as well as the thermal analysis (TG), and characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The results obtained suggested that Amoxicillin reacted with metal ions as tridentate ligands, coordinating the metal ion through its amino, imino, and β-lactamic carbonyl. The kinetic thermodynamic parameters such as: Ea, ΔH(*), ΔS(*) and ΔG(*) were estimated from the DTG curves.

  19. Novel polycarboxylated EDTA-type cyclodextrins as ligands for lanthanide binding: study of their luminescence, relaxivity properties of Gd(iii) complexes, and PM3 theoretical calculations.

    Science.gov (United States)

    Maffeo, Davide; Lampropoulou, Maria; Fardis, Michael; Lazarou, Yannis G; Mavridis, Irene M; Mavridou, Despoina A I; Urso, Elena; Pratsinis, Harris; Kletsas, Dimitris; Yannakopoulou, Konstantina

    2010-04-21

    Novel -type cyclodextrin (CD) derivatives, , and , bearing 6, 7 and 8 bis(carboxymethyl)amino (iminodiacetic acid) groups, respectively, were prepared, and their complexation with Eu(iii), Tb(iii) and Gd(iii) ions was studied. Luminescence titrations and mass spectrometry showed formation of multimetal complexes ( 2 to 3, mainly 3 and exactly 4 metal ions), whereas luminescence lifetime measurements revealed the presence of exchangeable water molecules. Semiempirical quantum mechanical calculations, performed by the PM3 method and assessed by DFT calculations on model ligands, indicated efficient multi-metal complexation, in agreement with the experiment. The structures showed coordination of the metal ions in the outer primary side of the CDs via 4 carboxylate O atoms, 2 N atoms and a glucopyranose O atom per metal ion. Coordination of water molecules was also predicted, in accordance with experimental results. Calculated bond lengths and angles were in agreement with literature experimental values of lanthanide complexes. Calculated energies showed that complex stability decreases in the order > > . (1)H NMR molecular relaxivity measurements for the Gd(iii) complexes of , or in water afforded values 4 to 10 times higher than the relaxivity of a commercial contrast agent at 12 MHz, and 6 to 20 times higher at 100 MHz. Solutions of and Gd(iii) complexes in human blood plasma displayed relaxivity values at 100 MHz 7 and 12 times, respectively, higher than the commercial agent. MTT tests of the Gd(iii) complexes using human skin fibroblasts did not show toxicity. Attempts to supramolecularly sensitize the luminescence of the lanthanide complexes using various aromatic CD guests were ineffective, evidently due to large guest-metal distances and inefficient inclusion. The described lanthanide complexes, could be useful as contrast agents in MRI.

  20. Synthesis, Characterization of La(III, Nd(III, and Er(III Complexes with Schiff Bases Derived from Benzopyran-4-one and Thier Fluorescence Study

    Directory of Open Access Journals (Sweden)

    Aida L. El-Ansary

    2012-01-01

    Full Text Available The Schiff bases, L1, L2, and L3, are synthesized from the condensation of 5,7-dihydroxy-6-formyl-2-methylbenzopyran-4-one (L with 2-aminopyridine (1, p-phenylenediamine (2, and o-phenylenediamine (3. The prepared Schiff bases react with lanthanum (III, neodymium (III, and erbium (III nitrate to give complexes with stoichiometric ratio (1 : 1 (ligand : metal. The binuclear complexes of Er(III with L3 and the three metal ions with L2 are separated. The complexes have been characterized by elemental analysis, molar conductance, electronic absorption, and infrared, 1H-NMR spectral studies. The presence of hydrated and coordinated water molecules is inferred from thermogravimetric analysis. Thermal degradation studies show that the final product is the metal oxide. The luminescence properties of the Nd(III and Er(III complexes in dimethylformamide (DMF solutions were investigated.

  1. Preparation, spectroscopic and thermal characterization of new La(III), Ce(III), Sm(III) and Y(III) complexes of enalapril maleate drug. In vitro antimicrobial assessment studies

    Science.gov (United States)

    Refat, Moamen S.; Al-Azab, Fathi M.; Al-Maydama, Hussein M. A.; Amin, Ragab R.; Jamil, Yasmin M. S.

    2014-02-01

    The 1:1 M ratio metal complexes of enalapril maleate hypertensive drug with La(III), Ce(III), Sm(III) and Y(III) were synthesized. The suggested structures of the resulted complexes based on the results of elemental analyses, molar conductivity, (infrared, UV-visible and fluorescence) spectra, effective magnetic moment, thermal analysis (TG), X-ray powder diffraction (XRD) and scanning electron microscopy (SEM) were discussed. The infrared spectral data were suggested that enalapril reacts with metal ions as an ionic bidentate ligand through its carboxylate oxygen and the amide carbonyl oxygen, but in case of the Sm(III) complex, it reacted as a monodentate through its amide carbonyl oxygen. Maleate moiety acts with all these metals as bidentate ligand through its carboxylate or carbonyl oxygen. The kinetic and thermodynamic parameters such as: Ea, ΔH*, ΔS* and ΔG* were estimated from the DTG curves. The antibacterial evaluation of the enalapril maleate and their complexes were also performed against some gram positive and negative bacteria as well as fungi.

  2. Solvation structure and thermodynamics for Pr(III), Nd(III) and Dy(III) complexes in ionic liquids evaluated by Raman spectroscopy and DFT calculation

    Science.gov (United States)

    Kuribara, Keita; Matsumiya, Masahiko; Tsunashima, Katsuhiko

    2016-12-01

    The coordination states of trivalent praseodymium, neodymium, and dysprosium complexes in the ionic liquid, triethyl-n-pentylphosphonium bis(trifluoromethyl-sulfonyl) amide ([P2225][TFSA]) were investigated by Raman spectroscopy. The effect of the concentration of rare earth ions on the Raman spectra was investigated, ranging from 0.23 to 0.45 mol kg-1 of Pr(III), Nd(III), and Dy(III) in [P2225][TFSA]. Based on a conventional analysis, the solvation numbers, n, of Pr(III), Nd(III), and Dy(III) in [P2225][TFSA] were determined to be 4.99, 5.01, and 5.00 at 298 K and 5.04, 5.06, and 5.07 at 373 K, respectively. Thermodynamic properties such as ΔisoG, ΔisoH, and ΔisoS for the isomerism of [TFSA]- from trans- to cis-coordinated isomer in the bulk and the first solvation sphere of the central RE3+ (RE = Pr, Nd, and Dy) cation in [P2225][TFSA] were evaluated from the temperature dependence of the Raman bands, measured at temperatures ranging from 298 to 398 K. Regarding the bulk properties, ΔisoG(bulk), ΔisoH(bulk), and TΔisoS(bulk) at 298 K were found to be -1.06, 6.86, and 7.92 kJ mol-1, respectively. The trans-[TFSA]- was a dominant contributor to the enthalpy, as shown by the positive value of ΔisoH(bulk). The value of TΔisoS(bulk) was slightly larger than that of ΔisoH(bulk), and cis-[TFSA]- was, therefore, entropy-controlled in [P2225][TFSA]. In contrast, in the first solvation sphere of the RE3+ cation, ΔisoH(RE) became remarkably negative, suggesting that cis-[TFSA]- isomers were stabilized by enthalpic contributions. Furthermore, ΔisoH(RE) contributed to the remarkable decrease in ΔisoG(RE), and this result clearly indicates that cis-[TFSA]- conformers bound to RE3+ cations are the preferred coordination state of [RE(III)(cis-TFSA)5]2- in [P2225][TFSA]. Moreover, optimized geometries and binding energies of [Pr(III)(cis-TFSA)5]2-, [Nd(III)(cis-TFSA)5]2-, and [Dy(III)(cis-TFSA)5]2- clusters were also investigated by DFT calculations using the ADF

  3. The synthesis and determination of the octacoordinated structure of Pr(III) and Nd(III) complexes with β-diketones and diols in non aqueous solutions: evidence of some participation of π-electron density of diols with Pr(III) and Nd(III) in complexation

    Science.gov (United States)

    Misra, Sudhindra N.; Devi, M. Indira

    1997-10-01

    The synthesized complexes are of the general structure Ln(β-diketonate) 3 diol (where β-diketonate = benzoyl acetonate (bzac), dibenzoyl methanoate (dbm) and thionyl trifluoroacetonate (ttfa) and (diols) (= butane-1,4- and cis-butene-1,4-diols). The absorption intensity data in non aqueous solvents has been analysed in terms of Judd Ofelt intensity Tλ(λ = 2, 4, 6) parameters for electric dipole 4f-4f transitions. β-diketones are bidentate and function as monofunctional ligands coordinating through oxygen donor atoms forming substantially stable chelate rings, while diols behave as neutral biodentate ligands coordinating through oxygen. β-diketone ligands differ only in the substituents R 1 and R 2 (Fig. 1) while diols differ in the nature of the bond formed between second and third carbon atoms of the molecules. These small chemical and structural differences have been shown to produce significant variation of oscillator strength of certain absorption bands. Again, their relative perturbations of 4f-4f transition intensities are quite evident in Tλ-parameters estimated for different complexes. Attempts have been made to correlate between the intensity parameter Tλ and oscillator strengths determined from observed spectra of these complexes. The intensity analysis of absorption spectral bands have given sufficient evidence of some sort of interaction between Pr(III) and Nd(III) with π-electron density of the double bond found in butene-1,4-diol.

  4. Spectroscopy of new Sm(III) orange emitting phosphors of the type Na[Sm(SP)4], Na[Sm(WO)4] (where SP = C6H5S(O)2NP(O)(OCH3)2-; WO = CCl3C(O)NP(O)(OCH3)2-) and the polymeric materials obtained on their base

    Science.gov (United States)

    Cybińska, Joanna; Guzik, Małgorzata; Gerasymchuk, Yuriy; Trush, Victor A.; Lisiecki, Radosław; Legendziewicz, Janina

    2017-01-01

    Among a wide variety of solid state materials lanthanide beta-diketonates, their derivatives and polymeric materials based on them have become essential for advance technologies. Thus they are the subject of extensive spectroscopic studies. Using appropriate lanthanide chelates for the emission layer one can achieve electroluminescence covering the spectrum from blue to infrared. Moreover, compounds with proper chromophores can be the best way to excite and enhance the emission although the f-f transitions have forbidden character. Two types of new Sm(III) chelates; phosphoro and sulfono-derivatives of beta-diketones and polymeric materials on their base were obtained and characterized by the high resolution photoluminescence spectroscopy at 293, 77 and 4 K, as well as by luminescence decay times. Those new type of phosphors shows strong orange emission after excitation at 404 nm Sm(III) states and 280 nm ligand bands. Radiative transition probabilities were calculated from absorption spectra and Judd- Ofelt parameters evaluated. Effects of the temperature, rigidity of polymeric lattice and the energy of excitation on intensities of the Sm(III) fluorescence were studied. The paths of energy transfer are analysed and mechanism of this process is proposed.

  5. Experimental and Theoretical Studies on Biologically Active Lanthanide (III) Complexes

    Science.gov (United States)

    Kostova, I.; Trendafilova, N.; Georgieva, I.; Rastogi, V. K.; Kiefer, W.

    2008-11-01

    The complexation ability and the binding mode of the ligand coumarin-3-carboxylic acid (HCCA) to La(III), Ce(III), Nd(III), Sm(III), Gd(III) and Dy(III) lanthanide ions (Ln(III)) are elucidated at experimental and theoretical level. The complexes were characterized using elemental analysis, DTA and TGA data as well as 1H NMR and 13C NMR spectra. FTIR and Raman spectroscopic techniques as well as DFT quantum chemical calculations were used for characterization of the binding mode and the structures of lanthanide(III) complexes of HCCA. The metal—ligand binding mode is predicted through molecular modeling and energy estimation of different Ln—CCA structures using B3LYP/6-31G(d) method combined with a large quasi-relativistic effective core potential for lanthanide ion. The energies obtained predict bidentate coordination of CCA- to Ln(III) ions through the carbonylic oxygen and the carboxylic oxygen. Detailed vibrational analysis of HCCA, CCA- and Ln(III) complexes based on both calculated and experimental frequencies confirms the suggested metal—ligand binding mode. The natural bonding analysis predicts strongly ionic character of the Ln(III)-CCA bonding in the- complexes studied. With the relatively resistant tumor cell line K-562 we obtained very interesting in-vitro results which are in accordance with our previously published data concerning the activity of lanthanide(III) complexes with other coumarin derivatives.

  6. Complexes with Mercaptosuccinic Acid and Hydrazine as Ligands

    Directory of Open Access Journals (Sweden)

    S. Devipriya

    2013-01-01

    Full Text Available Reaction of hydrazine and mercaptosuccinic acid with metal ions forms\tcomplexes with general formula [Ln(N2H42CH2(COOCH(SH(COO1.5]·(H2O, where Ln = La(III, Pr(III, Nd(III, Sm(III, and Gd(III at pH 5. The complexes have been characterized by elemental analysis, IR and UV-visible spectroscopic, thermal and X-ray diffraction studies. The IR data reveal that the acid moiety in the complexes is present as dianion due to the deprotonation of COOH groups by lanthanides in these complexes, leaving –SH group unionized and hydrazine as bidental neutral ligand showing absorptions in the range of 945–948 cm−1. The thermoanalytical data evince that the complexes are stable up to 103°C and undergo complete decomposition in the range of 550–594°C resulting in metal oxides. SEM images of La2O3 and Gd2O3 residues show their nano sized clusters suggesting that the complexes may be used as precursors for nano La2O3 and Gd2O3, respectively. X-ray powder diffraction patterns show isomorphism among the complexes. The kinetic parameters of the decomposition of the complexes have been computed by Coats-Redfern equation.

  7. Synthesis, spectroscopic characterization, DNA cleavage and antibacterial studies of a novel tridentate Schiff base and some lanthanide(III) complexes

    Institute of Scientific and Technical Information of China (English)

    K. Mohanan; R. Aswathy; L.P. Nitha; Niecy Elsa Mathews; B. Sindhu Kumari

    2014-01-01

    A novel potential tridentate Schiff base was prepared by condensing equimolar quantities of 2-hydroxyacetophenone and 2-aminopyrimidine in methanol. This ligand was versatile in forming a series of complexes with lanthanide ions such as La(III), Pr(III), Nd(III), Sm(III), Gd(III), Dy(III) and Yb(III). The ligand and the metal complexes were characterized through elemental analysis, molar conductance, UV-Visible, IR, 1H NMR, and mass spectral studies. The spectral studies indicated that the ligand was coordinated to the metal ion in neutral tridentate fashion through the azomethine nitrogen, one of the nitrogen atoms in the pyrimidine ring and the phenolic oxygen without deprotonation. Thermal decomposition and luminescence property of lanthanum(III) complex were also examined. The X-ray diffraction patterns showed the crystalline nature of the ligand and its lanthanum(III) complex. The DNA cleavage studies of the ligand and the metal complexes were carried out and it was observed that the lanthanum(III) and neo-dymium(III) complexes cleaved the pUC19 DNA effectively. The ligand and the metal complexes were screened for their antibacte-rial activities. The metal complexes were found to be more potent bactericides than the ligand.

  8. Evaluation of Stability of Complexes of Inner Transition Metal Ions with 2-Oxo-1-pyrrolidine Acetamide and Role of Systematic Errors

    Directory of Open Access Journals (Sweden)

    Sangita Sharma

    2011-01-01

    Full Text Available BEST FIT models were used to study the complexation of inner transition metal ions like Y(III, La(III, Ce(III, Pr(III, Nd(III, Sm(III, Gd(III, Dy(III and Th(IV with 2-oxo-1-pyrrolidine acetamide at 30 °C in 10%, 20, 30, 40, 50% and 60% v/v dioxane-water mixture at 0.2 M ionic strength. Irving Rossotti titration method was used to get titration data. Calculations were carried out with PKAS and BEST Fortran IV computer programs. The expected species like L, LH+, ML, ML2 and ML(OH3, were obtained with SPEPLOT. Stability of complexes has increased with increasing the dioxane content. The observed change in stability can be explained on the basis of electrostatic effects, non electrostatic effects, solvating power of solvent mixture, interaction between ions and interaction of ions with solvents. Effect of systematic errors like effect of dissolved carbon dioxide, concentration of alkali, concentration of acid, concentration of ligand and concentration of metal have also been explained here.

  9. The specific sorption of Np(V) on the corundum (α-Al2O3) surface in the presence of trivalent lanthanides Eu(III) and Gd(III): A batch sorption and XAS study.

    Science.gov (United States)

    Virtanen, S; Bok, F; Ikeda-Ohno, A; Rossberg, A; Lützenkirchen, J; Rabung, T; Lehto, J; Huittinen, N

    2016-12-01

    The sorption of pentavalent neptunium, Np(V), on corundum (α-Al2O3) was investigated in the absence and presence of trivalent europium or gadolinium as a competing element under CO2-free conditions. The objective of this study was to investigate how a trivalent metal ion with a higher charge than that of the neptunyl(V) ion would affect the sorption of Np(V) when allowed to adsorb on the mineral surface before the addition of Np(V). Batch sorption experiments conducted as a function of pH (pH-edges) and as a function of Np(V) concentration (isotherms) in the absence and presence of 1×10(-5)M Eu(III) showed no sign of Eu being able to block Np sorption sites. Surface complexation modelling using the diffuse double layer model was applied to the batch data to obtain surface complexation constants for the formed Np(V) complexes on corundum. To account for potential changes occurring in the coordination environment of the neptunium ion in the presence of a trivalent lanthanide, X-ray absorption spectroscopy (XAS) measurements were carried out on the samples containing only Np(V) and Np(V)+Gd(III). The results reveal the presence of a bidentate Np(V) edge-sharing complex on the corundum surface in the absence of Gd(III), while the coordination environment of Np(V) on the corundum surface could be changed when Gd(III) is added to the sample before the sorption of Np(V). Copyright © 2016 Elsevier Inc. All rights reserved.

  10. An interplay between infrared multiphoton dissociation Fourier-transform ion cyclotron resonance mass spectrometry and density functional theory computations in the characterization of a tripodal quinolin-8-olate Gd(III) complex.

    Science.gov (United States)

    De Bonis, Margherita; Bianco, Giuliana; Amati, Mario; Belviso, Sandra; Cataldi, Tommaso R I; Lelj, Francesco

    2013-04-01

    A new hexadentate, tripodal 8-hydroxyquinoline based ligand (QH3) and its gadolinium(III) tris-chelated (GdQ) complex with hemicage structure was investigated by using high resolution Fourier-transform ion cyclotron resonance mass spectrometry (FTICRMS). The protonated adduct of the free ligand and its hemicage tripodal Gd(III) complex, [GdQ + H](+), were first observed in experiments of electrospray ionization (ESI) with a linear ion trap (LTQ) mass spectrometer and further investigated by using high resolution FTICRMS. Gas-phase dissociation of the protonated Gd(III) complex, by infrared multiphoton dissociation (IRMPD) FTICR MS, demonstrated a fragmentation pattern with six main product cluster ions labeled as [Fn](+) (n = 1 up to 6). These product ions suggest the elimination of 7-amino-alkyl or 7-alkyl chains of the hemicage moiety. High resolution MS conditions allowed the elucidation of the fragmentation pattern and product ion structures along with the determination, among the isotopic pattern of Gd, of the chemical compositions of closely related species, which differ in terms of hydrogen content. Among the Gd six naturally stable isotopes, (158)Gd is the most abundant, and its peak within each cluster was used as a reference for distinguishing each product ions. Computational DFT investigations were applied to give support to some hypothesis of fragmentation pathways, which could not have been easily justified on the basis of the experimental work. Furthermore, computational studies suggested the coordination geometry of the protonated parent complex and the five- and four-coordinated complexes, which derive from its fragmentation. Furthermore, experimental and computational evidences were collected about the octet spin state of the parent compound.

  11. Synthesis and characterization of Silica/polyvinyl imidazole/H2PO4-core-shell nanoparticles as recyclable adsorbent for efficient scavenging of Sm(III) and Dy(III) from water.

    Science.gov (United States)

    Ettehadi Gargari, Jafar; Sid Kalal, Hossein; Shakeri, Alireza; Khanchi, Alireza

    2017-11-01

    In this study, we used Silica/polyvinyl imidazole core-shell nanoparticles impregnated with sodium dihydrogen phosphate (SiO2/PVI/H2PO4(-) NPs) for adsorption of samarium and dysprosium ions from aqueous solutions. The effects of the pH, adsorbent dose, contact time, and initial concentration of the adsorbate on the Core-shell nanoparticles adsorption capacity have been studied. The pH value for maximum removal of Sm (III) and Dy (III) on the core-shell nanoparticles surface were found to be 4. The saturated capacity of SiO2/PVI/H2PO4(-) NPs was up to 160mg.g(-1) and 150mg.g(-1)at 25°C for Sm (III) and Dy (III) ions respectively. The obtained uptake data were analyzed by the Langmuir and Freundlich equations using a linearized correlation coefficient at room temperature. The Freundlich isotherm was found to fit well with the equilibrium data. The adsorption kinetics could be modeled by a pseudo-second-order rate expression. Thermodynamic investigation revealed the adsorption process of the studied ions is entropy driven. Furthermore, the performance of regeneration and reutilization were studied. The adsorbed Sm (III) and Dy (III) can be desorbed by 0.5mol/L HCl, with the desorption percentage of 90% for Sm (III) and Dy (III). After five adsorption-desorption cycles, the adsorption capacity shows a slight decrease (about 15%), implying that the SiO2/PVI/H2PO4(-) NPs can be used as an effective adsorbent for the removal and recovery of Sm(III) and Dy(III) from aqueous solution. The colloid stability of the SiO2/PVI/H2PO4(-) NPs was investigated by dynamic light scattering measurements. The SiO2/PVI/H2PO4(-) NPs are stable in adsorption media after five adsorption - desorption cycles. The high stability of SiO2/PVI/H2PO4(-) NPs can be attributed to steric stabilization by polyvinyl imidazole adsorbed on SiO2 nanoparticle surfaces. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. Fixation of carbon dioxide by macrocyclic lanthanide(III) complexes under neutral conditions producing self-assembled trimeric carbonato-bridged compounds with μ3-η2:η2:η2 bonding.

    Science.gov (United States)

    Bag, Pradip; Dutta, Supriya; Biswas, Papu; Maji, Swarup Kumar; Flörke, Ulrich; Nag, Kamalaksha

    2012-03-28

    A series of mononuclear lanthanide(III) complexes [Ln(LH(2))(H(2)O)(3)Cl](ClO(4))(2) (Ln = La, Nd, Sm, Eu, Gd, Tb, Lu) of the tetraiminodiphenolate macrocyclic ligand (LH(2)) in 95 : 5 (v/v) methanol-water solution fix atmospheric carbon dioxide to produce the carbonato-bridged trinuclear complexes [{Ln(LH(2))(H(2)O)Cl}(3)(μ(3)-CO(3))](ClO(4))(4)·nH(2)O. Under similar conditions, the mononuclear Y(III) complex forms the dimeric compound [{Y(LH(2))(H(2)O)Cl}(μ(2)-CO(3)){Y(LH(2))(H(2)O)(2)}](ClO(4))(3)·4H(2)O. These complexes have been characterized by their IR and NMR ((1)H, (13)C) spectra. The X-ray crystal structures have been determined for the trinuclear carbonato-bridged compounds of Nd(III), Gd(III) and Tb(III) and the dinuclear compound of Y(III). In all cases, each of the metal centers are 8-coordinate involving two imine nitrogens and two phenolate oxygens of the macrocyclic ligand (LH(2)) whose two other imines are protonated and intramolecularly hydrogen-bonded with the phenolate oxygens. The oxygen atoms of the carbonate anion in the trinuclear complexes are bonded to the metal ions in tris-bidentate μ(3)-η(2):η(2):η(2) fashion, while they are in bis-bidentate μ(2)-η(2):η(2) mode in the Y(III) complex. The magnetic properties of the Gd(III) complex have been studied over the temperature range 2 to 300 K and the magnetic susceptibility data indicate a very weak antiferromagnetic exchange interaction (J = -0.042 cm(-1)) between the Gd(III) centers (S = 7/2) in the metal triangle through the carbonate bridge. The luminescence spectral behaviors of the complexes of Sm(III), Eu(III), and Tb(III) have been studied. The ligand LH(2) acts as a sensitizer for the metal ions in an acetonitrile-toluene glassy matrix (at 77 K) and luminescence intensities of the complexes decrease in the order Eu(3+) > Sm(3+) > Tb(3+).

  13. Calculation and Comparison of Energy Interaction and Intensity Parameters for the Interaction of Nd(III with DL-Valine, DL-Alanine and β-Alanine in Presence and Absence of Ca2+/Zn2+ in Aqueous and Different Aquated Organic Solvents Using 4f-4f Transition Spectra as Probe

    Directory of Open Access Journals (Sweden)

    H. Debecca Devi

    2009-01-01

    Full Text Available Absorption difference and comparative absorption spectrophotometric studies involving 4f-4f transitions of Nd(III and different amino acids: DL-valine, DL-alanine, and β-alanine in presence and absence of Ca(II and Zn(II in aqueous and different aquated organic solvents have been carried out. Variations in the spectral energy parameters: Slater-Condon (FK factor, Racah (EK, Lande factor (ξ4f, nephelauxetic ratio (β, bonding (b1/2, percentage covalency (δ are calculated to explore the mode of interaction of Nd(III with different amino acids: DL-valine, DL-alanine, and β-alanine. The values of experimentally calculated oscillator strength (P and computed values of Judd-Ofelt electric dipole intensity parameters, Tλ (λ = 2,4,6, are also determined for different 4f-4f transitions. The variation in the values of P and Tλ parameters explicitly shows the relative sensitivities of the 4f-4f transitions as well as the specific correlation between relative intensities, ligand structures, and nature of Nd(III-ligand interaction.

  14. Heterometallic octanuclear RE(III)3Ni(II)5 (RE = Dy(III), Gd(III) and Y(III)) clusters with slow magnetic relaxation for the dysprosium derivative.

    Science.gov (United States)

    Wang, Huiyu; Ke, Hongshan; Lin, Shuang-Yan; Guo, Yang; Zhao, Lang; Tang, Jinkui; Li, Yun-Hui

    2013-04-21

    Reactions of rare earth benzoate and nickel perchlorate with a Schiff-base ligand, 2-([(2-hydroxyphenyl)imino]methyl) phenol (H2L), in the presence of triethylamine yielded three heterobimetallic octanuclear clusters of general formula [RE3Ni5L5(PhCOO)3(μ3-OH)5(μ3-OCH3)(CH3OH)4(H2O)]·xCH3OH·yH2O (RE = Dy(III), x = 4, y = 4 (1), RE = Gd(III), x = 5, y = 4 (2), RE = Y(III), x = 5, y = 3 (3)). Single-crystal X-ray diffraction reveals that the metal core of each cluster consists of two distorted [RE2Ni2O4] cubane-like moieties and a heterobimetallic triangular [RE2NiO2] unit, with RE ions arranged in a typical triangular fashion. Variable-temperature solid state magnetic susceptibilities of these complexes were measured in the temperature range 2-300 K and the results indicate that an overall ferromagnetic interaction among the metal ions is operative for compounds 2 and 3. Under zero external field, the Dy3Ni5 compound shows a frequency dependence of the out-of-phase (χ'') signals, which indicates slow relaxation of the magnetization.

  15. A general method for preparing lanthanide oxide nanoparticles via thermal decomposition of lanthanide(III) complexes with 1-hydroxy-2-naphthoic acid and hydrazine ligands

    Science.gov (United States)

    Parimalagandhi, Karuppannan; Premkumar, Thathan; Vairam, Sundararajan

    2016-09-01

    Six new lanthanide(III) complexes (i.e., [Ln(L)2(NA)1.5]·3H2O, where Ln=La(III), Pr(III), Nd(III), Sm(III), Gd(III), and Ce(III) and L and NA indicate N2H4 and C10H6(1-O)(2-COO), respectively) with 1-hydroxy-2-naphthoic acid [C10H6(1-O)(2-COOH)] and hydrazine (N2H4) as co-ligands were characterized by elemental, FTIR, UV-visible, and XRD techniques. In the FT-IR spectra, the N-N stretching frequency in the range of 981-949 cm-1 demonstrates evidence of the presence of coordinated N2H4, indicating the bidentate bridging nature of hydrazine in the complexes. These complexes show symmetric and asymmetric COO- stretching from 1444 to 1441 cm-1 and 1582 to 1557 cm-1, respectively, indicating bidentate coordination. TG-DTA studies revealed that the compounds underwent endothermic dehydration from 98 to 110 °C. This was followed by the exothermic decomposition of oxalate intermediates to yield the respective metal oxides as the end products. From SEM images, the average size of the metal oxide particles prepared by thermal decomposition of the complexes was determined to be 39-42 nm. The powder X-ray and SEM coupled with energy dispersive X-ray (EDX) studies revealed the presence of the respective nano-sized metal oxides. The kinetic parameters of the decomposition of the complexes were calculated using the Coats-Redfern equation.

  16. Synthesis and Spectral Characterization of Lanthanide Complexes Derived from 2-[(4-Bromo-2,6-Dichloro-Phenylimino-Methyl]-4,6-Diiodo-Phenol

    Directory of Open Access Journals (Sweden)

    V. R. Rajewar

    2014-12-01

    Full Text Available The solid complexes of La(III, Pr (III, Tb(III ,Sm(III and Nd(III were prepared from bidentate Schiff base, 2-[(4-bromo-2,6-dichloro-phenylimino-methyl]-4,6-diiodo-phenol. The Schiff base ligand was synthesized from 3,5 diiodosalicylaldehyde and 4-bromo-2,6-dichlorobenzenamine . These metal complexes were characterized by molar conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, FTIR, 1H-NMR and UV-Vis. The analytical data of these metal complexes showed metal:ligand ratio of 1:2 La(III, Pr (III, Tb(III ,Sm(III and 1:1 for Nd(III complexes. The physico-chemical study supports the presence of octahedral geometry around La(III, Pr (III, Tb(III ,Sm(III and Nd(III ions. The IR spectral data reveal that the ligand behaves as bidentate with ON donor atom sequence towards central metal ion. The molar conductance values of metal complexes suggest their electrolyte nature except Nd(III complex. The X-ray diffraction data suggest monoclinic crystal system for Pr (III, Nd (III complexes. Thermal behavior (TG/DTA shows breakdown of complexes.

  17. Metal-ligand interaction of lanthanides with coumarin derivatives. Part I. Complexation of 3-(1-aminoethylidene)-2H-chromene-2,4(3H)-dione with La(III), Ce(III), Nd(III) and Ho(III).

    Science.gov (United States)

    Swiatek, Mirosława; Kufelnicki, Aleksander

    2012-01-01

    Solutions of lanthanum(III), cerium(III), neodymium(III) and holmium(III) nitrates with 3-(1-aminoethylidene)-2H-chromene-2,4(3H)-dione (1) in 10% v/v dioxane-water medium were used. Coordination modes of 1 with the selected lanthanides have been examined. Hydroxo-complexes with deprotonated water molecules from the inner coordination sphere have been stated in basic medium. Stability constants of the forming complex species were determined by potentiometric titrations using Superquad and Hyperquad2003 programs. The most stable complexes are formed with La(III). The UV-Vis spectra of the Nd(III)-1 system confirmed the L:M = 1:1 stoichiometry evaluated potentiometrically.

  18. A Comparison of Apparent Diffusion Coefficients Measured in Compacted Kunigel V1 Bentonite with those Calculated from Batch Sorption Measurements and D{sub e} (HTO) Data: A Case Study for Cs(I), Ni(II), Sm(III), Am(III), Zr(IV) and Np(V)

    Energy Technology Data Exchange (ETDEWEB)

    Bradbury, M.; Baeyens, B

    2003-02-01

    Recently, a bentonite sorption data base, comprising values taken from batch sorption data, was developed for a performance assessment study for high-level waste and spent fuel (Entsorgungsnachweis). Thus distribution coefficients (K{sub d}) determined on dispersed systems were used to calculate apparent diffusion coefficients (D{sub a}) subsequently applied in diffusive transport calculations for the highly compacted system. Whenever such a procedure is adopted, questions invariably arise as to whether this is conservative or not. On the occasions when K{sub d} values have been extracted from (mainly) indiffusion experiments and compared with those obtained from batch tests, apparent discrepancies have been found. In the majority of cases the batch values are larger, sometimes significantly. Hypotheses from 'surface diffusion' to 'double layer pore constrictivity effects' have been proposed to explain the inconsistencies. However, although such discrepancies have been reported periodically over the past twenty years or so, and have become generally accepted facts of life, there are surprisingly few quantitative studies directly dealing with this issue. Further, two other points are worthy of mention. The first is that a diffusion model (including the associated assumptions) is needed in order to deduce K{sub d} values from diffusion measurements. Thus the sorption values calculated are model dependent. The second is that too little attention has been paid to the potential effects of water chemistry, i.e. a comparison between sorption values is only valid when the water chemistry in the batch tests is the same as, or very close to, the porewater chemistry in the intact material. In practice, this condition is difficult to achieve because of the uncertainties concerning the latter. This report describes a study in which K{sub d} values for Cs(I), Ni(II), Sm(III), Am(III), Zr(IV) and Np(V) were calculated from in-diffusion data published in the

  19. Homodinuclear lanthanide complexes of phenylthiopropionic acid: Synthesis, characterization, cytotoxicity, DNA cleavage, and antimicrobial activity

    Science.gov (United States)

    Shiju, C.; Arish, D.; Kumaresan, S.

    2013-03-01

    Lanthanide complexes of La(III), Pr(III), Nd(III), Sm(III), and Ho(III) with phenylthiopropionic acid were synthesized and characterized by elemental analysis, mass, IR, electronic spectra, molar conductance, TGA, and powder XRD. The results show that the lanthanide complexes are homodinuclear in nature. The two lanthanide ions are bridged by eight oxygen atoms from four carboxylate groups. Thermal decomposition profiles are consistent with the proposed formulations. Powder XRD studies show that all the complexes are amorphous in nature. Antimicrobial studies indicate that these complexes exhibit more activity than the ligand itself. The DNA cleavage activity of the ligand and its complexes were assayed on Escherichia coli DNA using gel electrophoresis in the presence of H2O2. The result shows that the Pr(III) and Nd(III) complexes have completely cleaved the DNA. The anticancer activities of the complexes have also been studied towards human cervical cancer cell line (HeLa) and colon cancer cells (HCT116) and it was found that the La(III) and Nd(III) complexes are more active than the corresponding Pr(III), Sm(III), Ho(III) complexes, and the free ligand on both the cancer cells.

  20. Homodinuclear lanthanide complexes of phenylthiopropionic acid: synthesis, characterization, cytotoxicity, DNA cleavage, and antimicrobial activity.

    Science.gov (United States)

    Shiju, C; Arish, D; Kumaresan, S

    2013-03-15

    Lanthanide complexes of La(III), Pr(III), Nd(III), Sm(III), and Ho(III) with phenylthiopropionic acid were synthesized and characterized by elemental analysis, mass, IR, electronic spectra, molar conductance, TGA, and powder XRD. The results show that the lanthanide complexes are homodinuclear in nature. The two lanthanide ions are bridged by eight oxygen atoms from four carboxylate groups. Thermal decomposition profiles are consistent with the proposed formulations. Powder XRD studies show that all the complexes are amorphous in nature. Antimicrobial studies indicate that these complexes exhibit more activity than the ligand itself. The DNA cleavage activity of the ligand and its complexes were assayed on Escherichia coli DNA using gel electrophoresis in the presence of H(2)O(2). The result shows that the Pr(III) and Nd(III) complexes have completely cleaved the DNA. The anticancer activities of the complexes have also been studied towards human cervical cancer cell line (HeLa) and colon cancer cells (HCT116) and it was found that the La(III) and Nd(III) complexes are more active than the corresponding Pr(III), Sm(III), Ho(III) complexes, and the free ligand on both the cancer cells.

  1. Separation of Y(dcta– complexes from Nd(dcta– and Sm(dcta– complexes on polyacrylate anion-exchangers

    Directory of Open Access Journals (Sweden)

    DOROTA KOLODYNSKA

    2003-03-01

    Full Text Available The formation of anion rare earth element complexes with aminopolycarboxylic acids gives new possibilities for the separation of these elements on anion-exchangers. The higher affinity of the Nd(dcta- and Sm(dcta- complexes for the anion-exchangers compared to Y(dcta- complexes indicates the possibility of yttrium purification as a macrocomponent from the former by frontal analysis. The weakly basic polyacrylate gel anion-exchanger Amberlite IRA 68 was more effective in the purification of Y(III from Nd(III and Sm(III complexes with DCTA than the strongly basic anion-exchangers of this type.

  2. Evaluation of Alkali Bromide Salts for Potential Pyrochemical Applications

    Energy Technology Data Exchange (ETDEWEB)

    Prabhat K. Tripathy; Steven D. Herrmann; Guy L. Fredrickson; Tedd E. Lister; Toni Y. Gutknecht

    2013-10-01

    Transient techniques were employed to study the electrochemical behavior, reduction mechanism and transport properties of REBr3 (RE - La, Nd and Gd) in pure LiBr, LiBr-KBr (eutectic) and LiBr-KBr-CsBr (eutectic) melts. Gd(III) showed a reversible single step soluble-insoluble exchange phenomenon in LiBr melt at 973K. Although La (III), Nd(III) and Gd(III) ions showed reversible behavior in eutectic LiBr-KBr melts, these ions showed a combination of temperature dependent reversible and pseudo-reversible behavior. While both La(III) and Gd(III) showed one step reduction, the reduction of Nd(III) was observed to be a two step process. La metal could be electrodeposited from the ternary electrolyte at a temperature of 673K. Various electrochemical measurements suggest that both binary and ternary bromide melts can potentially be used to electrodeposit high purity RE metals at comparatively lower operating temperatures.

  3. Synthesis and Structural Investigation of New Bio-Relevant Complexes of Lanthanides with 5-Hydroxyflavone: DNA Binding and Protein Interaction Studies

    Directory of Open Access Journals (Sweden)

    Alexandra-Cristina Munteanu

    2016-12-01

    Full Text Available In the present work, we attempted to develop new metal coordination complexes of the natural flavonoid 5-hydroxyflavone with Sm(III, Eu(III, Gd(III, Tb(III. The resultant hydroxo complexes have been characterized by a variety of spectroscopic techniques, including fluorescence, FT-IR, UV-Vis, EPR and mass spectral studies. The general chemical formula of the complexes is [Ln(C15H9O33(OH2(H2Ox]·nH2O, where Ln is the lanthanide cation and x = 0 for Sm(III, x = 1 for Eu(III, Gd(III, Tb(III and n = 0 for Sm(III, Gd(III, Tb(III, n = 1 for Eu(III, respectively. The proposed structures of the complexes were optimized by DFT calculations. Theoretical calculations and experimental determinations sustain the proposed structures of the hydroxo complexes, with two molecules of 5-hydroxyflavone acting as monoanionic bidentate chelate ligands. The interaction of the complexes with calf thymus DNA has been explored by fluorescence titration and UV-Vis absorption binding studies, and revealed that the synthesized complexes interact with DNA with binding constants (Kb ~ 104. Human serum albumin (HSA and transferrin (Tf binding studies have also been performed by fluorescence titration techniques (fluorescence quenching studies, synchronous fluorescence spectra. The apparent association constants (Ka and thermodynamic parameters have been calculated from the fluorescence quenching experiment at 299 K, 308 K, and 318 K. The quenching curves indicate that the complexes bind to HSA with smaller affinity than the ligand, but to Tf with higher binding affinities than the ligand.

  4. Octanuclear [Ni(II)₄Ln(III)₄] complexes. Synthesis, crystal structures and magnetocaloric properties.

    Science.gov (United States)

    Pasatoiu, Traian D; Ghirri, Alberto; Madalan, Augustin M; Affronte, Marco; Andruh, Marius

    2014-06-28

    Two original heterooctanuclear [Ni(II)4Ln(III)4] complexes (Ln(III) = Sm(III), Gd(III)) have been obtained starting from the [Ni(II)(valpn)(H2O)2] mononuclear precursor [H2valpn = 1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol)] and the corresponding lanthanide nitrates, in the presence of azide anions, through slow capture of atmospheric CO2. Three weak and competitive exchange interactions, J(GdGd), J(GdNi), J(NiNi), make the ground state of this magnetic system degenerate at cryogenic temperature and zero field. This, along with the high spin of Gd(III), lead to a significant magnetocaloric effect spread in the temperature range 1 to 20 K (ΔSm[0-7 T, 3.5 K] = 19 J kg(-1) K(-1)).

  5. Carbonato-bridged Ni(II)2Ln(III)2 (Ln(III) = Gd(III), Tb(III), Dy(III)) complexes generated by atmospheric CO2 fixation and their single-molecule-magnet behavior: [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH or H2O)Ln(III)(NO3)}2]·solvent [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato].

    Science.gov (United States)

    Sakamoto, Soichiro; Fujinami, Takeshi; Nishi, Koshiro; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Re, Nazzareno

    2013-06-17

    Atmospheric CO2 fixation of [Ni(II)(3-MeOsaltn)(H2O)2]·2.5H2O [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato], Ln(III)(NO3)3·6H2O, and triethylamine occurred in methanol/acetone, giving a first series of carbonato-bridged Ni(II)2Ln(III)2 complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH)Ln(III)(NO3)}2] (1Gd, 1Tb, and 1Dy). When the reaction was carried out in acetonitrile/water, it gave a second series of complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(H2O)Ln(III)(NO3)}2]·2CH3CN·2H2O (2Gd, 2Tb, and 2Dy). For both series, each Ni(II)2Ln(III)2 structure can be described as two di-μ-phenoxo-bridged Ni(II)Ln(III) binuclear units bridged by two carbonato CO3(2-) units to form a carbonato-bridged (μ4-CO3)2{Ni(II)2Ln(III)2} structure. The high-spin Ni(II) ion has octahedral coordination geometry, and the Ln(III) ion is coordinated by O9 donor atoms from Ni(II)(3-MeOsaltn), bidentate NO3(-), and one and two oxygen atoms of two CO3(2-) ions. The NO3(-) ion for the first series roughly lie on Ln-O(methoxy) bonds and are tilted toward the outside, while for the second series, the two oxygen atoms roughly lie on one of the Ln-O(phenoxy) bonds due to the intramolecular hydrogen bond. The temperature-dependent magnetic susceptibilities indicated a ferromagnetic interaction between the Ni(II) and Ln(III) ions (Ln(III) = Gd(III), Tb(III), Dy(III)) for all of the complexes, with a distinctly different magnetic behavior between the two series in the lowest-temperature region due to the Ln(III)-Ln(III) magnetic interaction and/or different magnetic anisotropies of the Tb(III) or Dy(III) ion. Alternating-current susceptibility measurements under the 0 and 1000 Oe direct-current (dc) bias fields showed no magnetic relaxation for the Ni(II)2Gd(III)2 complexes but exhibited an out-of-phase signal for Ni(II)2Tb(III)2 and Ni(II)2Dy(III)2, indicative of slow relaxation of magnetization. The energy barriers, Δ/kB, for the spin flipping were estimated from the Arrhenius

  6. Controllable formation of heterotrimetallic coordination compounds: systematically incorporating lanthanide and alkali metal ions into the manganese 12-metallacrown-4 framework.

    Science.gov (United States)

    Azar, Michael R; Boron, Thaddeus T; Lutter, Jacob C; Daly, Connor I; Zegalia, Kelcie A; Nimthong, Ruthairat; Ferrence, Gregory M; Zeller, Matthias; Kampf, Jeff W; Pecoraro, Vincent L; Zaleski, Curtis M

    2014-02-01

    The inclusion of Ln(III) ions into the 12-MC-4 framework generates the first heterotrimetallic complexes of this molecular class. The controllable and deliberate preparations of these compounds are demonstrated through 12 crystal structures of the Ln(III)M(I)(OAc)4[12-MCMn(III)(N)shi-4](H2O)4·6DMF complex, where OAc(-) is acetate, shi(3-) is salicylhydroximate, and DMF is N,N-dimethylformamide. Compounds 1-12 have M(I) as Na(I), and Ln(III) can be Pr(III) (1), Nd(III) (2), Sm(III) (3), Eu(III) (4), Gd(III) (5), Tb(III) (6), Dy(III) (7), Ho(III) (8), Er(III) (9), Tm(III) (10), Yb(III) (11), and Y(III) (12). An example with M(I) = K(I) and Ln(III) = Dy(III) is also reported (Dy(III)K(OAc)4[12-MCMn(III)(N)shi-4](DMF)4·DMF (14)). When La(III), Ce(III), or Lu(III) is used as the Ln(III) ions to prepare the Ln(III)Na(I)(OAc)4[12-MCMn(III)(N)shi-4] complex, the compound Na2(OAc)2[12-MCMn(III)(N)shi-4](DMF)6·2DMF·1.60H2O (13) results. For compounds 1-12, the identity of the Ln(III) ion affects the 12-MCMn(III)(N)shi-4 framework as the largest Ln(III), Pr(III), causes an expansion of the 12-MCMn(III)(N)shi-4 framework as demonstrated by the largest metallacrown cavity radius (0.58 Å for 1 to 0.54 Å for 11), and the Pr(III) causes the 12-MCMn(III)(N)shi-4 framework to be the most domed structure as evident in the largest average angle about the axial coordination of the ring Mn(III) ions (103.95° for 1 to 101.69° for 11). For 14, the substitution of K(I) for Na(I) does not significantly affect the 12-MCMn(III)(N)shi-4 framework as many of the structural parameters such as the metallacrown cavity radius (0.56 Å) fall within the range of compounds 1-12. However, the use of the larger K(I) ion does cause the 12-MCMn(III)(N)shi-4 framework to become more planar as evident in a smaller average angle about the axial coordination of the ring Mn(III) ions (101.35°) compared to the analogous Dy(III)/Na(I) (7) complex (102.40°). In addition to broadening the range of

  7. Syntheses, structures, and magnetic properties of acetato- and diphenolato-bridged 3d-4f binuclear complexes [M(3-MeOsaltn)(MeOH)x(ac)Ln(hfac)2] (M = Zn(II), Cu(II), Ni(II), Co(II); Ln = La(III), Gd(III), Tb(III), Dy(III); 3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato; ac = acetato; hfac = hexafluoroacetylacetonato; x = 0 or 1).

    Science.gov (United States)

    Towatari, Masaaki; Nishi, Koshiro; Fujinami, Takeshi; Matsumoto, Naohide; Sunatsuki, Yukinari; Kojima, Masaaki; Mochida, Naotaka; Ishida, Takayuki; Re, Nazzareno; Mrozinski, Jerzy

    2013-05-20

    A series of 3d-4f binuclear complexes, [M(3-MeOsaltn)(MeOH)x(ac)Ln(hfac)2] (x = 0 for M = Cu(II), Zn(II); x = 1 for M = Co(II), Ni(II); Ln = Gd(III), Tb(III), Dy(III), La(III)), have been synthesized and characterized, where 3-MeOsaltn, ac, and hfac denote N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, acetato, and hexafluoroacetylacetonato, respectively. The X-ray analyses demonstrated that all the complexes have an acetato- and diphenolato-bridged M(II)-Ln(III) binuclear structure. The Cu(II)-Ln(III) and Zn(II)-Ln(III) complexes are crystallized in an isomorphous triclinic space group P1, where the Cu(II) or Zn(II) ion has square pyramidal coordination geometry with N2O2 donor atoms of 3-MeOsaltn at the equatorial coordination sites and one oxygen atom of the bridging acetato ion at the axial site. The Co(II)-Ln(III) and Ni(II)-Ln(III) complexes are crystallized in an isomorphous monoclinic space group P2(1)/c, where the Co(II) or Ni(II) ion at the high-spin state has an octahedral coordination environment with N2O2 donor atoms of 3-MeOsaltn at the equatorial sites, and one oxygen atom of the bridged acetato and a methanol oxygen atom at the two axial sites. Each Ln(III) ion for all the complexes is coordinated by four oxygen atoms of two phenolato and two methoxy oxygen atoms of "ligand-complex" M(3-MeOsaltn), four oxygen atoms of two hfac(-), and one oxygen atom of the bridging acetato ion; thus, the coordination number is nine. The temperature dependent magnetic susceptibilities from 1.9 to 300 K and the field-dependent magnetization up to 5 T at 1.9 K were measured. Due to the important orbital contributions of the Ln(III) (Tb(III), Dy(III)) and to a lesser extent the M(II) (Ni(II), Co(II)) components, the magnetic interaction between M(II) and Ln(III) ions were investigated by an empirical approach based on a comparison of the magnetic properties of the M(II)-Ln(III), Zn(II)-Ln(III), and M(II)-La(III) complexes. The differences of χ(M)T and M

  8. Two New Octadecanuclear Copper(II)-Lanthanide(III) Clusters Encapsulating μ9-NO -3 Anions. Synthesis, Structures, and Magnetic Properties of [Cu 12Ln6( μ3-OH) 24(C 5H 5NCH 2CO 2) 12(H 2O) 18( μ9-NO 3)](PF 6) 10(NO 3) 7·12H 2O ( LnIII=Sm III or Gd III)

    Science.gov (United States)

    Yang, Yang-Yi; Chen, Xiao-Ming; Ng, Seik Weng

    2001-11-01

    Two new octadecanuclear clusters [Cu12Ln6(μ3-OH)24(C5H5NCH2CO2)12(H2O)18(μ9-NO3)](PF6)10(NO3)7·12H2O [LnIII=SmIII (1) or GdIII (2)] have been synthesized and characterized by X-ray diffraction. They are isomorphous and crystallize in the triclinic space group Poverline1 with Z=1. The cell dimensions of 1 are a=17.366(1), b=17.790(1), and c=19.002(1) Å, α=117.279(1), β=91.763(1), and γ=111.585(1)°. In the cluster, 6 SmIII atoms are positioned at the vertices of an octahedron, while 12 CuII atoms are at the midpoints of the edges of the octahedron. The CuII-SmIII metal framework is interconnected by the 24 similar μ3-OH- groups, each bridging one SmIII and two CuII atoms. The octahedral cage encapsulates an unusual μ9-NO-3 anion with each oxygen atom coordinated to three CuII atoms. The 12 carboxylate ligands act as μ2-carboxylate-O,O‧ bridges, each linking a SmIII and a CuII atom. The PF-6 counteranion plays an important role in crystallization of the two complexes.

  9. Rare earth complexes with a novel ligand N-(naphthalen-2-yl)- N-phenyl-2-(quinolin-8-yloxy)acetamide: Preparation and spectroscopic studies

    Science.gov (United States)

    Wu, Wei-Na; Tang, Ning; Yan, Lan

    2008-12-01

    Six complexes of rare earth nitrates (Ln = La, Sm, Eu, Gd, Tb, Dy) with a new amide type ligand, N-(naphthalen-2-yl)- N-phenyl-2-(quinolin-8-yloxy)acetamide (L) have been prepared and characterized by elemental analysis, conductivity measurements, IR and and 1H NMR spectra. Under excitation, Eu(III) and Sm(III) complexes exhibited strong red emissions. And the luminescence intensity of Sm(III) complex is higher than that of Eu(III) complex. Thus the Eu(III) and Sm(III) complexes are the potential light conversion agent. However, the Tb(III) and Dy(III) complexes cannot exhibit characteristic emissions of terbium and dysprosium ions, respectively. The results of phosphorescence spectrum show that the triplet-state energy level of the ligand matches better to the resonance level of Eu(III) than Tb(III) ion. In addition, the luminescence of the Eu(III) complex is also relatively strong in highly diluted tetrahydrofuran solution (2 × 10 -4 mol/L) compared with the powder. This is not only due to the solvate effects but also to the changes of the structure of the Eu(III) complex after being dissolved into the solvents. Furthermore, owing to the co-luminescence effect, the proper La(III) or Gd(III) doped Eu(III) complexes show stronger luminescence than the pure Eu(III) complex.

  10. Synthesis, Characterization, and Physicochemical Studies of Mixed Ligand Complexes of Inner Transition Metals with Lansoprazole and Cytosine

    Directory of Open Access Journals (Sweden)

    Sarika Verma

    2013-01-01

    Full Text Available Few complexes of inner transition metals [Th(IV, Ce(IV, Nd(III, Gd(III] have been synthesized by reacting their metal salts with lansoprazole, 2-([3-methyl-4-(2,2,2-trifluoroethoxypyridin-2-yl]methylsulfinyl-1H-benzoimidazole and cytosine. All the complexes were synthesized in ethanolic medium. The yield percentage rangs from 80 to 90%. The complexes are coloured solids. The complexes were characterized through elemental analyses, conductance measurements, and spectroscopic methods (FT IR, FAB Mass, 1H NMR and UV. An IR spectrum indicates that the ligand behaves as bidentate ligands. The metal complexes have been screened for their antifungal activity towards Aspergillus niger fungi. The interaction of inner transition metals with lansoprazole, in presence of cytosine, has also been investigated potentiometrically at two different temperatures 26±1°C and 36±1°C and at 0.1 M (KNO3 ionic strength. The stability constants of ternary complexes indicate the stability order as Th(IV < Ce(IV < Gd(III < Nd(III. logK values obtained are positive and suggest greater stabilization of ternary complexes. The values of thermodynamic parameters (free energy (ΔG, enthalpy (ΔH, and entropy (ΔS are also calculated.

  11. Novel gadolinium poly(vinyl chloride) membrane sensor based on a new S-N Schiff's base

    Energy Technology Data Exchange (ETDEWEB)

    Ganjali, Mohammad Reza; Emami, Mahdi; Rezapour, Morteza; Shamsipur, Mojtaba; Maddah, Bozorgmehr; Salavati-Niasari, Masoud; Hosseini, Morteza; Talebpoui, Zahra

    2003-10-24

    In this work, a novel gadolinium membrane sensor based on new S-N Schiff',s base (2-[{l_brace}3-[(2-sulfanylphenyl)imino)-1-methylbutylideneamino]phenyl hydrosulfide (SMPH) is presented. The sensor displays a linear dynamic range between 1.0x10{sup -1} and 1.0x10{sup -5} M, with a nice Nernstian slope of 19.8{+-}0.3 mV per decade and a detection limit of 3.0x10{sup -6} M. The best performance was obtained with a membrane composition of 33% poly(vinyl chloride), 61% benzyl acetate, 2% sodium tetraphenyl borate and 5% SMPH. The potentiometric response of the sensor is independent of the pH of the solution in the pH range of 4.0-8.0. The sensor possesses the advantages of short conditioning time, very fast response time, and especially, very good selectivity towards a large number of cations, such as Sm(III), Ce(III), La(III), Cu(II), Pb(II) and Hg(II). The electrode can be used for at least 9 weeks without any considerable divergence in the potentials. It was used as an indicator electrode in potentiometric titration of Gd(III) ions with EDTA, and recovery of Gd(III) from various binary mixtures. The electrode was also applied to the determination of Gd(III) in a urine sample.

  12. Polymeric chains, hydrogen bonds and magnetism in Nd(III) adipates

    Energy Technology Data Exchange (ETDEWEB)

    Echeverria, G. [LANADI e IFLP, Universidad Nacional de La Plata, CC67, 1900 La Plata (Argentina) and Departamento de Fisica, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC67, 1900 La Plata (Argentina)]. E-mail: geche@fisica.unlp.edu.ar; Punte, G. [LANADI e IFLP, Universidad Nacional de La Plata, CC67, 1900 La Plata (Argentina); Departamento de Fisica, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC67, 1900 La Plata (Argentina); Sives, F. [Departamento de Fisica, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC67, 1900 La Plata (Argentina); Brusau, E.V. [Area de Quimica General e Inorganica ' Dr. G. F. Puelles' , Facultad de Quimica, Bioquimica y Farmacia, Universidad Nacional de San Luis, Chacabuco y Pedernera, 5700 San Luis (Argentina); Pedregosa, J.C. [Area de Quimica General e Inorganica ' Dr. G. F. Puelles' , Facultad de Quimica, Bioquimica y Farmacia, Universidad Nacional de San Luis, Chacabuco y Pedernera, 5700 San Luis (Argentina); Narda, G.E. [Area de Quimica General e Inorganica ' Dr. G. F. Puelles' , Facultad de Quimica, Bioquimica y Farmacia, Universidad Nacional de San Luis, Chacabuco y Pedernera, 5700 San Luis (Argentina); Ellena, J. [Instituto de Fisica Sao Carlos, Universidade de Sao Paulo, CP 369, CEP 13560-970, Sao Carlos, SP (Brazil)

    2004-12-31

    An AC susceptibility study of [Nd{sub 2}(O{sub 2}C(CH{sub 2}){sub 4}CO{sub 2}){sub 3}(H{sub 2}O){sub 2}] (1) obtained from a solution at ambient conditions was performed in the range 14-320K. An ordering transition, T{sub C}=280(2)K, not related to a structural phase transition, a ferromagnetic like Curie-Weiss behavior above T{sub C}, an antiferromagnetic like dependence of {chi}'-1 at the lowest temperatures and a non-linear thermal dependence of {chi}'-1 in the in-between region have been observed. Samples prepared by hydration of 1 during different periods showed enhancement of the observed features. Links between water content, crystal structure and magnetic response are discussed.

  13. Non-stoichiometry and optical spectra of Nd(III) substituted PbTiO3

    NARCIS (Netherlands)

    Bouwma, J.; Heilbron, M.A.

    1976-01-01

    The non-stoichiometry of the perovskite (ABO3)-type phase in the system PbO---TiO2---Nd2O3 has been studied. Monophasic compounds of composition Pb1−αxNdxTiO3+x(1.5−α) with x 0.21 and 0.09 α 1.5 were prepared. The ferroelectric Curie temperature (Tc) shows a decrease of 18.5 K/at% Nd with increas

  14. Visible and NIR photoluminescence properties of a series of novel lanthanide-organic coordination polymers based on hydroxyquinoline-carboxylate ligands.

    Science.gov (United States)

    Gai, Yan-Li; Xiong, Ke-Cai; Chen, Lian; Bu, Yang; Li, Xing-Jun; Jiang, Fei-Long; Hong, Mao-Chun

    2012-12-17

    A series of novel two-dimensional (2D) lanthanide coordination polymers with 4-hydroxyquinoline-2-carboxylate (H(2)hqc) ligands, [Ln(Hhqc)(3)(H(2)O)](n)·3nH(2)O (Ln = Eu (1), Tb (2), Sm (3), Nd (4), and Gd (5)) and [Ln(Hhqc)(ox)(H(2)O)(2)](n) (Ln = Eu (6), Tb (7), Sm (8), Tm (9), Dy (10), Nd (11), Yb (12), and Gd (13); H(2)ox = oxalic acid), have been synthesized under hydrothermal conditions. Complexes 1-5 are isomorphous, which can be described as a two-dimensional (2D) hxl/Shubnikov network based on Ln(2)(CO(2))(4) paddle-wheel units, and the isomorphous complexes 6-13 feature a 2D decker layer architecture constructed by Ln-ox infinite chains cross-linked alternatively by bridging Hhqc(-) ligands. The room-temperature photoluminescence spectra of complexes Eu(III) (1 and 6), Tb(III) (2 and 7), and Sm(III) (3 and 8) exhibit strong characteristic emissions in the visible region, whereas Nd(III) (4 and 11) and Yb(III) (12) complexes display NIR luminescence upon irradiation at the ligand band. Moreover, the triplet state of H(2)hqc matches well with the emission level of Eu(III), Tb(III), and Sm(III) ions, which allows the preparation of new optical materials with enhanced luminescence properties.

  15. Lanthanide(III and Yttrium(III Complexes of Benzimidazole-2-Acetic Acid: Synthesis, Characterisation and Effect of La(III Complex on Germination of Wheat

    Directory of Open Access Journals (Sweden)

    2006-01-01

    Full Text Available The synthesis and characterisation of lanthanide(III and yttrium(III nitrate complexes of benzimidazole-2-acetic acid (HBIA are reported. The complexes have been characterised by elemental analysis, molar conductance, magnetic studies, IR, 1 H NMR, UV-visible, EPR, and TG/DTA studies. They have the stoichiometry [ Ln 3 ( BIA 2 ( NO 3 7 ( H 2 O 4 ]⋅3 H 2 O where Ln=La(III, Pr(III, Nd(II, Sm(III, Eu(III, Gd(III, Tb(III, Dy(III, and Y(III. The effect of La(III complex on germination, coleoptile, and root length of two local varieties of wheat DWR-195 and GW-349 for different treatment periods has been investigated. The complex was found to exhibit enhanced activity, compared to HBIA or metal salt alone at lower treatment periods.

  16. Synthesis, structural characterization and thermal studies of lanthanide complexes with Schiff base ligand N,N′-di-(4′-pentyloxybenzoate-salicylidene-1,3-diaminopropane

    Directory of Open Access Journals (Sweden)

    Sadeem M. Al-Barody

    2015-12-01

    Full Text Available New mesogen Schiff base ligand N,N′-di-(4′-pentyloxybenzoatesalicylidene-1,3-diaminopropane [H2L] was synthesized by the reaction of substituted 4-pentyloxy(4′-formyl-3′-hydroxy-benzoate and 1,3-diaminopropane in 2:1 molar ratio. Four mononuclear lanthanide complexes of the type [Ln(H2LLCl] (Ln = LaIII, CeIII, SmIII and GdIII were synthesized and characterized by 1H,13CNMR, fourier transform infrared (FT-IR spectroscopy, elemental analysis (C.H.N.O, gas chromotography-mass, magnetic susceptibility and molar conductivity. Thermal properties of the title compounds were studied using the thermogravimetric analysis/differential scanning calorimetry (TGA/DSC and optical polarizing microscopy (OPM. The ligand and coordination compounds exhibit liquid crystalline properties (smectic A.

  17. Highly Luminescent Lanthanide Complexes of 1 Hydroxy-2-pyridinones

    Energy Technology Data Exchange (ETDEWEB)

    University of California, Berkeley; Lawrence National Laboratory; Raymond, Kenneth; Moore, Evan G.; Xu, Jide; Jocher, Christoph J.; Castro-Rodriguez, Ingrid; Raymond, Kenneth N.

    2007-11-01

    The synthesis, X-ray structure, stability, and photophysical properties of several trivalent lanthanide complexes formed from two differing bis-bidentate ligands incorporating either alkyl or alkyl ether linkages and featuring the 1-hydroxy-2-pyridinone (1,2-HOPO) chelate group in complex with Eu(III), Sm(III) and Gd(III) are reported. The Eu(III) complexes are among some of the best examples, pairing highly efficient emission ({Phi}{sub tot}{sup Eu} {approx} 21.5%) with high stability (pEu {approx} 18.6) in aqueous solution, and are excellent candidates for use in biological assays. A comparison of the observed behavior of the complexes with differing backbone linkages shows remarkable similarities, both in stability and photophysical properties. Low temperature photophysical measurements for a Gd(III) complex were also used to gain insight into the electronic structure, and were found to agree with corresponding TD-DFT calculations for a model complex. A comparison of the high resolution Eu(III) emission spectra in solution and from single crystals also revealed a more symmetric coordination geometry about the metal ion in solution due to dynamic rotation of the observed solid state structure.

  18. Highly Luminescent Lanthanide Complexes of 1 Hydroxy-2-pyridinones

    Energy Technology Data Exchange (ETDEWEB)

    University of California, Berkeley; Lawrence National Laboratory; Raymond, Kenneth; Moore, Evan G.; Xu, Jide; Jocher, Christoph J.; Castro-Rodriguez, Ingrid; Raymond, Kenneth N.

    2007-11-01

    The synthesis, X-ray structure, stability, and photophysical properties of several trivalent lanthanide complexes formed from two differing bis-bidentate ligands incorporating either alkyl or alkyl ether linkages and featuring the 1-hydroxy-2-pyridinone (1,2-HOPO) chelate group in complex with Eu(III), Sm(III) and Gd(III) are reported. The Eu(III) complexes are among some of the best examples, pairing highly efficient emission ({Phi}{sub tot}{sup Eu} {approx} 21.5%) with high stability (pEu {approx} 18.6) in aqueous solution, and are excellent candidates for use in biological assays. A comparison of the observed behavior of the complexes with differing backbone linkages shows remarkable similarities, both in stability and photophysical properties. Low temperature photophysical measurements for a Gd(III) complex were also used to gain insight into the electronic structure, and were found to agree with corresponding TD-DFT calculations for a model complex. A comparison of the high resolution Eu(III) emission spectra in solution and from single crystals also revealed a more symmetric coordination geometry about the metal ion in solution due to dynamic rotation of the observed solid state structure.

  19. Oxoselenido clusters of the lanthanides: rational introduction of oxo ligands and near-IR emission from Nd(III).

    Science.gov (United States)

    Banerjee, Santanu; Huebner, Louise; Romanelli, Michael D; Kumar, G Ajith; Riman, Richard E; Emge, Thomas J; Brennan, John G

    2005-11-16

    Reactions of Ln(SePh)3 with SeO2 in THF give octanuclear oxoselenido clusters with the general formula (THF)8Ln8O2Se2(SePh)16 (Ln = Ce, Pr, Nd, Sm). In this isomorphous series, the eight Ln(III) ions are connected in the center by a pair of mu3-O2- ligands and mu5-Se2- ligands, with 14 bridging and two terminal selenolate ligands capping the cluster surface. Thermal decomposition at 700 degrees C of the Nd compound in vacuo led to the formation of a phase mixture of NdSe2, Nd2Se3, and Nd2O3. Near-IR emission experiments on the (THF)8Nd8O2Se2(SePh)16 and the fluorinated thiolate compound (DME)2Nd(SC6F5)3 demonstrate that clusters with oxo ligands are not only highly emissive, but also they emit at wavelengths not found in conventional oxides.

  20. Complexation Studies of Bidentate Heterocyclic N-Donor Ligands with Nd(III) and Am(III)

    Energy Technology Data Exchange (ETDEWEB)

    Ogden, Mark; Hoch, Courtney L.; Sinkov, Sergey I.; Meier, Patrick; Lumetta, Gregg J.; Nash, Kenneth L.

    2011-11-28

    A new bidentate nitrogen donor complexing agent that combines pyridine and triazole functional groups, 2-((4-phenyl-1H-1,2,3-triazol-1-yl)methyl)pyridine (PTMP), has been synthesized. The strength of its complexes with trivalent americium (Am3+) and neodymium (Nd3+) in anhydrous methanol has been evaluated using spectrophotometric techniques. The purpose of this investigation is to assess this ligand (as representative of a class of similarly structured species) as a possible model compound for the challenging separation of trivalent actinides from lanthanides. This separation, important in the development of advanced nuclear fuel cycles, is best achieved through the agency of multidentate chelating agents containing some number of nitrogen or sulfur donor groups. To evaluate the relative strength of the bidentate complexes, the derived constants are compared to those of the same metal ions with 2,2*-bipyridyl (bipy), 1,10-phenanthroline (phen), and 2-pyridin-2-yl-1H-benzimidazole (PBIm). At issue is the relative affinity of the triazole moiety for trivalent f element ions. For all ligands, the derived stability constants are higher for Am3+ than Nd3+. In the case of Am3+ complexes with phen and PBIm, the presence of 1:2 (AmL2) species is indicated. Possible separations are suggested based on the relative stability and stoichiometry of the Am3+ and Nd3+ complexes. It can be noted that the 1,2,3-triazolyl group imparts a potentially useful selectivity for trivalent actinides (An(III)) over trivalent lanthanides (Ln(III)), though the attainment of higher complex stoichiometries in actinide compared with lanthanide complexes may be an important driver for developing successful separations.

  1. Development of Gd(III) porphyrin-conjugated chitosan nanoparticles as contrast agents for magnetic resonance imaging.

    Science.gov (United States)

    Jahanbin, Tania; Sauriat-Dorizon, Hélène; Spearman, Peter; Benderbous, Soraya; Korri-Youssoufi, Hafsa

    2015-01-01

    A novel magnetic resonance imaging (MRI) contrast agent based on gadolinium meso-tetrakis(4-pyridyl)porphyrin [Gd(TPyP)] conjugated with chitosan nanoparticles has been developed. The chitosan nanoparticles were synthesized following an ionic gelation method and the conditions optimized to generate small nanoparticles (CNs) with a narrow size distribution of 35-65 nm. The gadolinium meso-tetrakis(4-pyridyl)porphyrin [Gd(TPyP)] was loaded into chitosan nanoparticles by passive adsorption. The interaction of chitosan with Gd(TPyP) has been examined by UV-visible, Fourier transform infrared spectroscopies (FT-IR) and inductively coupled plasma mass spectrometry (ICP-MS), which indicate the successful association of Gd(TPyP) without any structural distortion throughout the chitosan nanoparticles. The potential of Gd(TPyP)-CNs as MRI contrast agent has been investigated by magnetic resonance imaging (MRI) in-vitro. Relaxivities of Gd(TPyP)-CNs obtained from T1-weighted images, increased with Gd concentration and attained an optimum r1 of 38.35 mM(-1) s(-1), which is 12-fold higher compared to commercial Gd-DOTA (~4 mM(-1) s(-1) at 3T). The combination of such strong MRI contrast with the known properties of porphyrins in photodynamic therapy and biocompatibility of chitosan, presents a new perspective in using these compounds in cancer theranostics.

  2. Development of Gd(III) porphyrin-conjugated chitosan nanoparticles as contrast agents for magnetic resonance imaging

    Energy Technology Data Exchange (ETDEWEB)

    Jahanbin, Tania [Université Paul Sabatier, Toulouse III, INSERM U825, CHU Purpan, 31059 Toulouse Cedex 9 (France); Sauriat-Dorizon, Hélène [Institut de Chimie Moléculaire et des Matériaux d' Orsay, UMR CNRS 8182, ECBB, Université Paris-Sud, 91405 Orsay (France); Spearman, Peter [Faculty of Science, Engineering and Computing, University of Kingston, Penrhyn Road Kingston upon Thames Surrey KT1 2EE, London (United Kingdom); Benderbous, Soraya, E-mail: soraya.benderbous@univ-tlse3.fr [Université Paul Sabatier, Toulouse III, INSERM U825, CHU Purpan, 31059 Toulouse Cedex 9 (France); Korri-Youssoufi, Hafsa, E-mail: hafsa.korri-youssoufi@u-psud.fr [Institut de Chimie Moléculaire et des Matériaux d' Orsay, UMR CNRS 8182, ECBB, Université Paris-Sud, 91405 Orsay (France)

    2015-07-01

    A novel magnetic resonance imaging (MRI) contrast agent based on gadolinium meso-tetrakis(4-pyridyl)porphyrin [Gd(TPyP)] conjugated with chitosan nanoparticles has been developed. The chitosan nanoparticles were synthesized following an ionic gelation method and the conditions optimized to generate small nanoparticles (CNs) with a narrow size distribution of 35–65 nm. The gadolinium meso-tetrakis(4-pyridyl)porphyrin [Gd(TPyP)] was loaded into chitosan nanoparticles by passive adsorption. The interaction of chitosan with Gd(TPyP) has been examined by UV–visible, Fourier transform infrared spectroscopies (FT-IR) and inductively coupled plasma mass spectrometry (ICP-MS), which indicate the successful association of Gd(TPyP) without any structural distortion throughout the chitosan nanoparticles. The potential of Gd(TPyP)-CNs as MRI contrast agent has been investigated by magnetic resonance imaging (MRI) in-vitro. Relaxivities of Gd(TPyP)-CNs obtained from T{sub 1}-weighted images, increased with Gd concentration and attained an optimum r{sub 1} of 38.35 mM{sup −1} s{sup −1}, which is 12-fold higher compared to commercial Gd-DOTA (~ 4 mM{sup −1} s{sup −1} at 3T). The combination of such strong MRI contrast with the known properties of porphyrins in photodynamic therapy and biocompatibility of chitosan, presents a new perspective in using these compounds in cancer theranostics. - Highlights: • Synthesis of chitosan nanoparticles with small size • Study of loading properties with gadolinium porphyrins • In vitro properties of the conjugated complex as contrast agent for MRI imaging • Comparison of MRI properties with commercial contrast agent Gd-DOTA.

  3. Two Gd(III) coordination polymers based on a flexible tricarboxylate: Syntheses, structures, luminescence and catalytic properties

    Science.gov (United States)

    Zhu, Yu; Zhu, Min; Liu, Pan; Xia, Li; Wu, Yunlong; Xie, Jimin

    2017-02-01

    Two Gadolinium coordination polymers {[Gd·(TTTA)·(H2O)2]·2H2O}n (1) and [Gd·(TTTA)·DMF]n (2) have been synthesized based on Gd(NO3)3·6H2O and the flexible tripodal ligand 2,2‧,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid (H3TTTA) under hydrothermal conditions. In the structure of 1, the tridentate TTTA3- ligands connect the dimeric metal centers into an infinite one dimensional chain. While 2 shows a two dimensional network with tridentate TTTA3- ligands. The two complexes all quench the emission spectra after coordinated to the Gd3+ ions. The catalytic results indicate that two complexes show excellent activities for the cyanosilylation of benzaldehyde and its derivatives. Besides, 2 is better than 1 in the catalytic reactions due to more possibility of metal open sites.

  4. Lanthanide complexes derived from hexadentate macrocyclic ligand: synthesis, spectroscopic and thermal investigation.

    Science.gov (United States)

    Chandra, Sulekh; Tyagi, Monika; Rani, Soni; Kumar, Sumit

    2010-02-01

    The lanthanide complexes derived from (3,5,13,15-tetramethyl 2,6,12,16,21-22-hexaazatricyclo[15.3.I(1-17)I(7-11)]cosa-1(21),2,5,7,9,11(22),12,15,17,19-decane) were synthesized. The complexes were found to have general composition [Ln(L)X(2).H(2)O]X, where Ln=La(3+), Ce(3+), Nd(3+), Sm(3+) and Eu(3+) and X=NO(3)(-) and Cl(-). The ligand was characterized by elemental analyses, IR, Mass, and (1)H NMR spectral studies. All the complexes were characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, Mass, electronic spectral techniques and thermal studies. The ligand acts as a hexadentate and coordinates through four nitrogen atoms of azomethine groups and two nitrogen of pyridine ring. The lanthanum complexes are diamagnetic while the other Ln(III) complexes are paramagnetic. The spectral parameters i.e. nephelauxetic ratio (beta), covalency factor (b(1/2)), Sinha parameter (delta%) and covalency angular overlap parameter (eta) have been calculated from absorption spectra of Nd(III) and Sm(III) complexes. These parameters suggest the metal-ligand covalent bonding. In the present study, the complexes were found to have coordination number nine.

  5. Lanthanide-directed synthesis of luminescent self-assembly supramolecular structures and mechanically bonded systems from acyclic coordinating organic ligands.

    Science.gov (United States)

    Barry, Dawn E; Caffrey, David F; Gunnlaugsson, Thorfinnur

    2016-06-01

    Herein some examples of the use of lanthanide ions (f-metal ions) to direct the synthesis of luminescent self-assembly systems (architectures) will be discussed. This area of lanthanide supramolecular chemistry is fast growing, thanks to the unique physical (magnetic and luminescent) and coordination properties of the lanthanides, which are often transferred to the resulting supermolecule. The emphasis herein will be on systems that are luminescent, and hence, generated by using either visibly emitting ions (such as Eu(III), Tb(III) and Sm(III)) or near infrared emitting ions (like Nd(III), Yb(III) and Er(III)), formed through the use of templating chemistry, by employing structurally simple ligands, possessing oxygen and nitrogen coordinating moieties. As the lanthanides have high coordination requirements, their use often allows for the formation of coordination compounds and supramolecular systems such as bundles, grids, helicates and interlocked molecules that are not synthetically accessible through the use of other commonly used templating ions such as transition metal ions. Hence, the use of the rare-earth metal ions can lead to the formation of unique and stable species in both solution and in the solid state, as well as functional and responsive structures.

  6. Laser-induced lanthanide luminescence as a probe of metal ion-binding sites of human Factor Xa.

    Science.gov (United States)

    Rhee, M J; Horrocks, W D; Kosow, D P

    1984-06-25

    7F0 ---- 5D0 excitation spectroscopy of Eu(III) has shown that human Factor Xa has two high affinity lanthanide ion-binding sites. The deuterium isotope effect on the reciprocal lifetime (tau-1) of excited Eu(III) in human Factor Xa has indicated that 2 to 3 water molecules remain on Eu(III) after being complexed by Factor Xa, suggesting that 3-6 ligand atoms are provided by the protein, probably through two or three gamma-carboxyglutamic acids (GLA). F orster -type interlanthanide energy transfer has been utilized to measure the distance between the high affinity metal ion-binding sites of human Factor Xa using Tb(III) as an energy donor and Nd(III), Ho(III), or Er(III) as energy acceptors. Tau-1 values of Tb(III) in the presence of the acceptor ions Nd(III), Ho(III), and Er(III) were 1.90, 1.66, and 1.76 ms-1, respectively, which compared to 1.31 ms-1 in the presence of the nonacceptor ion Gd(III), yield energy transfer efficiencies of 0.29, 0.20, and 0.24, respectively. From these efficiencies and published critical distances (R0) ( Horrocks , W. DeW ., Jr., Rhee , M-J., Snyder, A. P., and Sudnick , D. R. (1980) J. Am. Chem. Soc. 102, 3650-3652), the distance between two high affinity sites is estimated to be 10.7 A. Based on these data, we propose that the two high affinity sites of human Factor Xa consist of two paired GLA residues; GLA-19, GLA-20 and GLA-25, GLA-26 together with one of the remaining single GLA residues for each site.

  7. Hydrothermal synthesis, crystal structure and luminescence property of a three dimensional Sm(III) coordination polymer with 2,5-pyridinedicarboxylic acid

    Indian Academy of Sciences (India)

    Kranthi Kumar Gangu; Anima S Dadhich; Saratchandra Babu Mukkamala

    2015-12-01

    A novel three dimensional coordination polymer [Sm(2,5-pydc)(NO3)(H2O)]·(H2O) (2,5-pydc = 2,5-pyridine dicarboxylate) (1) had been synthesized hydrothermally and characterized by elemental analysis, FT-IR and single-crystal X-ray diffraction analysis. This coordination polymer crystallized in the monoclinic space group P2/n with cell parameters = 9.3610(4) Å, = 8.3498(3) Å, = 16.7159(8) Å, = 106.31(0)°, = 1253.98(184) Å3. Thermogravimetric analysis revealed that complex 1 is stable up to 400°C which on photoexcitation at 365 nm exhibited yellow emission at 583 nm.

  8. Synthesis, characterization and DNA-binding studies of 2-carboxybenzaldehydeisonicotinoylhydrazone and its La(III), Sm(III) and Eu(III) complexes

    Science.gov (United States)

    Wang, Yuan; Wang, Yan; Yang, Zheng-Yin

    2007-02-01

    2-Carboxybenzaldehydeisonicotinoylhydrazone (HL), and its three lanthanide complexes, LnL 3·4H 2O [Ln = La( 1), Sm( 2), Eu( 3)], have been synthesized and characterized on the basis of elemental analyses, molar conductivities, IR spectra and thermal analyses. In addition, the DNA-binding properties of the ligand and its complexes have been investigated by absorption, fluorescence and viscosity measurements. The experimental results indicated that the complexes ( 2) and ( 3) can bind to DNA, but the ligand and the complex ( 1) cannot; the binding affinity of the complex ( 3) is higher than that of the complex ( 2) and the intrinsic binding constant Kb of the complex ( 3) is 7.86 × 10 4 M -1.

  9. Highly luminescent Sm(III) complexes with intraligand charge-transfer sensitization and the effect of solvent polarity on their luminescent properties.

    Science.gov (United States)

    Lo, Wai-Sum; Zhang, Junhui; Wong, Wing-Tak; Law, Ga-Lai

    2015-04-20

    Samarium complexes with the highest quantum yields to date have been synthesized, and their luminescence properties were studied in 12 solvents. Sensitization via a nontriplet intraligand charge-transfer pathway was also successfully demonstrated in solution states with good quantum yields.

  10. Synthesis, characterization and DNA interaction studies of complexes of lanthanide nitrates with tris{2-[(3,4-dihydroxybenzylidene)imino]ethyl}amine

    Science.gov (United States)

    Liu, Min; Yuan, Wen-bing; Zhang, Qi; Yan, Lan; Yang, Ru-dong

    2008-10-01

    A new tripodal, hydroxyl-rich ligand, tris{2-[(3,4-dihydroxybenzylidene)imino]ethyl}amine (L), and its complexes with lanthanide nitrates were synthesized. These complexes which are stable in air with the general formula of [LnL(NO 3) 2]NO 3·H 2O (Ln = La, Sm, Eu, Gd, Y) were characterized by molar conductivity, elemental analysis, IR spectra and thermal analysis. The NO 3- groups coordinated to lanthanide mono-dentately, and the coordination number in these complexes may be 8. The interaction of complexes with DNA were investigated by ultraviolet and fluorescent spectra, which showed that the binding mode of complexes with DNA was intercalation, and the binding affinity with DNA were La(III) complex > Sm(III) complex > Eu(III) complex > Gd(III) complex > Y(III) complex. Based on these results, it can be shown that the La(III)complex is promising candidate for therapeutic reagents and DNA probes.

  11. Solvothermal synthesis and structure of 3D frameworks of Nd(III) and Y(III) with thiophene-2,5-dicarboxylate and N,N‧-diethylformamide

    Science.gov (United States)

    Sharma, Swati; Yawer, Mohd; Kariem, Mukaddus; Sheikh, Haq Nawaz

    2016-08-01

    Two new 3D MOFs [Nd2(TDA)3(DEF)2(H2O)]n (1) and [Y4(TDA)6(DEF)4]n (2) [Thiophene-2,5-dicarboxylic acid (H2TDA) and N,N‧-diethylformamide (DEF)] were synthesized by solvothermal method. They were characterized by elemental analyses, infrared spectroscopy and single crystal X-ray diffraction studies. The two MOFs (1) and (2) belong to the monoclinic system with space group P21/n and C 2 respectively. Structural characterizations by single-crystal X-ray crystallography reveal that 1 and 2 adopt three-dimensional frameworks constructed by cross-linking of rod shaped infinite chain secondary building unit (SBU) by thiophene-2,5-dicarboxylates as linker. These frameworks feature rhomboidal channels, inside which coordinated DEF/H2O solvent molecules are located. DEF plays pivotal role in reaction and design of MOFs. Thermogravimetric analysis shows that both MOFs are thermally robust.

  12. Lanthanide complexes containing 5-methyl-1,2,4-triazolo[1,5-a] pyrimidin-7(4H)-one and their therapeutic potential to fight leishmaniasis and Chagas disease.

    Science.gov (United States)

    Caballero, Ana B; Rodríguez-Diéguez, Antonio; Salas, Juan M; Sánchez-Moreno, Manuel; Marín, Clotilde; Ramírez-Macías, Inmaculada; Santamaría-Díaz, Noelia; Gutiérrez-Sánchez, Ramón

    2014-09-01

    In the last years, numerous and significant advances in lanthanide coordination chemistry have been achieved. The unique chemical nature of these metal ions which is conferred by their f-electrons has led to a wide range of coordination compounds with interesting structural, physical and also biological properties. Consequently, lanthanide complexes have found applications mainly in catalysis, gas adsorption, photochemistry and as diagnostic tools. However, research on their therapeutic potential and the understanding of their mechanism of action is still taking its first steps, and there is a distinct lack of research in the parasitology field. In the present work, we describe the synthesis and physical properties of seven new lanthanide complexes with the anionic form of the bioactive ligand 5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7(4H)-one (HmtpO), namely [Ln(mtpO)3(H2O)6]·9H2O (Ln=La(III), Nd(III), Eu(III), Gd(III), Tb(III), Dy(III) and Er(III)). In addition, results on the in vitro antiproliferative activity against Leishmania spp. and Trypanosoma cruzi are described. The high activity of the new compounds against parasite proliferation and their low cytotoxicity against reference host cell lines show a great potential of this type of compounds to become a new generation of highly effective and non-toxic antiparasitic agents to fight the so considered neglected diseases leishmaniasis and Chagas disease.

  13. Nanozeolite-LTL with Gd(III) deposited in the large and Eu(III) in the small cavities as a magnetic resonance optical imaging probe.

    Science.gov (United States)

    Mayer, Florian; Zhang, Wuyuan; Brichart, Thomas; Tillement, Olivier; Bonnet, Célia S; Tóth, Éva; Peters, Joop A; Djanashvili, Kristina

    2014-03-17

    The immense structural diversity of more than 200 known zeolites is the basis for the wide variety of applications of these fascinating materials ranging from catalysis and molecular filtration to agricultural uses. Despite this versatility, the potential of zeolites in medical imaging has not yet been much exploited. In this work a novel strategy is presented to selectively deposit different ions into distinct framework locations of zeolite-LTL (Linde type L) and it is demonstrated that the carefully ion-exchanged Gd/Eu-containing nanocrystals acquire exceptional magnetic properties in combination with enhanced luminescence. This smart exploitation of the framework structure yields the highest relaxivity density (13.7 s(-1)  L g(-1) at 60 MHz and 25 °C) reported so far for alumosilicates, rendering these materials promising candidates for the design of dual magnetic resonance/optical imaging probes, as demonstrated in preliminary phantom studies.

  14. GdDOTAGA(C18)2: an efficient amphiphilic Gd(iii) chelate for the preparation of self-assembled high relaxivity MRI nanoprobes.

    Science.gov (United States)

    Filippi, M; Remotti, D; Botta, M; Terreno, E; Tei, L

    2015-12-21

    A new amphiphilic GdDOTA-like complex functionalized with two octadecyl chains was synthesised and incorporated into the bilayer of liposomes and dendrimersomes. (1)H NMR relaxometric studies and in vivo MRI experiments on mice bearing a syngeneic melanoma tumour have shown a great improvement in performance.

  15. A benzene-core trinuclear GdIII complex: towards the optimization of relaxivity for MRI contrast agent applications at high magnetic field.

    Science.gov (United States)

    Livramento, João Bruno; Helm, Lothar; Sour, Angélique; O'Neil, Conlin; Merbach, André E; Tóth, Eva

    2008-03-07

    A novel ligand, H(12)L, based on a trimethylbenzene core bearing three methylenediethylenetriamine-N,N,N'',N''-tetraacetate moieties (-CH(2)DTTA(4-)) for Gd(3+) chelation has been synthesized, and its trinuclear Gd(3+) complex [Gd(3)L(H(2)O)(6)](3-) investigated with respect to MRI contrast agent applications. A multiple-field, variable-temperature (17)O NMR and proton relaxivity study on [Gd(3)L(H(2)O)(6)](3-) yielded the parameters characterizing water exchange and rotational dynamics. On the basis of the (17)O chemical shifts, bishydration of Gd(3+) could be evidenced. The water exchange rate, k(ex)(298)=9.0+/-3.0 s(-1) is around twice as high as k(ex)(298) of the commercial [Gd(DTPA)(H(2)O)](2-) and comparable to those on analogous Gd(3+)-DTTA chelates. Despite the relatively small size of the complex, the rotational dynamics had to be described with the Lipari-Szabo approach, by separating global and local motions. The difference between the local and global rotational correlation times, tau(lO)(298)=170+/-10 ps and tau(gO)(298)=540+/-100 ps respectively, shows that [Gd(3)L(H(2)O)(6)](3-) is not fully rigid; its flexibility originates from the CH(2) linker between the benzene core and the poly(amino carboxylate) moiety. As a consequence of the two inner-sphere water molecules per Gd(3+), their close to optimal exchange rate and the appropriate size and limited flexibility of the molecule, [Gd(3)L(H(2)O)(6)](3-) has remarkable proton relaxivities when compared with commercial contrast agents, particularly at high magnetic fields (r(1)=21.6, 17.0 and 10.7 mM(-1)s(-1) at 60, 200 and 400 MHz respectively, at 25 degrees C; r(1) is the paramagnetic enhancement of the longitudinal water proton relaxation rate, referred to 1 mM concentration of Gd(3+)).

  16. A family of acetato-diphenoxo triply bridged dimetallic Zn(II)Ln(III) complexes: SMM behavior and luminescent properties.

    Science.gov (United States)

    Oyarzabal, Itziar; Artetxe, Beñat; Rodríguez-Diéguez, Antonio; García, JoséÁngel; Seco, José Manuel; Colacio, Enrique

    2016-06-21

    Eleven dimetallic Zn(II)-Ln(III) complexes of the general formula [Zn(µ-L)(µ-OAc)Ln(NO3)2]·CH3CN (Ln(III) = Pr (1), Nd (2), Sm (3), Eu (4), Gd (5), Tb (6), Dy (7), Ho (8), Er (9), Tm (10), Yb (11)) have been prepared in a one-pot reaction from the compartmental ligand N,N'-dimethyl-N,N'-bis(2-hydroxy-3-formyl-5-bromo-benzyl)ethylenediamine (H2L). In all these complexes, the Zn(II) ions occupy the internal N2O2 site whereas the Ln(III) ions show preference for the O4 external site. Both metallic ions are bridged by an acetate bridge, giving rise to triple mixed diphenoxido/acetate bridged Zn(II)Ln(III) compounds. The Nd, Dy, Er and Yb complexes exhibit field induced single-ion magnet (SIM) behaviour, with Ueff values ranging from 14.12 to 41.55 K. The Er complex shows two relaxation processes, but only the second relaxation process with an energy barrier of 21.0 K has been characterized. The chromophoric L(2-) ligand is able to act as an "antenna" group, sensitizing the near-infrared (NIR) Nd(III) and Yb(III)-based luminescence in complexes 2 and 11 and therefore, both compounds can be considered as magneto-luminescent materials. In addition, the Sm(III), Eu(III) and Tb(III) derivatives exhibit characteristic emissions in the visible region.

  17. Lanthanoid Template Isolation of the α-1,5 Isomer of Dicobalt(II)-Substituted Keggin Type Phosphotungstates: Syntheses, Characterization, and Magnetic Properties.

    Science.gov (United States)

    Gupta, Rakesh; Hussain, Firasat; Sadakane, Masahiro; Kato, Chisato; Inoue, Katsuya; Nishihara, Sadafumi

    2016-09-06

    A new series of heterometallic 3d-4f sandwich type phosphotungstates, [Ln{PCo2W10O38(H2O)2}2](11-) (Ln = Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), and Lu(III), denoted 1a-10a, respectively), have been synthesized by a one-pot reaction procedure on reacting the dilacunary K14[P2W19O69(H2O)]·24H2O precursor with Ln(NO3)3·nH2O and Co(NO3)2·6H2O in an aqueous potassium chloride solution. All the compounds were isolated as potassium salts and further characterized with different analytical techniques such as single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, high-resolution electrospray ionization mass spectrometry, elemental analysis by inductively coupled plasma atomic emission spectroscopy, magnetic measurement, and thermogravimetric analysis. Single-crystal X-ray diffraction analysis of the compounds reveals that all these compounds are isostructural and crystallized in the orthorhombic crystal system in space group Iba2. The polyanions contain the α-1,5 isomer of dicobalt-substituted α-Keggin phosphotungstate, which sandwiched lanthanoid cation and formed novel heterometallic dimer species. The temperature-dependent magnetic susceptibilities of 1a, 2a, 4a, and 7a-10a indicate the dominant contribution of the ferromagnetic interaction between Co(II) and Co(II) within the cluster, while the antiferromagnetic interaction between Co(II) and Ln(III) dominates for 3a, 5a, and 6a. The isothermal magnetizations of 1a-10a show a gradual increase in magnetization at low fields and do not reach saturation even at 50 kOe.

  18. Application of High-Resolution Magic-Angle Spinning NMR Spectroscopy to Define the Cell Uptake of MRI Contrast Agents

    Science.gov (United States)

    Calabi, Luisella; Alfieri, Goffredo; Biondi, Luca; De Miranda, Mario; Paleari, Lino; Ghelli, Stefano

    2002-06-01

    A new method, based on proton high-resolution magic-angle spinning ( 1H HR-MAS) NMR spectroscopy, has been employed to study the cell uptake of magnetic resonance imaging contrast agents (MRI-CAs). The method was tested on human red blood cells (HRBC) and white blood cells (HWBC) by using three gadolinium complexes, widely used in diagnostics, Gd-BOPTA, Gd-DTPA, and Gd-DOTA, and the analogous complexes obtained by replacing Gd(III) with Dy(III), Nd(III), and Tb(III) (i.e., complexes isostructural to the ones of gadolinium but acting as shift agents). The method is based on the evaluation of the magnetic effects, line broadening, or induced lanthanide shift (LIS) caused by these complexes on NMR signals of intra- and extracellular water. Since magnetic effects are directly linked to permeability, this method is direct. In all the tests, these magnetic effects were detected for the extracellular water signal only, providing a direct proof that these complexes are not able to cross the cell membrane. Line broadening effects (i.e., the use of gadolinium complexes) only allow qualitative evaluations. On the contrary, LIS effects can be measured with high precision and they can be related to the concentration of the paramagnetic species in the cellular compartments. This is possible because the HR-MAS technique provides the complete elimination of bulk magnetic susceptibility (BMS) shift and the differentiation of extra- and intracellular water signals. Thus with this method, the rapid quantification of the MRI-CA amount inside and outside the cells is actually feasible.

  19. Luminescence study of Sm 3 absorbed in NaZr{sub 2}(PO{sub 4}){sub 3}; Estudio de luminiscencia del Sm(III) sorbido en NaZr{sub 2}(PO{sub 4}){sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Contreras R, A.; Ordonez R, E.; Fernandez V, S. M. [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)], e-mail: aida.contreras@inin.gob.mx

    2009-10-15

    The proposal more viable and technologically accepted for disposal of high level radioactive wastes is deep geologic storage. It built with multi barriers system, one of those which have as objective to avoid or to slow the radio elements dispersion to nearby environment of deep geologic storages. For this study is expose the use of zirconium and sodium mixed phosphates as structural materials of contention barriers. In laboratory tests have been made to determine the absorption grade and its reaction mechanism using samarium, which is a lanthanide that is find on spent fuel assemblies and it is chemically homologous of trivalent actinide elements, therefore results of interest its study. In this work, the methodology is shown to study the absorption of Sm 3 + zirconium and sodium mixed phosphates in function of p H of suspension by means the half life time analysis of phosphorescence produced by samarium species that are absorbed in active locations of zirconium and sodium mixed phosphates. The life time of phosphorescence of Sm(ClO{sub 4}){sub 3} is determined in solution, of dry and hydrated zirconium and sodium mixed phosphates with a solution of NaClO{sub 4} and the absorbed samarium in zirconium and sodium mixed phosphates of hydrated way and the absorbed samarium after to dry the solid. (Author)

  20. Use of Sm(III)-{1,2-propanediamine-N,N,N',N'-tetra(alpha,alpha-dideuterioacetate)} complex for NMR determination of absolute configuration of each alpha-amino acid in peptide hydrolysate mixtures.

    Science.gov (United States)

    Omata, Kenji; Fujioka, Mika; Kabuto, Kuninobu; Sasaki, Yoichi

    2008-10-28

    (1)H NMR analyses of individual alpha-amino acids in their mixture were simultaneously conducted in the presence of Sm-(pdta-d(8)) in water: high regularity, promising for direct simultaneous determination of absolute configurations of each alpha-amino acids in peptide hydrolysate mixtures, was observed between absolute configuration and the induced shifts.

  1. Construction of Polynuclear Lanthanide (Ln = Dy(III), Tb(III), and Nd(III)) Cage Complexes Using Pyridine-Pyrazole-Based Ligands: Versatile Molecular Topologies and SMM Behavior.

    Science.gov (United States)

    Bala, Sukhen; Sen Bishwas, Mousumi; Pramanik, Bhaskar; Khanra, Sumit; Fromm, Katharina M; Poddar, Pankaj; Mondal, Raju

    2015-09-08

    Employment of two different pyridyl-pyrazolyl-based ligands afforded three octanuclear lanthanide(III) (Ln = Dy, Tb) cage compounds and one hexanuclear neodymium(III) coordination cage, exhibiting versatile molecular architectures including a butterfly core. Relatively less common semirigid pyridyl-pyrazolyl-based asymmetric ligand systems show an interesting trend of forming polynuclear lanthanide cage complexes with different coordination environments around the metal centers. It is noteworthy here that construction of lanthanide complex itself is a challenging task in a ligand system as soft N-donor rich as pyridyl-pyrazol. We report herein some lanthanide complexes using ligand containing only one or two O-donors compare to five N-coordinating sites. The resultant multinuclear lanthanide complexes show interesting magnetic and spectroscopic features originating from different spatial arrangements of the metal ions. Alternating current (ac) susceptibility measurements of the two dysprosium complexes display frequency- and temperature-dependent out-of-phase signals in zero and 0.5 T direct current field, a typical characteristic feature of single-molecule magnet (SMM) behavior, indicating different energy reversal barriers due to different molecular topologies. Another aspect of this work is the occurrence of the not-so-common SMM behavior of the terbium complex, further confirmed by ac susceptibility measurement.

  2. Modeling of retention of some fission products and actinides by ion-exchange chromatography with a complexing agent. Application to the determination of selectivity coefficients; Modelisation de la retention de quelques produits de fission et d'actinides en chromatographie d'echange d'ions en presence d'un agent complexant. Application a la determination de constantes d'echange

    Energy Technology Data Exchange (ETDEWEB)

    Gurdale-Tack, K.; Aubert, M.; Chartier, F. [CEA Saclay, Dept. d' Entreposage et de Stockage des Dechets (DCC/DPE/SPCP/LAIE), 91 - Gif-sur-Yvette (France)

    2000-07-01

    For an accurate determination of the isotopic and elemental composition of americium (Am), curium (Cm), neodymium (Nd) and cesium (Cs) in spent nuclear fuels, performed by Thermal Ionization Mass Spectrometry (TIMS) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS), it is necessary to separate these elements before analysis. This separation is mandatory because of isobaric interferences between americium and curium, neodymium and samarium (Sm) and between cesium and barium (Ba). This is the reason why Ba and Sm are analyzed with the other four elements. Separation is carried out by cation-exchange chromatography on a silica-based stationary phase in the presence of a complexing eluent. The complexing agent is 2-hydroxy-2-methyl butanoic acid (HMB), a monoprotic acid (HL) with a pK{sub a} of 3.6. Cations (M{sup n+}) interact with it to form ML{sub y}{sup (n-y)+} complexes. Optimization of chromatographic separation conditions requires monitoring of the pH and eluent composition. The influence of each parameter on metal ion retention and on selectivity was investigated. The first studies on standard solutions with Sm(III), Nd(III), Cs(I) and Ba(II) showed that four conditions allow efficient separation. However, only one allows good separation with a real solution of spent nuclear fuels. This condition is a chelating agent concentration of 0.1 mol.l{sup -1} and a pH of 4.2. With the other conditions, co-elution is observed for Cs(I) and Am(III). The overall results were used to study the retention mechanisms. The aim of this modeling is a closer knowledge of the form in which (M{sup n+} and/or ML{sub y}{sup (n-y)+}...) each cationic element is extracted into the stationary phase. In fact, while cations can exist in the eluent in various forms depending on the analytical conditions, their forms may be different in the stationary phase. (authors)

  3. Single-molecule magnet behavior and magnetocaloric effect in ferromagnetically coupled Ln(III)-Ni(II)-Ni(II)-Ln(III) (Ln(III) = Dy(III) and Gd(III)) linear complexes.

    Science.gov (United States)

    Meseguer, Carlos; Titos-Padilla, Silvia; Hänninen, Mikko M; Navarrete, R; Mota, A J; Evangelisti, Marco; Ruiz, José; Colacio, Enrique

    2014-11-17

    New types of linear tetranuclear Ln(III)-Ni(II)-Ni(II)-Ln(III) (Ln(III) = Dy (1), Gd (2)) complexes have been prepared using the multidentate ligand N,N'-bis(3-methoxysalicylidene)-1,3-diaminobenzene, which has two sets of NO and OO' coordination pockets that are able to selectively accommodate Ni(II) and Ln(III) ions, respectively. The X-ray structure analysis reveals that the Ni(II) ions are bridged by phenylenediimine groups forming a 12-membered metallacycle in the central body of the complex, whereas the Ln(III) ions are located at both sides of the metallacycle and linked to the Ni(II) ions by diphenoxo bridging groups. Phenylenediimine and diphenoxo bridging groups transmit ferromagnetic exchange interactions between the two Ni(II) ions and between the Ni(II) and the Ln(III) ions, respectively. Complex 1 shows slow relaxation of the magnetization at zero field and a thermal energy barrier Ueff = 7.4 K with HDC = 1000 Oe, whereas complex 2 exhibits an S = 9 ground state and significant magnetocaloric effect (-ΔSm = 18.5 J kg(-1) K(-1) at T = 3 K and ΔB = 5 T).

  4. Some metal complexes of three new potentially heptadentate (N4O3) tripodal Schiff base ligands; synthesis, characterizatin and X-ray crystal structure of a novel eight coordinate Gd(III) complex

    Science.gov (United States)

    Golbedaghi, Reza; Moradi, Somaeyh; Salehzadeh, Sadegh; Blackman, Allan G.

    2016-03-01

    The symmetrical and asymmetrical potentially heptadentate (N4O3) tripodal Schiff base ligands (H3L1-H3L3) were synthesized from the condensation reaction of three tripodal tetraamine ligands tpt (trpn), tris (3-aminopropyl) amine; ppe (abap), (2-aminoethyl)bis(3-aminopropyl)amine, and tren, tris(2-aminoethyl)amine, with 5-methoxysalicylaldehyde. Then, the reaction of Ln(III) (Ln = Gd, La and Sm), Al(III), and Fe(III) metal ions with the above ligands was investigated. The resulting compounds were characterized by IR, mass spectrometry and elemental analysis in all cases and NMR spectroscopy in the case of the Schiff base ligands. The X-ray crystal structure of the Gd complex of H3L3 ligand showed that in addition to all donor atoms of the ligand one molecule of H2O is also coordinated to the metal ion and a neutral eight-coordinate complex is formed.

  5. Synthesis, structural characterization, luminescent properties and theoretical study of three novel lanthanide metal-organic frameworks of Ho(III), Gd(III) and Eu(III) with 2,5-thiophenedicarboxylate anion

    Energy Technology Data Exchange (ETDEWEB)

    Marques, Lippy F. [Instituto de Química, Universidade do Estado do Rio de Janeiro, Rio de Janeiro 20550-013 (Brazil); Correa, Charlane C. [Departamento de Química-ICE, Universidade Federal de Juiz de Fora, Juiz de Fora-MG, 36036-330 (Brazil); Ribeiro, Sidney J.L.; Santos, Molíria V. dos [Institute of Chemistry, São Paulo State University − UNESP, CP 355 Araraquara-SP 14801-970 Brazil (Brazil); Dutra, José Diogo L.; Freire, Ricardo O. [Pople Computational Chemistry Laboratory, Departamento de Química, Universidade Federal de Sergipe, São Cristóvão-SE 49100-000 (Brazil); Machado, Flávia C., E-mail: flavia.machado@ufjf.edu.br [Departamento de Química-ICE, Universidade Federal de Juiz de Fora, Juiz de Fora-MG, 36036-330 (Brazil)

    2015-07-15

    In this paper, the synthesis of three new metal-organic frameworks of lanthanides (LnMOFs) ([Ln{sub 2}(2,5-tdc){sub 3}(dmso){sub 2}]·H{sub 2}O){sub n} (Ln=Ho (1); Gd (2); Eu (3); 2,5-tdc=2,5-thiophenedicarboxylate anion; dmso=dimethylsulfoxide), and their complete characterization, including single crystal X-ray diffraction, FTIR spectroscopy and thermogravimetric analysis are reported. In especial, photophysical properties of Eu(III) complex have been studied in detail via both theoretical and experimental approaches. Crystal structure of (1) reveals that each lanthanide ion is seven-coordinated by oxygen atoms in an overall distorted capped trigonal – prismatic geometry. The 2,5-tdc{sup 2−} ligands connect four Ln(III) centers, adopting (κ{sup 1}–κ{sup 1})–(κ{sup 1}–κ{sup 1})–μ{sub 4} coordination mode, generating an 8-connected uninodal 3D network. In addition, theoretical studies for Eu(III) complex were performed using the Sparkle model for lanthanide complexes. - Graphical abstract: Three new metal-organic frameworks of lanthanides (LnMOFs) ([Ln{sub 2}(2,5-tdc){sub 3}(dmso){sub 2}]·H{sub 2}O){sub n} (Ln=Ho (1); Gd (2); Eu (3); 2,5-tdc=2,5-thiophenedicarboxylate anion; dmso=dimethylsulfoxide), were synthesized and their complete characterization, including single crystal X-ray diffraction, FTIR spectroscopy and thermogravimetric analysis are reported. In especial, photophysical properties of Eu(III) complex have been studied in detail via both theoretical and experimental approaches. - Highlights: • Three new LnMOFs were synthesized and fully characterized. • Ho{sup 3+}, Gd{sup 3+} and Eu{sup 3+} complexes photoluminescence properties were investigated. • Theoretical approaches for Eu{sup 3+} complex luminescence has been performed. • An energy level diagram is used to establish the ligand-to-metal energy transfer. • These metal−organic frameworks can act as light conversion molecular devices.

  6. Theoretical and experimental spectroscopic studies of the first highly luminescent binuclear hydrocinnamate of Eu(III), Tb(III) and Gd(III) with bidentate 2,2'-bipyridine ligand

    Energy Technology Data Exchange (ETDEWEB)

    Marques, Lippy F.; Correa, Charlane C.; Garcia, Humberto C. [Departamento de Química-ICE, Universidade Federal de Juiz de Fora, Juiz de Fora-MG 36036-330 (Brazil); Martins Francisco, Thiago [Departamento de Física-ICEx, Universidade Federal de Minas Gerais, Pampulha, Belo Horizonte-MG 30123-970 (Brazil); Ribeiro, Sidney J.L. [Instituto de Química, Universidade Estadual Paulista Júlio de Mesquita Filho-UNESP, CP 355, Araraquara-SP 14801-970 (Brazil); Dutra, José Diogo L.; Freire, Ricardo O. [Pople Computational Chemistry Laboratory, Departamento de Química, Universidade Federal de Sergipe, São Cristóvão-SE 49100-000 (Brazil); Machado, Flávia C., E-mail: flavia.machado@ufjf.edu.br [Departamento de Química-ICE, Universidade Federal de Juiz de Fora, Juiz de Fora-MG 36036-330 (Brazil)

    2014-04-15

    In this paper, the synthesis of three new binuclear lanthanide (III) complexes [Ln{sub 2}(cin){sub 6}(bpy){sub 2}] (Ln=Eu (1), Tb (2), Gd (3), cin=hydrocinnamate anion; bpy=2,2'-bipyridine), and their complete characterization, including single crystal X-ray diffraction, FTIR spectroscopy and thermal analysis (TGA/DTA) are reported. In especial, photophysical properties of Eu(III) complex have been studied in detail via both theoretical and experimental approaches. Crystal structures of 1–3 reveal that all compounds are isostructural and that each lanthanide ion is nine-coordinated by oxygen and nitrogen atoms in an overall distorted tricapped trigonal-prismatic geometry. Eu(III) complex structure was also calculated using the Sparkle model for lanthanide complexes and the intensity parameters (Ω{sub 2}, Ω{sub 4}, and Ω{sub 6}), calculated from the experimental data and from Sparkle/PM3 model. The theoretical emission quantum efficiencies obtained for Sparkle/PM3 structures are in excellent agreement with the experimental values, clearly attesting to the efficacy of the theoretical models. The theoretical procedure applied here shows that the europium binuclear compound displays a quantum yield about 65% suggesting that the system can be excellent for the development of efficient luminescent devices. Highlights: • First binuclear Ln{sup 3+}-hydrocinnamate have been synthesized and characterized. • Eu{sup 3+}, Tb{sup 3+} and Gd{sup 3+} complexes photoluminescence properties were investigated. • Theoretical approaches for Eu{sup 3+} complex luminescence has been performed. • An energy level diagram is used to establish the ligand-to-metal energy transfer. • 65% Quantum yield suggests an excellent system for luminescent devices.

  7. Multifunctionality in bimetallic Ln(III)[W(V)(CN)8]3- (Ln = Gd, Nd) coordination helices: optical activity, luminescence, and magnetic coupling.

    Science.gov (United States)

    Chorazy, Szymon; Nakabayashi, Koji; Arczynski, Mirosław; Pełka, Robert; Ohkoshi, Shin-ichi; Sieklucka, Barbara

    2014-06-02

    Two chiral luminescent derivatives of pyridine bis(oxazoline) (Pybox), (SS/RR)-iPr-Pybox (2,6-bis[4-isopropyl-2-oxazolin-2-yl]pyridine) and (SRSR/RSRS)-Ind-Pybox (2,6-bis[8H-indeno[1,2-d]oxazolin-2-yl]pyridine), have been combined with lanthanide ions (Gd(3+), Nd(3+)) and octacyanotungstate(V) metalloligand to afford a remarkable series of eight bimetallic CN(-)-bridged coordination chains: {[Ln(III)(SS/RR-iPr-Pybox)(dmf)4]3[W(V)(CN)8]3}n ⋅dmf⋅4 H2O (Ln = Gd, 1-SS and 1-RR; Ln = Nd, 2-SS and 2-RR) and {[Ln(III)(SRSR/RSRS-Ind-Pybox)(dmf)4][W(V)(CN)8]}n⋅5 MeCN⋅4 MeOH (Ln = Gd, 3-SRSR and 3-RSRS; Ln = Nd, 4-SRSR and 4-RSRS). These materials display enantiopure structural helicity, which results in strong optical activity in the range 200-450 nm, as confirmed by natural circular dichroism (NCD) spectra and the corresponding UV/Vis absorption spectra. Under irradiation with UV light, the Gd(III)-W(V) chains show dominant ligand-based red phosphorescence, with λmax ≈660 nm for 1-(SS/RR) and 680 nm for 3-(SRSR/RSRS). The Nd(III)-W(V) chains, 2-(SS/RR) and 4-(SRSR/RSRS), exhibit near-infrared luminescence with sharp lines at 986, 1066, and 1340 nm derived from intra-f (4)F3/2 → (4)I9/2,11/2,13/2 transitions of the Nd(III) centers. This emission is realized through efficient ligand-to-metal energy transfer from the Pybox derivative to the lanthanide ion. Due to the presence of paramagnetic lanthanide(III) and [W(V)(CN)8](3-) moieties connected by cyanide bridges, 1-(SS/RR) and 3-(SRSR/RSRS) are ferrimagnetic spin chains originating from antiferromagnetic coupling between Gd(III) (SGd = 7/2) and W(V) (SW = 1/2) centers with J1-(SS) = -0.96(1) cm(-1), J1-(RR) =-0.95(1) cm(-1), J3-(SRSR) = -0.91(1) cm(-1), and J3-(RSRS) =-0.94(1) cm(-1). 2-(SS/RR) and 4-(SRSR/RSRS) display ferromagnetic coupling within their Nd(III)-NC-W(V) linkages.

  8. Evidentiation of Paramyosin (Sm-97 as a Modulating Antigen on Granulomatous Hypersensitivity to Schistosoma mansoni Eggs

    Directory of Open Access Journals (Sweden)

    Hirsch Cristine

    1997-01-01

    Full Text Available A Schistosoma mansoni adult worm anionic fraction (PIII has previously been shown to protect mice against challenge infection and to reduce pulmonary and hepatic granulomatous hypersensitivity. Serum from PIII-immunized rabbit was used to screen a lgt11 cDNA library from S. mansoni adult worm in order to identify antigens capable of modulating granulomatous hypersensitivity. We obtained four clones with 400 (Sm-III.11, 900 (Sm-III.16, 1100 (Sm-III.10 and 1300 (Sm-III.12 bp of length. All clone-specific antibodies were able to recognize most of the PIII components. The sequence analysis showed that these clones presented high homology with S. mansoni paramyosin (Sm-97. These findings ascribe a new function to this antigen with an important role in modulation of granulomatous hypersensitivity to S. mansoni eggs

  9. Observation of unusual slow-relaxation of the magnetisation in a Gd-EDTA chelate.

    Science.gov (United States)

    Holmberg, Rebecca J; Ho, Le Tuan Anh; Ungur, Liviu; Korobkov, Ilia; Chibotaru, Liviu F; Murugesu, Muralee

    2015-12-21

    A Gadolinium EDTA chelate displays characteristic isotropic behaviour common of Gd(III) complexes under zero applied magnetic field, and anisotropic behaviour arising from dipolar coupling and weak spin-phonon coupling under an applied magnetic field. This surprising magnetic behaviour for Gd(III) is investigated using SQUID magnetometry and rationalized through theoretical calculations.

  10. Low-vibrational luminescent polymers including tris(bis-perfluoromethane and ethanesulfonylaminate)neodymium(III) with 8 coordinated DMSO-d{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Hasegawa, Yasuchika; Sogabe, Kensaku; Wada, Yuji; Yanagida, Shozo E-mail: yanagida@chem.eng.osaka-u.ac.jp

    2003-03-01

    Novel Nd(III) complexes, tris(bis-perfluoromethane and ethanesulfonylaminato)neodymium(III)octa(deuterated dimethylsulfoxide) were designed and synthesized to apply to luminescent materials in plastic optical fiber. The IR and the near-IR spectra analyses has been done to estimate the radiationless transition via vibrational excitation of the Nd(III) complexes. [Nd(pms){sub 3}(DMSO-d{sub 6}){sub 8}] and [Nd(pes){sub 3}(DMSO-d{sub 6}){sub 8}] in polyhexafluoroisopropylmethacrylate gave a emission quantum yield of 1.3% and 1.6%, which was the largest in luminescent Nd(III) polymers. A research field for telecommunication network using 1.3 {mu}m light would be achieved by luminescent Nd(III) materials encapsulated low-vibrational coordination sites.

  11. Removal of trivalent samarium from aqueous solutions by activated biochar derived from cactus fibres

    Institute of Scientific and Technical Information of China (English)

    Loukia Hadjittofi; Styliana Charalambous; Ioannis Pashalidis

    2016-01-01

    The efficiency of activated biochar fibres obtained fromOpuntia Ficus Indica regarding the sorption of trivalent samarium (Sm(III)) from aqueous solutions was investigated by batch experiments. The effect of various physicochemical parameters (e.g. pH, initial metal concentration, ionic strength, temperature and contact time) on the Sm(III) adsorption was studied and the surface species were characterized by FTIR spectroscopy prior to and after the lanthanide sorption. The experimental results showed that the acti-vated biochar fibres possessed extraordinary sorption capacity for Sm(III) in acidic solutions (qmax=90 g/kg, pH 3.0) and near neutral solutions (qmax=350 g/kg, pH 6.5). This was attributed to the formation of samarium complexes with the surface carboxylic moieties, available in high density on the lamellar structures of the bio-sorbent.

  12. Investigation of gas discharge impulse image intensifiers

    Energy Technology Data Exchange (ETDEWEB)

    Gushchin, E.M. E-mail: evgeni@phep.mephi.msk.su; Somov, S.V.; Timofeev, M.K

    1999-08-21

    The gas discharge impulse image intensifiers (GDIII) operated in the streamer mode are studied in this work. The GDIII has a resolution of 5-15 lines/cm and light amplification up to {approx}10{sup 10}. The possibility to design a single-electron GDIII for RICH-detectors is considered. For this purpose the emission of photoelectrons in He, Ne, Ar, Xe, CO{sub 2}, iC{sub 4}H{sub 10} and their mixtures in the 50-760 Torr pressure range have been investigated. The best working gas for the GDIII is Ne+({approx}0.1%)iC{sub 4}H{sub 10} mixture having an electron output factor up to 0.45.

  13. Investigation of gas discharge impulse image intensifiers

    CERN Document Server

    Gushchin, E M; Timofeev, M K

    1999-01-01

    The gas discharge impulse image intensifiers (GDIII) operated in the streamer mode are studied in this work. The GDIII has a resolution of 5-15 lines/cm and light amplification up to approx 10 sup 1 sup 0. The possibility to design a single-electron GDIII for RICH-detectors is considered. For this purpose the emission of photoelectrons in He, Ne, Ar, Xe, CO sub 2 , iC sub 4 H sub 1 sub 0 and their mixtures in the 50-760 Torr pressure range have been investigated. The best working gas for the GDIII is Ne+(approx 0.1%)iC sub 4 H sub 1 sub 0 mixture having an electron output factor up to 0.45.

  14. catena-Poly[[[tetraaquasamarium(III]-di-μ-isonicotinato-κ4O:O′] chloride

    Directory of Open Access Journals (Sweden)

    Ke-Jun Wu

    2008-01-01

    Full Text Available In the structure of the title compound, {[Sm(C6H4NO22(H2O4]Cl}n, the unique SmIII atom lies on a crystallographic twofold axis and is eight-coordinated by four O atoms from four isonicotinate ligands and four water molecules in a slightly distorted square-antiprismatic coodination environment. The SmIII atoms are bridged by two carboxylate groups of two isonicotinate ligands, forming an extended chain along the c-axis direction. These chains are cross-linked through hydrogen bonds, forming a three-dimensional framework, with channels which accommodate the chloride anions.

  15. Trichloridotris{N-[phenyl(pyridin-2-ylmethylidene]hydroxylamine-κ2N,N′}samarium(III

    Directory of Open Access Journals (Sweden)

    Yahong Li

    2012-03-01

    Full Text Available The SmIII ion in the title compound, [SmCl3(C12H10N2O3], shows a coordination number of nine with a slightly distorted tricapped trigonal prismatic geometry based on a Cl3N6 donor set. The molecular structure is stabilized by three intramolecular O—H...Cl hydrogen bonds.

  16. Solid-Liquid Extraction of Some Lanthanide Complexes with 1-Nitroso-2-Naphthol

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The extraction behavior of Sm(III), Eu(III) ,Er(III) and Yb(III) with 1- nitroso -2- naphthol (HA) in paraffin has been studied. The composition of extracted complexes has been determined to be LnA3 by slope analysis method. The effect of temperature on extraction system is also investigated and thermodynamic parameters are obtained.

  17. Crystal structure of a samarium(III nitrate chain cross-linked by a bis-carbamoylmethylphosphine oxide ligand

    Directory of Open Access Journals (Sweden)

    Julie A. Stoscup

    2014-10-01

    Full Text Available In the title compound poly[aquabis(μ-nitrato-κ4O,O′:O,O′′tetrakis(nitrato-κ2O,O′{μ4-tetraethyl [(ethane-1,2-diylbis(azanediylbis(2-oxoethane-2,1-diyl]diphosphonate-κ2O,O′}disamarium(III], [Sm2(NO36(C14H30N2O8P2(H2O]n, a 12-coordinate SmIII and a nine-coordinate SmIII cation are alternately linked via shared bis-bidentate nitrate anions into a corrugated chain extending parallel to the a axis. The nine-coordinate SmIII atom of this chain is also chelated by a bidentate, yet flexible, carbamoylmethylphoshine oxide (CMPO ligand and bears one water molecule. This water molecule is hydrogen bonded to nitrate groups bonded to the 12-coordinate SmIII cation. The CMPO ligand, which lies about an inversion center, links neighboring chains along the c axis, forming sheets parallel to the ac plane. Hydrogen bonds between the amide NH group and metal-bound nitrate anions are also present in these sheets. The sheets are packed along the b axis through only van der Waals interactions.

  18. First example of dissymmetrical lanthanide cryptates: synthesis and steady state photophysical properties

    Energy Technology Data Exchange (ETDEWEB)

    Bodar-Houillon, F.; Heck, R.; Bohnenkamp, W.; Marsura, A

    2002-11-15

    A new cryptate incorporating an unsymmetrical arch as 6-methyl-2-[3-(methyl)pyrazol-1'-yl]pyridine has been obtained in a good yield. The effect of the dissymmetry introduced by the pyrazole moiety on the corresponding Eu(III), Tb(III) and Sm(III) complex fluorescence behavior is discussed.

  19. Diglycolamide-functionalized calix[4]arene for Am(III) recovery from radioactive wastes: liquid membrane studies using a hollow fiber contactor

    NARCIS (Netherlands)

    Ansari, S.A.; Mohapatra, P.K.; Kandwal, P.; Verboom, Willem

    2016-01-01

    The transport of Am(III) from nitric acid feeds was investigated using hollow fiber supported liquid membrane (HFSLM) containing a diglycolamide-functionalized calix[4]arene (C4DGA) as the carrier extractant. The effect of feed acidity and Nd(III) concentration (used to represent Am(III)) in the

  20. Neodymium(III) Complexes of Dialkylphosphoric and Dialkylphosphonic Acids Relevant to Liquid-Liquid Extraction Systems

    Energy Technology Data Exchange (ETDEWEB)

    Lumetta, Gregg J.; Sinkov, Sergey I.; Krause, Jeanette A.; Sweet, Lucas E.

    2016-01-27

    The complexes formed during the extraction of neodymium(III) into hydrophobic solvents containing acidic organophosphorus extractants were probed by single-crystal X-ray diffractometry, visible spectrophotometry, and Fourier-transform infrared spectroscopy. The crystal structure of the compound Nd(DMP)3 (1, DMP = dimethyl phosphate) revealed a polymeric arrangement in which each Nd(III) center is surrounded by six DMP oxygen atoms in a pseudo-octahedral environment. Adjacent Nd(III) ions are bridged by (MeO)2POO– anions, forming the polymeric network. The diffuse reflectance visible spectrum of 1 is nearly identical to that of the solid that is formed when an n-dodecane solution of di-(2-ethylhexyl)phosphoric acid (HA) is saturated with Nd(III), indicating a similar coordination environment around the Nd center in the NdA3 solid. The visible spectrum of the HA solution fully loaded with Nd(III) is very similar to that of the NdA3 material, both displaying hypersensitive bands characteristic of an pseudo-octahedral coordination environment around Nd. These spectral characteristics persisted across a wide range of organic Nd concentrations, suggesting that the pseudo-octahedral coordination environment is maintained from dilute to saturated conditions.

  1. Synthesis and luminescence properties of encapsulated sol-gel glass samarium complexes.

    Science.gov (United States)

    Zaitoun, M A; Momani, K; Jaradat, Q; Qurashi, I M

    2013-11-01

    Luminescence efficiency of lanthanide complexes generally largely depend on the choice of the organic ligand and the host matrix in which these complexes are doped. Two Sm(III) complexes, namely: Sm(III) dithicarbamate - Sm(L1)3B [L1=(R)2NCS2B, R=C2H5 and B=1,10-phenanthroline] and Sm(III) complex with the polytonic ligand L2=N', N'(2)-bis[(1E)-1-(2-pyridyl)ethylidene]ethanedihydrazide {Sm2-L2-(CH3COO)2; L2=C16H16N6O2} are synthesized, these complexes are then trapped in sol-gel glass. Room temperature luminescence of Sm(L1)3B and {Sm2-L2-(CH3COO)2} complexes encapsulated in sol-gel glass are studied using a spectrofluorometer. Up on excitation by a UV light, ligand L1B absorbs this light and transfers it into the Sm(III) ions and emission bands were observed in the visible region and were attributed to f-f transitions of Sm(III). The observed emission indicated an efficient L1B ligand as a sensitizer, while ligand L2 shows no ability to work as a sensitizer. The branching ratio I4G5/2→6H9/2/I4G5/2→6H7/2) of electric dipole transition to magnetic dipole transition was used as an effective spectroscopic probe to predict symmetry of the site in which Sm(III) is located. The encapsulation of the Samaium complexes was performed for three reasons: (i) before rare earth (RE)-doped sol-gel glasses can be used in applications such as laser materials, several fluorescence quenching mechanisms must be overcome, we show in this work that lanthanide fluorescence is greatly enhanced by chelation and selecting a suitable host matrix (sol-gel) to accommodate the lanthanide complex, (ii) to improve the stability of the phosphor with efficient and high color-purity characteristics under ultraviolet excitation and (iii) this work provides a framework for preparing transparent composite glasses that are robust hosts to study the fundamental interactions between nano-materials and light.

  2. Ab initio study of the spin distribution and conductive properties of a Malonato-bridged gadolinium (III) complex

    Science.gov (United States)

    Zhu, L.; Yao, K. L.; Liu, Z. L.

    2007-10-01

    Ab initio computations within the full potential linearized augmented plane wave method with the generalized gradient approximation plus Hubbard potential approach were applied in the study of the electronic structures of the compound [Gd2(mal)3(H2O)6] . The present calculations show that the major part of the spin magnetic moment is from Gd(III) ions, and the origin of the ferromagnetic intermolecular interaction of the two interacting Gd(III) ions comes from the spin polarization effect through the oxo-carboxylato and carboxylato bridges. By analysis of the band structure, we find that the compound has a metallic property.

  3. Tetraaquabis(2,6-dihydroxybenzoato-κO1(2,6-dihydroxybenzoato-κ2O1,O1′gadolinium(III dihydrate

    Directory of Open Access Journals (Sweden)

    Juangang Wang

    2011-06-01

    Full Text Available In the title compound, [Gd(C7H5O43(H2O4]·2H2O, the GdIII ion shows a distorted square antiprismatic coordination formed by four aqua ligands and four O atoms from the three 2,6-dihydroxybenzoate (L ligands. Two L ligands coordinate the GdIII ion in a monodentate mode, while the third coordinates it in a bidentate–chelating coordination mode. An extensive three-dimensional O—H...O hydrogen-bonding network consolidates the crystal packing.

  4. Exceptional Oxygen Sensing Properties of New Blue Light-Excitable Highly Luminescent Europium(III) and Gadolinium(III) Complexes

    OpenAIRE

    Borisov, Sergey M.; Fischer, Roland; Saf, Robert; Klimant, Ingo

    2014-01-01

    New europium(III) and gadolinium(III) complexes bearing 8-hydroxyphenalenone antenna combine efficient absorption in the blue part of the spectrum and strong emission in polymers at room temperature. The Eu(III) complexes show characteristic red luminescence whereas the Gd(III) dyes are strongly phosphorescent. The luminescence quantum yields are about 20% for the Eu(III) complexes and 50% for the Gd(III) dyes. In contrast to most state-of-the-art Eu(III) complexes the new dyes are quenched v...

  5. Short-range correlations in d-f cyanido-bridged assemblies with XY and XY-Heisenberg anisotropy

    NARCIS (Netherlands)

    Tanase, S.; Evangelisti, M.; de Jongh, L. J.

    2011-01-01

    Two new d-f cyanido-bridged 1D assemblies [RE(pzam)3(H2O)Mo(CN)8]·H2O (RE = Sm(III), Er(III)) were synthesized and their magneto-structural properties have been studied by field-dependent magnetization and specific heat measurements at low temperatures (≥0.3 K). Below ≈ 10 K the ground state of both

  6. Two lanthanide-hydroxo clusters with different nuclearity: Synthesis, structures, luminescent and magnetic properties

    Science.gov (United States)

    Li, Xi-Li; Zhu, Cancan; Zhang, Xue-Li; Hu, Ming; Wang, Ai-Ling; Xiao, Hong-Ping

    2017-01-01

    Under the identical reaction conditions, two new TbIII and SmIII-hydroxo clusters with different nuclearity have been prepared and characterized by X-ray crystallography, spectroscopic methods and magnetic measurements. Solid-state structure analyses reveal that the TbIII cluster shows a pentanuclear square pyramidal shape of the composition [Tb5(μ3-OH)4(μ4-OH)(dbm)10]·2H2O (1, dbm- = dibenzoylmethanate) with the dbm ligands presenting two types of coordination modes [η2-and (μ-O)-η2-]. The SmIII species presents a tetranuclear parallelogram structure formulated as [Sm4(μ3-OH)2(dbm)10]·12H2O (2), and three types of coordination modes [η2-, (μ-O)-η2- and (μ-O)2-η2-] for dbm ligands are observed. The measurements of magnetic properties indicate that the direct-current (dc) magnetic behaviors of two clusters mainly result from the thermal depopulation of the Stark sublevels of the TbIII and SmIII ions, respectively. Meanwhile, alternating current (ac) magnetic susceptibility of 1 is also assessed. Investigations on luminescence properties show that 2 displays characteristic emission of the SmIII ion in visible range, while 1 does not exhibit any detectable emission. The interpretations of different emission behaviors for 1 and 2 are also presented in detail.

  7. 78 FR 77471 - Prospective Grant of Exclusive License for: Convection Enhanced Delivery of a Therapeutic Agent...

    Science.gov (United States)

    2013-12-23

    ... macromolecular MRI contrast agents such as chelated Gd(III). These macromolecular imaging agents have clearance... Enhanced Delivery of a Therapeutic Agent With a Surrogate Tracer for Treating Cancer and Urological... Agents'', U.S. Provisional Patent Application 60/413,673 (filed September 24, 2002;...

  8. Study on sorption of D155 resin for gadolinium

    Institute of Scientific and Technical Information of China (English)

    XIONG Chunhua

    2008-01-01

    The sorption behavior and mechanism of a Macroporous weak acid resin,(D155 resin,)for Gd(III) were investigated. The statically saturated sorption capacity is 283 mg/g resin at 298 K in HAc-NaAc medium. The Gd(III) adsorbed on macroporous weak acid resin,(D155 resin,)could be reductively eluted with the mixed solution of HCl and NaCl, and the elution percentage was as high as 100%. The resin could be regenerated and reused without remarkable decrease in sorption capacity. The apparent sorption rate constant was k298=1.98×10-5 s-1. The apparent activation energy was Ea=2.78 kJ/mol. The sorption behavior of D155 resin for Gd(III) obeyed the Langmuir isotherm. The thermodynamic sorption parameters were (H=33.0 kJ/mol, (S=192 J/mol/K, and (G298=-24.3 kJ/mol. The sorption mechanism of D155 resin for Gd(III) was examined by using chemical method and IR spectrometry. The coordination compound was formed between oxygen atoms in the functional group of D155 resin and Gd (III).

  9. Molybdate templated assembly of Ln12Mo4-type clusters (Ln = Sm, Eu, Gd) containing a truncated tetrahedron core.

    Science.gov (United States)

    Zheng, Yong; Zhang, Qian-Chong; Long, La-Sheng; Huang, Rong-Bin; Müller, Achim; Schnack, Jürgen; Zheng, Lan-Sun; Zheng, Zhiping

    2013-01-01

    Three heterometallic cluster complexes {Ln(12)Mo(4)} featuring an Ln(12) core of a distorted truncated tetrahedron were synthesized with the assistance of four MoO(4)(2-) anions as ancillary ligands. Magnetic studies of the {Gd(12)Mo(4)} cluster revealed a large magnetocaloric effect due to the presence of the large number of weakly coupled Gd(III) ions.

  10. Aqueous complexation of citrate with neodymium(III) and americium(III): a study by potentiometry, absorption spectrophotometry, microcalorimetry, and XAFS.

    Science.gov (United States)

    Brown, M Alex; Kropf, A Jeremy; Paulenova, Alena; Gelis, Artem V

    2014-05-07

    The aqueous complexation of Nd(III) and Am(III) with anions of citrate was studied by potentiometry, absorption spectrophotometry, microcalorimetry, and X-ray absorption fine structure (XAFS). Using potentiometric titration data fitting the metal-ligand (L) complexes that were identified for Nd(III) were NdHL, NdL, NdHL2, and NdL2; a review of trivalent metal-citrate complexes is also included. Stability constants for these complexes were calculated from potentiometric and spectrophotometric titrations. Microcalorimetric results concluded that the entropy term of complex formation is much more dominant than the enthalpy. XAFS results showed a dependence in the Debye-Waller factor that indicated Nd(iii)-citrate complexation over the pH range of 1.56-6.12.

  11. Tetrakis[μ-2-(4-hydroxyphenylacetato]-κ3O,O′:O;κ3O:O,O′-bis{aqua(4,4′-bipyridine-κNbis[2-(4-hydroxyphenylacetato-κ2O,O]neodymium(III} monohydrate

    Directory of Open Access Journals (Sweden)

    Jia-Lu Liu

    2010-11-01

    Full Text Available The title complex, [Nd2(C8H7O36(C10H8N22(H2O2]·H2O, contains two Nd atoms, six 4-hydroxyphenylacetate (hpaa anions, two 4,4′-bipyridine molecules (bipy and two water molecules; an additional water molecule of solvation is also present in the crystal structure. Each of the NdIII ions is nine-coordinated by seven O atoms from four hpaa ligands, an N atom from a bipy ligand and an O atom from a water molecule in a distorted tricapped trigonal-prismatic geometry. The hpaa ligands are coordinated to the NdIII ions in the bridging and bridging tridentate modes. Extensive O—H...O, O—H...N and C—H...O hydrogen bonding stabilizes the crystal structure.

  12. High Relaxivity Gd(III)–DNA Gold Nanostars: Investigation of Shape Effects on Proton Relaxation

    Science.gov (United States)

    Rotz, Matthew W.; Culver, Kayla S. B.; Parigi, Giacomo; MacRenaris, Keith W.; Luchinat, Claudio; Odom, Teri W.; Meade, Thomas J.

    2015-01-01

    Gadolinium(III) nanoconjugate contrast agents (CAs) have distinct advantages over their small-molecule counterparts in magnetic resonance imaging. In addition to increased Gd(III) payload, a significant improvement in proton relaxation efficiency, or relaxivity (r1), is often observed. In this work, we describe the synthesis and characterization of a nanoconjugate CA created by covalent attachment of Gd(III) to thiolated DNA (Gd(III)–DNA), followed by surface conjugation onto gold nanostars (DNA–Gd@stars). These conjugates exhibit remarkable r1 with values up to 98 mM−1 s−1. Additionally, DNA–Gd@stars show efficient Gd(III) delivery and biocompatibility in vitro and generate significant contrast enhancement when imaged at 7 T. Using nuclear magnetic relaxation dispersion analysis, we attribute the high performance of the DNA–Gd@stars to an increased contribution of second-sphere relaxivity compared to that of spherical CA equivalents (DNA–Gd@spheres). Importantly, the surface of the gold nanostar contains Gd(III)–DNA in regions of positive, negative, and neutral curvature. We hypothesize that the proton relaxation enhancement observed results from the presence of a unique hydrophilic environment produced by Gd(III)–DNA in these regions, which allows second-sphere water molecules to remain adjacent to Gd(III) ions for up to 10 times longer than diffusion. These results establish that particle shape and second-sphere relaxivity are important considerations in the design of Gd(III) nanoconjugate CAs. PMID:25723190

  13. Activity-Driven CNS Changes in Learning and Development

    Science.gov (United States)

    1991-04-14

    NY. 9. HICKEY, T. L. & R. W. GuiI.LERY. 1974. J. Comp. Neurol. 156: 239- 254. 10. SANDERSON , K. J. 1971. J. Cotmp. Neurol. 143: 101-118. I1. HUBEL. D...Neurocytol. 6: 211-230, 82 APpi M-oA ri. M. D., D. S. KLRR & P. W. L ND:III I1). 1987. Brain Res. 401: 401-400 83. BRANDON . J. G. & R. G. Coss. 1982

  14. Enhancing extraction ability by rational design of phosphoryl functionalized ionic liquids and mechanistic investigation on neodymium (III) extraction

    Institute of Scientific and Technical Information of China (English)

    王君平; 赵洁莹; 冯达; 康鑫淳; 孙云雨; 赵玲玲; 梁洪泽

    2016-01-01

    Four ionic liquids (ILs): 3-(diethoxyphosphoryl)propyl triphenylphosphinium hexafluorophosphate [Ph3PC3P(OEt)2][PF6] (IL-1), 3-(ethoxyphenylphosphoryl)propyl triphenylphosphinium hexafluorophosphate [Ph3PC3PPh(OEt)][PF6] (IL-2), 3-(diphenyl-phosphoryl)propyl triphenylphosphinium hexafluorophosphate [Ph3PC3P(Ph)2][PF6] (IL-3), and 3-(diethoxyphosphoryl)propyl triphenylphosphinium bis(trifluoromethanesulfonyl)imide [Ph3PC3P(OEt)2][NTf2] (IL-4) were synthesized and characterized by IR and31P,1H,13C NMR spectroscopy. The liquid-liquid extraction of neodymium(III) by these phosphorus functionalized ionic liquids (PFILs) diluted with common room temperature ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C6mim][NTf2] was studied. The extraction percentage of Nd(III) was measured as a function of various parameters, such as the ini-tial pH of aqueous phase, equilibrium time, temperature, and concentration of PFIL extractant. The influence of the nature of diluents and salting-out reagents on extraction was also investigated. The results indicated that the extraction process was exothermical and the extraction percentage of Nd(III) by IL-1 was the highest among the PFILs investigated. A possible metal complexation mechanism was proposed for the present PFIL/IL extraction system. And the loaded Nd(III) ions by PFIL could be stripped completely from the ionic liquid phase by 1 mol/L nitric acid.

  15. Gd(III)-induced Supramolecular Hydrogelation with Enhanced Magnetic Resonance Performance for Enzyme Detection

    Science.gov (United States)

    Hua, Yongquan; Pu, Guojuan; Ou, Caiwen; Zhang, Xiaoli; Wang, Ling; Sun, Jiangtao; Yang, Zhimou; Chen, Minsheng

    2017-01-01

    Here we report a supramolecular hydrogel based on Gd(III)-peptide complexes with dramatically enhanced magnetic resonance (MR) performance. The hydrogelations were formed by adding Gd(III) ion to the nanofiber dispersion of self-assembling peptides naphthalene-Gly-Phe-Phe-Tyr-Gly-Arg-Gly-Asp (Nap-GFFYGRGD) or naphthalene-Gly-Phe-Phe-Tyr-Gly-Arg-Gly-Glu (Nap-GFFYGRGE). We further showed that, by adjusting the molar ratio between Gd(III) and the corresponding peptide, the mechanical property of resulting gels could be fine-tuned. The longitudinal relaxivity (r1) of the Nap-GFFYGRGE-Gd(III) was 58.9 mM‑1 S‑1, which to our knowledge is the highest value for such peptide-Gd(III) complexes so far. Such an enhancement of r1 value could be applied for enzyme detection in aqueous solutions and cell lysates.

  16. catena-Poly[(μ2-3-carboxy-5-nitrobenzoato(μ3-5-nitrobenzene-1,3-dicarboxylato(1,10-phenanthrolinegadolinium(III

    Directory of Open Access Journals (Sweden)

    Zhi-Li Fang

    2010-10-01

    Full Text Available The crystal structure of the title complex, [Gd(C8H3NO6(C8H4NO6(C12H8N2]n, contains polymeric chains made up of GdIII atoms, 1,10-phenanthroline and fully or half-deprotonated 5-nitrobenzene-1,3-dicarboxylic acid (H2L ligands. The GdIII atom is coordinated in a distorted bicapped trigonal-prismatic fashion by six O atoms from two HL− and three L2− ligands, and by two N atoms from the 1,10-phenanthroline ligand. The L2− ligands bridge the Gd–phenanthroline units, forming chains running parallel to [100]. O—H...O hydrogen bonding as well as π–π stacking interactions with an interplanar distance of 3.599 (2 Å assemble neighboring polymeric chains.

  17. Electrochemical extraction of samarium from molten chlorides in pyrochemical processes

    Energy Technology Data Exchange (ETDEWEB)

    Castrillejo, Y., E-mail: ycastril@qa.uva.es [QUIANE/Dept Quimica Analitica, F. de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain); Fernandez, P. [QUIANE/Dept Quimica Analitica, F. de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain); Medina, J. [Dept Fisica Materia Condensada Cristalografia y Mineralogia, F. de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain); Hernandez, P. [Centro de Investigaciones Quimicas, Universidad Autonoma del Estado de Hidalgo, Carr. Pachuca-Tulancingo Km. 4.5, C.P. 42076 Pachuca, Hidalgo (Mexico); Barrado, E. [QUIANE/Dept Quimica Analitica, F. de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain)

    2011-10-01

    This work concerns the electrochemical extraction of samarium from molten chlorides. In this way, the electrochemical behaviour of samarium ions has been investigated in the eutectic LiCl-KCl at the surface of tungsten, aluminium and aluminium coated tungsten electrodes. On a W inert electrode the electro-reduction of Sm(III) takes place in only one soluble-soluble electrochemical step Sm(III)/Sm(II). The electrochemical system Sm(II)/Sm(0) has not been observed within the electrochemical window, because of the prior reduction of Li(I) ions from the solvent, which inhibits the electro-extraction of Sm species from the salt on such a substrate. Sm metal in contact with the melt react to give Li(0) according to the reaction: Sm(0) + 2Li(I) {r_reversible} Sm(II) + 2Li(0). On the contrary, on reactive Al electrodes the electrochemical system Sm(II)/Sm(0) was observed within the electroactive range. The potential shift of the redox couple is caused by the decrease of Sm activity in the metal phase due to the formation of Sm-Al alloys at the interface. The formation mechanism of the intermetallic compounds was studied in a melt containing: (i) both Sm(III) and Al(III) ions, using W and Al coated tungsten electrodes, and (ii) Sm(III) ions using an Al electrode. Analysis of the samples after potentiostatic electrolysis by X-ray diffraction and scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), allowed the identification of Al{sub 3}Sm and Al{sub 2}Sm.

  18. Electron paramagnetic resonance study of chosen gadolinium(III) sandwiched- and encapsulated-polyoxometalate complexes

    Energy Technology Data Exchange (ETDEWEB)

    Szyczewski, A.; Kruczynski, Z.; Pietrzak, J. [Uniwersytet Adama Mickiewicza, Poznan (Poland). Inst. Fizyki; Lis, S.; But, S.; Elbanowski, M. [Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan (Poland)

    1998-07-24

    The gadolinium(III) complexes with polyoxometalates were studied using X-band electron paramagnetic resonance (EPR) spectroscopy. We selected the following sandwiched complexes: Gd(SiW{sub 11}O{sub 39}){sub 2}{sup 13-} [I], GdW{sub 10}O{sub 36}{sup 9-} [II], Gd(P{sub 2}W{sub 17}O{sub 61}){sub 2}{sup 17-} [III], and encrypted [GdSb{sub 9}W{sub 17}O{sub 86}]{sup 16-} [IV], [GdP{sub 5}W{sub 30}O{sub 110}]{sup 12-} [V]. The EPR spectra obtained for the compounds I-III and IV-V differ markedly from the U-spectrum characteristic for Gd(III) in glasses. The values of the zero-field splitting parameter D for both kind of complexes studied have been estimated. Taking into account the spin-hamiltonian calculations, the existence of Gd(III) ion in two different surroundings, in a strong crystal field of rhombic symmetry and in a weak crystal field, is observed. The differences observed between the case I-III and IV-V seems to be related to a various coordination of the Gd(III) ion and its hydration degree. Our study shows a relation between the presence of particular g-values of the spectral lines and the number of the inner-sphere water molecules as well as the type of the Gd(III) complex (sandwiched and/or encrypted) in solid. (orig.) 14 refs.

  19. High performance magneto-fluorescent nanoparticles assembled from terbium and gadolinium 1,3-diketones

    OpenAIRE

    Zairov, Rustem; Mustafina, Asiya; Shamsutdinova, Nataliya; Nizameev, Irek; Moreira, Beatriz; Sudakova, Svetlana; Podyachev, Sergey; Fattakhova, Alfia; Safina, Gulnara; Lundstrom, Ingemar; Gubaidullin, Aidar; Vomiero, Alberto

    2017-01-01

    Polyelectrolyte-coated nanoparticles consisting of terbium and gadolinium complexes with calix[4]arene tetra-diketone ligand were first synthesized. The antenna effect of the ligand on Tb(III) green luminescence and the presence of water molecules in the coordination sphere of Gd(III) bring strong luminescent and magnetic performance to the core-shell nanoparticles. The size and the core-shell morphology of the colloids were studied using transmission electron microscopy and dynamic light sca...

  20. Tris(dibenzoylmethanido-κ2O,O′[(6S,8S-(+-7,7-dimethyl-3-(2-pyridyl-5,6,7,8-tetrahydro-6,8-methanoisoquinoline-κ2N,N′]gadolinium(III

    Directory of Open Access Journals (Sweden)

    Xi-Li Li

    2009-09-01

    Full Text Available In the title compound, [Gd(C15H11O23(C17H18N2], the GdIII atom is coordinated by six O atoms from three β-diketonate ligands and two N atoms from a chiral ligand LS,S-(+-7,7-dimethyl-3-(2-pyridyl-5,6,7,8-tetrahydro-6,8-methanoisoquinoline, in a coordination geometry best described as distorted square-antiprismatic.

  1. Tetrakis[μ-2-(3,4-dimethoxyphenylacetato]-κ4O:O′;κ3O,O′:O;κ3O:O,O′-bis{[2-(3,4-dimethoxyphenylacetato-κ2O,O′](1,10-phenanthroline-κ2N,N′samarium(III}

    Directory of Open Access Journals (Sweden)

    Jia-Lu Liu

    2010-11-01

    Full Text Available In the centrosymmetric dinuclear title complex, [Sm2(C10H11O46(C12H8N22], the SmIII ion is nine-coordinated by seven O atoms of five 2-(3,4-dimethoxyphenylacetate (DMPA ligands and two N atoms of one bis-chelating 1,10-phenanthroline (phen ligand, forming a distorted tricapped trigonal-prismatic environment. The DMPA ligands coordinate in bis-chelate, bridging and bridging tridentate modes. An intramolecular C—H...O hydrogen bond occurs. Intermolecular C—H...O interactions are also present in the crystal.

  2. Reductive Trapping of [(OC)5 W-W(CO)5 ](2-) in a Mixed-Valent Sm(II/III) Calix[4]pyrrolide Sandwich.

    Science.gov (United States)

    Deacon, Glen B; Guo, Zhifang; Junk, Peter C; Wang, Jun

    2017-07-10

    Reduction of tungsten hexacarbonyl by the divalent samarium(II) complex [Sm2 (N4 Et8 )(thf)4 ] ((N4 Et8 )(4-) =meso-octaethylcalix[4]pyrrolide) in toluene at ambient temperature gave the remarkable heteronuclear mixed-valent samarium(II/III)/tungsten complex [{(thf)2 Sm(II) (N4 Et8 )Sm(III) (thf)}2 {(μ-OC)2 W2 (CO)8 }], which features the trapping of a rare [W2 (CO)10 ](2-) anion with an unsupported W-W bond. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Synthesis and Structural Determination of Nine-Coordinate K[GdIII(edta)(H2O)3]·5H2O

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The title complex K[GdIII(edta)(H2O)3]·5H2O was synthesized, where edta denotes ethylenediamine-tetraacetic acid. The crystal and molecular structure of the complex were determined by single-crystal X-ray structure analysis. The crystal belongs to an orthorhombic crystal system and an Fdd2 space group. The complex anion [GdIII(edta)(H2O)3]- has a pseudo-monocapped square antiprismatic nine-coordinate structure in which six coordinate atoms (two N and four O) are from an edta ligand and three water molecules coordinate to GdIII ion directly. It can be predicted that GdIII ion can also form a nine-coordinate complex with ttha (triethylenetetraminehexaacetic acid) ligand, so the GdIII complex anion [GdIII(Httha)]2- can supply a free non-coordinate carboxyl group used for molecular embellishment in some biological molecules to form a contrast agent of Magnetic Resonance Imagine (MRI) with targeting function.

  4. Data acquisition in thermodynamic and electrochemical reduction in a Gd(III)/Gd system in LiF-CaF{sub 2} media

    Energy Technology Data Exchange (ETDEWEB)

    Nourry, C. [Laboratoire de Genie Chimique UMR 5503, Departement Procedes Electrochimiques, Universite Paul Sabatier, 31062 Toulouse cedex 9 (France); Massot, L. [Laboratoire de Genie Chimique UMR 5503, Departement Procedes Electrochimiques, Universite Paul Sabatier, 31062 Toulouse cedex 9 (France)], E-mail: massot@chimie.ups-tlse.fr; Chamelot, P.; Taxil, P. [Laboratoire de Genie Chimique UMR 5503, Departement Procedes Electrochimiques, Universite Paul Sabatier, 31062 Toulouse cedex 9 (France)

    2008-01-01

    The electrochemical reduction of GdF{sub 3} was studied in the LiF-CaF{sub 2} eutectic (77/23 mol%) on a tantalum electrode for various GdF{sub 3} concentrations in the 800-900 deg. C temperature range. A previous thermodynamic study showed that gadolinium trifluoride is reduced into metal in a one-step process: Gd{sup (III)}+3e{sup -}=Gd Cyclic voltammetry and square wave voltammetry were used to confirm this mechanism, and the results show that the electrochemical reduction process is limited by the diffusion of Gd(III) in the solution. The Gd(III) diffusion coefficient was calculated at different temperatures and the results obey the Arrhenius law with an activation energy of 83 {+-} 4 kJ mol{sup -1}. The activity coefficient of Gd(III) and the Gd(III)/Gd standard potential E{sup o} were determined in the melt at various temperatures and concentrations. The values obtained for the activity coefficients were close to 1 at the highest temperatures and between 1.3 and 1.6 at lower temperatures.

  5. First coordination compounds based on a bis(imino nitroxide) biradical and 4f metal ions: synthesis, crystal structures and magnetic properties.

    Science.gov (United States)

    Reis, Samira G; Briganti, Matteo; Martins, Daniel O T A; Akpinar, Handan; Calancea, Sergiu; Guedes, Guilherme P; Soriano, Stéphane; Andruh, Marius; Cassaro, Rafael A A; Lahti, Paul M; Totti, Federico; Vaz, Maria G F

    2016-02-21

    The synthesis, crystal structures and magnetic properties of two families of heterospin complexes containing lanthanide ions and a bis(imino nitroxide) biradical (IPhIN = 1-iodo-3,5-bis(4',4',5',5'-tetramethyl-4',5'-dihydro-1H-imidazole-1'-oxyl)benzene) are reported: in [Ln2(hfac)6(IPhIN)(H2O)2] compounds, two lanthanide ions [Ln = Gd(III) (1) and Dy(III) (2)] are coordinated to the biradical, and in [Ln(hfac)3(IPhIN)(H2O)] compounds, one lanthanide ion (Ln = Tb(III) (3), Gd(III) (4) or Dy(III) (5)) is coordinated to the biradical. Ferromagnetic intramolecular magnetic interactions between Gd(III) and the biradical were found for 1 and 4, while intramolecular magnetic interactions between the radicals were ferro- and antiferromagnetic, respectively. Compound 2 shows a field induced slow relaxation of magnetization, which (under an external applied field of 2 kOe) exhibits an activation energy barrier of ΔE/kB = 27 K and a pre-exponential factor of 1.4 × 10(-8) s. To support the magnetic characterization of compound 3ab initio calculations were also performed.

  6. Determination of gadolinium(III) ions in soil and sediment samples by a novel gadolinium membrane sensor based on 6-methyl-4-{l_brace}[1-(2-thienyl)methylidene]amino{r_brace}3-thioxo-3,4-dihydro-1,2,4 -triazin-5-(2H)-one

    Energy Technology Data Exchange (ETDEWEB)

    Zamani, Hassan Ali [Department of Chemistry, Quchan branch, Islamic Azad University, Quchan (Iran, Islamic Republic of)], E-mail: haszamani@yahoo.com; Rajabzadeh, Ghadir [Khorasan Science and Technology Park, Mashhad (Iran, Islamic Republic of); Ganjali, Mohammad Reza; Norouzi, Parviz [Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran (Iran, Islamic Republic of); Endocrine and Metabolism Research Center, Tehran University of Medical Sciences, Tehran (Iran, Islamic Republic of)

    2007-08-15

    Highly selective and sensitive poly(vinyl chloride) (PVC) membrane electrodes based on 6-methyl-4-{l_brace}[1-(2-thienyl)methylidene]amino{r_brace}3-thioxo-3,4-dihydro-1,2,4 -triazin-5-(2H)-one (MATDTO) as new carriers for gadolinium ion-selective electrode was reported. The membrane solutions containing PVC, o-nitrophenyl octyl ether (NPOE) as plasticizer, sodium tetraphenyl borate (NaTPB) as lipophilic ionic additive, and MATDTO, displays a calibration response for Gd{sup 3+} ions over a wide concentration range of 1.0 x 10{sup -6}-1.0 x 10{sup -1} M with Nernstian slopes of 19.8 {+-} 0.2 mV per decade and a detection limit as 5.8 x 10{sup -7} M. The sensor has a relatively fast response time of <10 s and can be used in the pH range 3.2-8.7 for at least 2 months without any significant divergence in potentials. The selectivity coefficients for mono-, di-, and trivalent cations indicate good selectivity for Gd(III) ions over a large number of interfering cations. The membrane sensor was used as an indicator electrode in the potentiometric titration of Gd(III) ions with EDTA. The proposed electrode was also applied to the determination of concentration of Gd(III) ions in soil and sediment samples and validation with CRMs.

  7. PARACEST properties of a dinuclear neodymium(III) complex bound to DNA or carbonate.

    Science.gov (United States)

    Nwe, Kido; Andolina, Christopher M; Huang, Ching-Hui; Morrow, Janet R

    2009-07-01

    A dinuclear Nd(III) macrocyclic complex of 1 (1,4-bis[1-(4,7,10-tris(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane]-p-xylene) and mononuclear complexes of 1,4,7-tris-1,4,7,10-tetraazacyclododecane, 2, and 1,4,7-tris[(N-N-diethyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane, 3, are prepared. Complexes of 1 and 2 give rise to a PARACEST (paramagnetic chemical exchange saturation transfer) peak from exchangeable amide protons that resonate approximately 12 ppm downfield from the bulk water proton resonance. The dinuclear Nd(III) complex is promising as a PARACEST contrast agent for MRI applications, because it has an optimal pH of 7.5 and the rate constant for amide proton exchange (2700 s(-1)) is nearly as large as it can be within slow exchange conditions with bulk water. Dinuclear Ln(2)(1) complexes (Ln(III) = Nd(III), Eu(III)) bind tightly to anionic ligands including carbonate, diethyl phosphate, and DNA. The CEST amide peak of Nd(2)(1) is enhanced by certain DNA sequences that contain hairpin loops, but decreases in the presence of diethyl phosphate or carbonate. Direct excitation luminescence studies of Eu(2)(1) show that double-stranded and hairpin-loop DNA sequences displace one water ligand on each Eu(III) center. DNA displaces carbonate ion despite the low dissociation constant for the Eu(2)(1) carbonate complex (K(d) = 15 microM). Enhancement of the CEST effect of a lanthanide complex by binding to DNA is a promising step toward the preparation of PARACEST agents containing DNA scaffolds.

  8. Extraction of neodymium on LiF-CaF{sub 2} eutectic mixture by formation of alloys on a reactive electrode; Extraction du neodyme du melange eutectique LiF-CaF{sub 2} par formation d'alliages sur electrode reactive

    Energy Technology Data Exchange (ETDEWEB)

    Nourry, C.; Massot, L.; Chamelot, P.; Taxil, P. [Universite Paul Sabatier, Lab. de Genie Chimique UMR 5503, Dept. Procedes Electrochimiques, 31 - Toulouse (France)

    2007-07-01

    This work deals more particularly with the extraction of the fission products of media of molten fluorides. During the running of a nuclear reactor, a lot of elements are produced whose a majority of rare earths; these last ones being neutron-absorbing, they diminish the yield of the fission reaction. It is then necessary to extract them of the reactional medium. Among the rare earths formed, neodymium is the main element. Its extraction is studied in molten fluoride media. The used solvent is the eutectic mixture LiF-CaF{sub 2} (79-21 % molar, T{sub f}=763 C). Experiments are carried out in 200 g of LiF-CaF{sub 2}, containing 1 g of NdF{sub 3}. In this medium, the neodymium is under an oxidized form Nd(III). Its extraction is carried out by electrochemical reduction under the form of Nd(0): Nd(III) + 3 e{sup -} {yields} Nd(0). The extraction rate of this element depends of the potential difference ({delta}E) between the reduction of Nd(III) into Nd(0) and the reduction of Li(I) into Li (solvent reduction). The reduction on inert electrode has been studied at first. This experiment type leads to extraction rates of about 95 %, insufficient for nuclear industry. This low yield is due to a weak value of {delta}E ({<=}0.2 V); a reduction on a reactive electrode has then been considered: Nd(III) + 3e{sup -} + xM {yields} M{sub x}Nd. The formation of alloy between the electrode substrate and the neodymium decreases the activity of this last ones, increasing thus {delta}E ({>=}0.5 V. This effect is called 'depolarization'. The electrodes substrates chosen for these experiments are the copper and the nickel. The alloys formation is revealed by electrochemical methods as well as by SEM-EDS. The formation enthalpies of different compounds defined are calculated with the 'potential relaxation' technique. The correlation between these results and the EDS observations allows to propose a formation mechanism of these different defined compounds. The

  9. Spectroscopic studies on unexpected complex azides of lanthanum(III) and neodymium(III)

    Science.gov (United States)

    Popitsch, A.; Mautner, A.; Fritzer, H. P.

    Solid azides of the types Cs 3La(N 3) 6, Cs 2Nd(N 3) 5, and Cs 4Nd(N 3) 7 can be prepared by metathetical reactions under special precautions. Electronic spectra in diffuse reflectance, infrared and Raman spectra, and magnetic susceptibilities versus temperature and field strength were measured on microcrystalline samples. The data of these new compounds are primarily discussed in view of vibrational properties of the azide ion N 3-, as ligand and in relation to first insights into the nature of the metal-nitrogen bonds within the coordination polyhedra of La(III) and Nd(III).

  10. Sensitization of visible and NIR emitting lanthanide(III) ions in noncentrosymmetric complexes of hexafluoroacetylacetone and unsubstituted monodentate pyrazole.

    Science.gov (United States)

    Ahmed, Zubair; Iftikhar, K

    2013-11-07

    A series of highly volatile eight-coordinate air and moisture stable lanthanide complexes of the type [Ln(hfaa)3(L)2] (Ln = Pr (1), Nd (2), Eu (3), Gd (4), Tb (5), Dy (6), Ho (7), Er (8), Tm (9), and Yb (10); hfaa = anion of hexafluoroacetylacetone and L = pyrazole) have been synthesized and characterized by elemental analysis, IR, ESI-MS(+), and NMR studies. Single-crystal X-ray structures have been determined for the Eu(III) and Dy(III) complexes. These complexes crystallize in the monoclinic space group P2(1)/c. The lanthanide ion in each of these complexes is eight-coordinate with six oxygen atoms from three hfaa and two N-atoms from two pyrazole units, forming a coordination polyhedron best describable as a distorted square antiprism. The NMR spectra reveal that both the pyrazole units remain attached to the metal in solution and the β-diketonate and pyrazole protons are shifted in opposite directions in the case of paramagnetic complexes. The lanthanide-induced chemical shifts are dipolar in nature. The hypersensitive transitions of Nd(III), Ho(III), and Er(III) are sensitive to the environment (solvent), which is reflected by the oscillator strength and band shape of these transitions. The band shape due to the hypersensitive transition of Nd(III) in noncoordinating chloroform and dichloromethane is similar to those of the typical eight-coordinate Nd(III) β-diketonate complexes. The quantum yield and lifetime of Pr(III), Eu(III), Tb(III), Dy(III), and Tm(III) in visible and Pr(III), Nd(III), Dy(III), Ho(III), Er(III) Tm(III), and Yb(III) in the NIR region are sizable. The environment around these metal ions is asymmetric, which leads to increased radiative rates and luminescence efficiencies. The quantum yield of the complexes reveal that ligand-to-metal energy transfer follows the order Eu(III) > Tb(III) ≫ Pr(III) > Dy(III) > Tm(III). Both ligands (hfaa and pyrazole) are good sensitizers for all the visible and NIR emitters effectively, except for Tb

  11. Spectroscopic characterization of bioactive carboxyamide with trinuclear lanthanide (III) ions

    Science.gov (United States)

    Singh, Bibhesh K.; Prakash, Anant; Adhikari, Devjani

    2009-10-01

    Complexes of La(III), Sm(III), Eu(III) and Tb(III) with bioactive carboxyamide ligands N',N″-bis(3-caboxy-1-oxophenelenyl)2-amino-N-arylbenzamidine have been synthesized and characterized by various physico-chemical techniques. Mass spectrum explains the successive degradation of the molecular species in solution and justifies ML complexes. Vibrational spectra indicate coordination of Ln(III) with amide and carboxylate oxygen of the ligand along with nitrate ions. The magnetic moment of Sm(III) and Eu(III) complexes showed slightly higher-values which originated due to low J- J separation leading to thermal population of next higher energy J levels and susceptibility due to first order Zeeman effect. The strong luminescence emitting peaks at 587 nm for Eu(III) and 543 nm for Tb(III) can be observed, which could be attributed to the ligand have an enhanced effect to the luminescence intensity of the Eu(III) and Tb(III). The thermal behaviour of complexes shows that water molecules and nitrate ion are removed in first step followed by the removal of two molecules of nitrate ions and then decomposition of the ligand molecule in subsequent step. Kinetic and thermodynamic parameters were computed from the thermal data using Coats and Redferm method, which confirm first order kinetics.

  12. Effect of second ligand on the luminescence of Samarium (III) dibenzoylmethane complexes: Syntheses, crystal structures, thermal analysis and luminescence study

    Indian Academy of Sciences (India)

    Muhammad Idiris Saleh; Min Yee Choo; Tai Wei Chan; Mohd R Razali

    2015-12-01

    The ternary complexes of Sm(III) with dibenzoylmethane (dbm) were synthesized by introducing 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dmphen), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen), 4,7-diphenyl-1,10-phenanthroline (dpphen), 2,2-bipyridyl (bpy), 4,4’-dimethyl-2,2-bipyridyl (4,4-dmbpy), 5,5’-dimethyl-2,2-bipyridyl (5,5-dmbpy) and 4,4’-di-tert-butyl-2,2-bipyridyl (4,4-dtbbpy) as a second ligand. The complexes were isolated and characterized by elemental analysis (CHN), thermogravimetric analysis (TGA), IR spectroscopy, luminescence spectroscopy and single crystal X-ray diffraction. Structural study shows that in all complexes Sm(III) is in square antiprism geometry. All complexes emit strong luminescence under ultraviolet excitation. The strongest emission is at 643 nm which can be assigned for 4G5/2 to 6H9/2 transition, equivalent to energy of 15550 cm−1. The addition of the second ligand has increased the emission intensity of the complexes while the transition is maintained.

  13. {6,6′-Dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne]diphenolato-1κ4O1,O1′,O6,O6′:2κ4O1,N,N′,O1′}(ethanol-1κO-μ-nitrato-1:2κ2O:O′-dinitrato-1κ4O,O′-samarium(IIIzinc(II

    Directory of Open Access Journals (Sweden)

    Qiang Huang

    2009-10-01

    Full Text Available In the title heteronuclear ZnII–SmIII complex, [SmZn(C18H18N2O4(NO33(CH3CH2OH], with the hexadentate Schiff base compartmental ligand N,N′-bis(3-methoxysalicylideneethylenediamine (H2L, the SmIII and ZnII ions are triply bridged by two phenolate O atoms from the Schiff base ligand and one nitrate anion. The five-coordinate ZnII ion is in a square-pyramidal geometry formed by the donor centers of two imine N atoms, two phenolate O atoms and one of the bridging nitrate O atoms. The SmIII center is in a ten-fold coordination of O atoms, involving the phenolate O atoms, two methoxy O atoms, one ethanol O atom, and two O atoms from two nitrate anions and one from the bridging nitrate anion. In the crystal, intermolecular O—H...O and C—H...O interactions generate a layer structure extending parallel to (101.

  14. Actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP): FY94 results

    Energy Technology Data Exchange (ETDEWEB)

    Novak, C.F. [ed.

    1995-08-01

    This document contains six reports on actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP). These reports, completed in FY94, are relevant to the estimation of the potential dissolved actinide concentrations in WIPP brines under repository breach scenarios. Estimates of potential dissolved actinide concentrations are necessary for WIPP performance assessment calculations. The specific topics covered within this document are: the complexation of oxalate with Th(IV) and U(VI); the stability of Pu(VI) in one WIPP-specific brine environment both with and without carbonate present; the solubility of Nd(III) in a WIPP Salado brine surrogate as a function of hydrogen ion concentration; the steady-state dissolved plutonium concentrations in a synthetic WIPP Culebra brine surrogate; the development of a model for Nd(III) solubility and speciation in dilute to concentrated sodium carbonate and sodium bicarbonate solutions; and the development of a model for Np(V) solubility and speciation in dilute to concentrated sodium Perchlorate, sodium carbonate, and sodium chloride media.

  15. Electrochemical extraction of neodymium by co-reduction with aluminum in LiCl-KCl molten salt

    Science.gov (United States)

    Yan, Yong-De; Xu, Yan-Lu; Zhang, Mi-Lin; Xue, Yun; Han, Wei; Huang, Ying; Chen, Qiong; Zhang, Zhi-Jian

    2013-02-01

    The electrochemical behavior of Nd(III) ions in LiCl-KCl and LiCl-KCl-AlCl3 melts on a Mo electrode at 723 K was studied by various electrochemical techniques. The results showed that Nd(III) ions are reduced to Nd(0) through two consecutive steps, and the underpotential deposition of neodymium on pre-deposited Al electrode formed two kinds of Al-Nd intermetallic compounds in LiCl-KCl-AlCl3 solutions. The electrochemical extraction of neodymium was carried out in LiCl-KCl-AlCl3 melts on a Mo electrode at 873 K by potentiostatic and galvanostatic electrolysis. The extraction efficiency was 99.25% after potentiostatic electrolysis for 30 h. Al-Li-Nd bulk alloy was obtained by galvanostatic electrolysis. X-ray diffraction (XRD) suggested that Al2Nd and Al3Nd phases were formed in Al-Li-Nd alloy. The microstructure and micro-zone chemical analysis of Al-Li-Nd alloy were characterized by scanning electron microscopy (SEM) with energy dispersive spectrometry (EDS), respectively.

  16. Electrochemical extraction of neodymium by co-reduction with aluminum in LiCl–KCl molten salt

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Yong-De, E-mail: y5d2006@hrbeu.edu.cn [Key Discipline Laboratory of Nuclear Safety and Simulation Technology, Harbin Engineering University, Harbin 150001 (China); Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); Xu, Yan-Lu [Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); Zhang, Mi-Lin, E-mail: zhangmilin@hrbeu.edu.cn [Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); Xue, Yun [Key Discipline Laboratory of Nuclear Safety and Simulation Technology, Harbin Engineering University, Harbin 150001 (China); Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); Han, Wei; Huang, Ying; Chen, Qiong [Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); Zhang, Zhi-Jian [Key Discipline Laboratory of Nuclear Safety and Simulation Technology, Harbin Engineering University, Harbin 150001 (China)

    2013-02-15

    The electrochemical behavior of Nd(III) ions in LiCl–KCl and LiCl–KCl–AlCl{sub 3} melts on a Mo electrode at 723 K was studied by various electrochemical techniques. The results showed that Nd(III) ions are reduced to Nd(0) through two consecutive steps, and the underpotential deposition of neodymium on pre-deposited Al electrode formed two kinds of Al–Nd intermetallic compounds in LiCl–KCl–AlCl{sub 3} solutions. The electrochemical extraction of neodymium was carried out in LiCl–KCl–AlCl{sub 3} melts on a Mo electrode at 873 K by potentiostatic and galvanostatic electrolysis. The extraction efficiency was 99.25% after potentiostatic electrolysis for 30 h. Al–Li–Nd bulk alloy was obtained by galvanostatic electrolysis. X-ray diffraction (XRD) suggested that Al{sub 2}Nd and Al{sub 3}Nd phases were formed in Al–Li–Nd alloy. The microstructure and micro-zone chemical analysis of Al–Li–Nd alloy were characterized by scanning electron microscopy (SEM) with energy dispersive spectrometry (EDS), respectively.

  17. Aquadipicrato(tetraethylene glycolgadolinium(III picrate methanol hemisolvate

    Directory of Open Access Journals (Sweden)

    Hoong-Kun Fun

    2008-09-01

    Full Text Available The asymmetric unit of the title compound [systematic name: aquabis(2,4,6-trinitrophenolato(3,6,9-trioxaundecane-1,11-diolgadolinium(III 2,4,6-trinitrophenolate methanol hemisolvate], [Gd(C6H2N3O72(C8H18O5(H2O](C6H2N3O7·0.5CH4O, contains two crystallographically independent GdIII complex cations with two uncoordinated picrate anions and one methanol molecule. Each GdIII atom has nine coordination sites occupied by five O atoms of tetraethylene glycol as a pentadentate ligand, one O atom of a water molecule and three O atoms of the two picrate anions as bidentate and monodentate ligands. The geometry is distorted tricapped trigonal prismatic. The mean planes of the two coordinated mono- and bidentate picrate ligands to the GdIII center are almost perpendicular to each other, as indicated by the dihedral angles of 89.92 (8 and 86.60 (8° in the two complex cations. The ions are arranged in a two-dimensional network parallel to the ac plane. Short O...O and N...O contacts between the nitro groups, intramolecular C—H...O hydrogen bonds, intermolecular O—H...O, O—H...N and C—H...O hydrogen bonds, and two π–π interactions between benzene rings [centroid–centroid distances = 3.8073 (10–3.9831 (10 Å] are observed. The methanol solvent molecule is disordered over two positions, with site-occupancy factors of ca 0.6 and 0.4.

  18. Lanthanide Coordination Polymers with 4,4'-Azobenzoic Acid: Enhanced Stability and Magnetocaloric Effect by Removing Guest Solvents.

    Science.gov (United States)

    Zhang, Shaowei; Duan, Eryue; Han, Zongsu; Li, Leilei; Cheng, Peng

    2015-07-06

    Three lanthanide coordination polymers (Ln-CPs) formulated as [Ln(azdc)(HCOO)]n [Ln = Gd(III) (1), Tb(III) (2), Dy(III) (3); H2azdc = 4,4'-azobenzoic acid] have been successfully obtained by the solvothermal reaction of Ln(III) ions with H2azdc ligands in the mixed solvent N,N-dimethylformamide (DMF)/H2O. Compared with our previous work on Ln-CPs with H2azdc ligands, [Gd2(azdc)3(DMA)2]n·2nDMA (1'; DMA = dimethylacetamide), in which the DMA molecules coordinate to Gd(III) ions that are replaced by HCOO(-) groups in 1, resulting in the distinct structures and properties of the final products. Adjacent Ln(III) ions in 1-3 are connected by HCOO(-) groups through bridging and chelating modes to give 2D layers, which are further linked by azdc(2-) ligands to produce 3D frameworks. Magnetic results declare that antiferromagnetic couplings exist in 1, although two different magnetic interactions among adjacent Gd(III) ions derived from antiferromagnetic interactions of the smaller Gd-O-Gd angles (Gd···Gd distances) and weak ferromagnetic interactions of the larger Gd-O-Gd angles (Gd···Gd distances) coexist in 1. Furthermore, the magnetocaloric effect (MCE) value of 1 is 1.5 times as large as that of 1'. More importantly, 1 exhibits excellent stabilities toward air, thermal, solvent, and acid/alkaline conditions. The results manifest that the crystalline structure of 1 can be stable at at least 425 °C supported by the in situ variable-temperature powder X-ray diffraction patterns and thermogravimetric analyses, in air for at least 3 months, and in common solvents for more than 1 week, as well as in aqueous solutions ranging from pH = 2 to 12 for more than 1 week.

  19. Increasing the luminescence of lanthanide(III) macrocyclic complexes by the use of polymers and lanthanide enhanced luminescence

    Science.gov (United States)

    Leif, Robert C.; Becker, Margie C.; Bromm, Alfred J., Jr.; Vallarino, Lidia M.; Williams, Steven A.; Yang, Sean

    2001-05-01

    A Eu (III)-macrocycle-isothiocyanate, Quantum DyeTM, has been reacted with lysine homo- and hetero-peptides to give polymers with multiple luminescent side chains. Contrary to the concentration quenching that occurs with conventional organic fluorophores, the attachment of multiple Quantum Dyes to a polymer results in a concomitant increase in luminescence. The emission intensity of the peptide-bound Quantum Dye units is approximately linearly related to their number. The attachment of peptides containing multiple lanthanide (III) macrocycles to analyte-binding species is facilitated by employing solid-phase technology. Bead-bound peptides are first labeled with multiple Quantum Dye units, then conjugated to an antibody, and finally released from the bead by specific cleavage with Proteinase K unedr physiological conditions. Since the luminescence of lanthanide(III) macrocycles is enhanced by the presence of GD(III) or Y(III) ions in a micellar system, a significant increase in signal can be achieved by attaching a polymer labeled with multiple Quantum Dye units to an analyte- binding species, such as a monoclonal antibody, or by taking advantage of the luminescence enhancing effects of Gd(III) or Y(III), or by both approaches concomitantly. A comparison between the integrated intensity and lifetime measurements of the Eu(III)-macrocycle under a variety of conditions show that the signal increase caused by Gd(III) can not be explained solely by the increase in lifetime, and must result in significant part from an energy transfer process invloving donors not directly bound to the Eu(III).

  20. Biodegradable Polysilsesquioxane Nanoparticles as Efficient Contrast Agents for Magnetic Resonance Imaging

    Science.gov (United States)

    Vivero-Escoto, Juan L.; Rieter, William J.; Lau, Honam; Huxford-Phillips, Rachel C.

    2013-01-01

    Polysilsesquioxane (PSQ) nanoparticles are crosslinked homopolymers formed by condensation of functionalized trialkoxysilanes, and provide an interesting platform for developing biologically and biomedically relevant nanomaterials. In this work, the design and synthesis of biodegradable PSQ particles with extremely high payloads of paramagnetic Gd(III) centers is explored, for use as efficient contrast agents for magnetic resonance imaging (MRI). Two new bis(trialkoxysilyl) derivatives of Gd(III) diethylenetriamine pentaacetate (Gd-DTPA) containing disulfide linkages are synthesized and used to form biodegradable Gd-PSQ particles by base-catalyzed condensation reactions in reverse microemulsions. The Gd-PSQ particles, PSQ-1 and PSQ-2, carry 53.8 wt% and 49.3 wt% of Gd-DTPA derivatives, respectively. In addition, the surface carboxy groups on the PSQ-2 particles can be modified with polyethylene glycol (PEG) and the anisamide (AA) ligand to enhance biocompatibility and cell uptake, respectively. The Gd-PSQ particles are readily degradable to release the constituent Gd(III) chelates in the presence of endogenous reducing agents such as cysteine and glutathione. The MR relaxivities of the Gd-PSQ particles are determined using a 3T MR scanner, with r1 values ranging from 5.9 to 17.8 mMs−1 on a per-Gd basis. Finally, the high sensitivity of the Gd-PSQ particles as T1-weighted MR contrast agents is demonstrated with in vitro MR imaging of human lung and pancreatic cancer cells. The enhanced efficiency of the anisamide-functionalized PSQ-2 particles as a contrast agent is corroborated by both confocal laser scanning microscopy imaging and ICP-MS analysis of Gd content in vitro. PMID:23613450

  1. Synthesis, structure and luminescence property of 2D lanthanide complexes with 3-fluorophthalate and oxalate

    Energy Technology Data Exchange (ETDEWEB)

    Cha, Yu-E [Department of Chemistry, Capital Normal University, Beijing 100048 (China); Li, Xia, E-mail: xiali@mail.cnu.edu.cn [Department of Chemistry, Capital Normal University, Beijing 100048 (China); Song, Shuang [Department of Chemistry, Capital Normal University, Beijing 100048 (China)

    2012-12-15

    Complexes [Ln{sub 2}(fpht){sub 2}(ox)(H{sub 2}O){sub 4}]{center_dot}H{sub 2}O (Ln=Sm 1, Eu 2, Tb 3 and Dy 4; fpht=3-fluorophthalate and ox=oxalate) have been synthesized and structurally characterized by single crystal X-ray diffraction. The four complexes possess similar 2D framework structures constructed from Ln-fpht double-stranded helices and ox linkages. Complexes 2 and 3 display the characteristic emission {sup 5}D{sub 0}{yields}{sup 7}F{sub J} (J=0-4) transitions of Eu(III) ion and {sup 5}D{sub 4}{yields}{sup 7}F{sub J} (J=6-3) transitions of Tb(III) ion, respectively. The emission decay curves reveal a monoexponential behavior yielding the lifetime values of 0.266{+-}0.002 ms for 2 and 0.733{+-}0.002 ms for 3. The emission spectrum of 1 shows three weak bands corresponding to the characteristic emission {sup 4}G{sub 5/2}{yields}{sup 6}H{sub 5/2}, {sup 4}G{sub 5/2}{yields}{sup 6}H{sub 7/2} and {sup 4}G{sub 5/2}{yields}{sup 6}H{sub 9/2} transitions of Sm(III) ion. The emission spectrum of 4 displays a broad band centered at 438 nm, which comes from the {pi}{sup Low-Asterisk }-{pi} transition of the ligand. - Graphical abstract: Complexes [Ln{sub 2}(fpht){sub 2}(ox)(H{sub 2}O){sub 4}]{center_dot}H{sub 2}O (fpht=3-fluorophthalate, ox=oxalate) possess 2D structures. Sm(III), Eu(III) and Tb(III) complexes show the characteristic fluorescent emission of the Ln(III). Dy(III) complex displays ligand-based luminescent behavior. Highlights: Black-Right-Pointing-Pointer [Ln{sub 2}(fpht){sub 2}(ox)(H{sub 2}O){sub 4}]{center_dot}H{sub 2}O (fpht=3-fluorophthalate; ox=oxalate) show 2D structures. Black-Right-Pointing-Pointer The 2D structures are constructed from Ln-fpht double-stranded helices and ox linkage. Black-Right-Pointing-Pointer The Sm(III), Eu(III) and Tb(III) complexes show the characteristic emission of the Ln(III) ions. Black-Right-Pointing-Pointer Dy(III) complex displays ligand-based luminescent behavior.

  2. Gadolinium oxalate derivatives with enhanced magnetocaloric effect via ionothermal synthesis.

    Science.gov (United States)

    Meng, Yan; Chen, Yan-Cong; Zhang, Ze-Min; Lin, Zhuo-Jia; Tong, Ming-Liang

    2014-09-02

    Two new oxalate-bridged Gd(III) coordination polymers, namely, (choline)[Gd(C2O4)(H2O)3Cl]Cl·H2O (1) and [Gd(C2O4)(H2O)3Cl] (2), were first obtained ionothermally by using a deep eutectic solvent (DES). The magnetic studies and heat capacity measurements reveal that the two-dimensional Gd(III)-based coordination polymer of 2 has the higher magnetic density and exhibits a larger cryogenic magnetocaloric effect (MCE) (ΔS(m) = 48 J kg(-1) K(-1) for ΔH = 7 T at 2.2 K).

  3. (4-Aminobenzenesulfonatoheptaaquagadolinium(III 4-aminobenzenesulfonate nitrate 4,4′-bipyridyl tetrasolvate dihydrate

    Directory of Open Access Journals (Sweden)

    Lujiang Hao

    2010-07-01

    Full Text Available In the title compound, [Gd(C6H6O3S(H2O7](C6H6O3S(NO3·4C10H8N2·2H2O, the GdIII ion is octacoordinated by seven water molecules and one O-bonded 4-aminobenzenesulfonate anion in a square-antiprismatic arrangement. In the crystal, the components are linked by N—H...O, O—H...N and O—H...O hydrogen bonds.

  4. μ-Acetato-diacetato{μ-6,6′-dimethoxy-2,2′-[o-phenylenebis(nitrilomethanylylidene]diphenolato}gadolinium(IIIzinc

    Directory of Open Access Journals (Sweden)

    Fan Yang

    2011-09-01

    Full Text Available In the heterodinuclear title complex, [GdZn(C22H18N2O4(CH3COO3], the ZnII ion is five-coordinated in a square-pyramidal environment defined by two O atoms and two N atoms from the ligand, forming the square plane, and one acetate O atom serving as the apex, while the GdIII ion is nine-coordinated in an approximate mono-capped tetragonal–antiprismatic environment defined by four O atoms from the ligand and five acetate O atoms.

  5. Gadolinium(III)-sensitized fluorescence of europium in its mixed-metal compounds with trifluroacetate

    Science.gov (United States)

    Kalinovskaya, I. V.; Zadorozhnaya, A. N.

    2017-04-01

    The fluorescence properties of mixed-metal compounds of Eu(III) and Gd(III) with trifluoroacetic acid, Eu1-xGdx(C2F3O2)3·yD·zH2O, where D - 1,10-phenanthroline, 2,2-dipyridil, diphenylguanidine, x = 0, 0.25, 0.5, or 0.7, were studied. Luminescence spectroscopic evidence and the examination of excitation spectra indicate the occurrence of efficient energy transfer from the gadolinium to the europium ion. The greatest promotion of Eu3+ photoluminescence at 615 nm is observed when Eu:Gd = 1:1.

  6. Proton Exchange in a Paramagnetic Chemical Exchange Saturation Transfer Agent from Experimental Studies and ab Initio Metadynamics Simulation.

    Science.gov (United States)

    Pollet, Rodolphe; Bonnet, Célia S; Retailleau, Pascal; Durand, Philippe; Tóth, Éva

    2017-03-27

    The proton-exchange process between water and a carbamate has been studied experimentally and theoretically in a lanthanide-based paramagnetic chemical exchange saturation transfer agent endowed with potential multimodality detection capabilities (optical imaging, or T1 MRI for the Gd(III) analogue). In addition to an in-depth structural analysis by a combined approach (using X-ray crystallography, NMR, and molecular dynamics), our ab initio simulation in aqueous solution sheds light on the reaction mechanism for this proton exchange, which involves structural Grotthuss diffusion.

  7. Assembly, crystal structure, and luminescent properties of three-dimensional (10,3)-a netted rare earth coordination polymers

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Solid complexes [REL(NO3)3]n with novel (10,3)-a type three-dimensional networks structure have been assembled using rare earth nitrates and an amide type semirigid tripodal bridging ligand, 1,3,5-tris {[(2′-benzylaminoformyl)phenoxyl]methyl}benzene (L), as building blocks. The complexes were crys- tallized in the orthorhombic system with chiral space group P212121. The whole structure consists of an infinite array of trigonal RE(III) ions bridged by tridentate ligands, and a novel (10,3)-a net is formed, which is very uncommon in the rare earth complexes. At room temperature, the Sm(III), Eu(III), Tb(III), Dy(III) complexes all exhibited characteristic luminescence emissions of central metal ions under UV light excitation.

  8. [(2R,3S-Butane-1,2,3,4-tetraol-κ3O1,O2,O3](ethanol-κOtris(nitrato-κ2O,O′samarium(III

    Directory of Open Access Journals (Sweden)

    Jun-Hui Xue

    2013-04-01

    Full Text Available The title SmIII–erythritol complex, [Sm(NO33(C2H6O(C4H10O4], is isotypic with its Nd, Eu, Y, Gd, Tb and Ho analogues. The SmIII cation exhibits a coordination number of ten and is chelated by a tridentate erythritol ligand and three bidentate nitrate anions. It is additionally coordinated by an O atom of an ethanol molecule, completing an irregular coordination sphere. The Sm—O bond lengths range from 2.416 (2 to 2.611 (2 Å. In the crystal, extensive O—H...O hydrogen bonding involving all hydroxy groups and some of the nitrate O atoms links the molecules into a three-dimensional network.

  9. Brilliant Sm, Eu, Tb and Dy chiral lanthanide complexes withstrong circularly polarized luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Petoud, Stephane; Muller, Gilles; Moore, Evan G.; Xu, Jide; Sokolnicki, Jurek; Riehl, James P.; Le, Uyen; Cohen, Seth M.; Raymond,Kenneth N.

    2006-07-10

    The synthesis, characterization and luminescent behavior of trivalent Sm, Eu, Dy and Tb complexes of two enantiomeric, octadentate, chiral, 2-hydroxyisophthalamide ligands are reported. These complexes are highly luminescent in solution. Functionalization of the achiral parent ligand with a chiral 1-phenylethylamine substituent on the open face of the complex in close proximity to the metal center yields complexes with strong circularly polarized luminescence (CPL) activity. This appears to be the first example of a system utilizing the same ligand architecture to sensitize four different lanthanide cations and display CPL activity. The luminescence dissymmetry factor, g{sub lum}, recorded for the Eu(III) complex is one of the highest values reported, and this is the first time the CPL effect has been demonstrated for a Sm(III) complex with a chiral ligand. The combination of high luminescence intensity with CPL activity should enable new bioanalytical applications of macromolecules in chiral environments.

  10. Synthesis, characterization and luminescent properties of lanthanide complexes with a novel multipodal ligand.

    Science.gov (United States)

    Yan, Zhen-Zhong; Hou, Na; Wang, Cong-Min

    2015-02-25

    Solid complexes of lanthanide nitrates with an novel multipodal ligand, 1,2,4,5-tetramethyl-3,6-bis{N,N-bis[((2'-furfurylaminoformyl)phenoxyl)ethyl]-aminomethyl}-benzene (L) have been synthesized and characterized by elemental analysis, infrared spectra and molar conductivity measurements. At the same time, the luminescent properties of the Sm(III), Eu(III), Tb(III) and Dy(III) nitrate complexes in solid state were investigated. Under the excitation of UV light, these complexes exhibited characteristic emission of central metal ions. The lowest triplet state energy level of the ligand indicates that the triplet state energy level (T1) of the ligand matches better the resonance level of Tb(III) than other lanthanide ions.

  11. Preparation of hollow core/shell microspheres of hematite and its adsorption ability for samarium.

    Science.gov (United States)

    Yu, Sheng-Hui; Yao, Qi-Zhi; Zhou, Gen-Tao; Fu, Sheng-Quan

    2014-07-01

    Hollow core/shell hematite microspheres with diameter of ca. 1-2 μm have been successfully achieved by calcining the precursor composite microspheres of pyrite and polyvinylpyrrolidone (PVP) in air. The synthesized products were characterized by a wide range of techniques including powder X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), and Brunauer-Emmett-Teller (BET) gas sorptometry. Temperature- and time-dependent experiments unveil that the precursor pyrite-PVP composite microspheres finally transform into hollow core/shell hematite microspheres in air through a multistep process including the oxidation and sulfation of pyrite, combustion of PVP occluded in the precursor, desulfation, aggregation, and fusion of nanosized hematite as well as mass transportation from the interior to the exterior of the microspheres. The formation of the hollow core/shell microspheres dominantly depends on the calcination temperature under current experimental conditions, and the aggregation of hematite nanocrystals and the core shrinking during the oxidation of pyrite are responsible for the formation of the hollow structures. Moreover, the adsorption ability of the hematite for Sm(III) was also tested. The results exhibit that the hematite microspheres have good adsorption activity for trivalent samarium, and that its adsorption capacity strongly depends on the pH of the solution, and the maximum adsorption capacity for Sm(III) is 14.48 mg/g at neutral pH. As samarium is a typical member of the lanthanide series, our results suggest that the hollow hematite microspheres have potential application in removal of rare earth elements (REEs) entering the water environment.

  12. Synthesis, structure, and magnetism of a family of heterometallic {Cu2Ln7} and {Cu4Ln12} (Ln = Gd, Tb, and Dy) complexes: the Gd analogues exhibiting a large magnetocaloric effect.

    Science.gov (United States)

    Langley, Stuart K; Moubaraki, Boujemaa; Tomasi, Corrado; Evangelisti, Marco; Brechin, Euan K; Murray, Keith S

    2014-12-15

    The syntheses, structures, and magnetic properties of two heterometallic Cu(II)-Ln(III) (Ln(III) = Gd, Tb, and Dy) families, utilizing triethanolamine and carboxylate ligands, are reported. The first structural motif displays a nonanuclear {Cu(II)2Ln(III)7} metallic core, while the second reveals a hexadecanuclear {Cu(II)4Ln(III)12} core. The differing nuclearities of the two families stem from the choice of carboxylic acid used in the synthesis. Magnetic studies show that the most impressive features are displayed by the {Cu(II)2Gd(III)7} and {Cu(II)4Gd(III)12} complexes, which display a large magnetocaloric effect, with entropy changes -ΔSm = 34.6 and 33.0 J kg(-1) K(-1) at T = 2.7 and 2.9 K, respectively, for a 9 T applied field change. It is also found that the {Cu(II)4Dy(III)12} complex displays single-molecule magnet behavior, with an anisotropy barrier to magnetization reversal of 10.1 K.

  13. Poly(acrylic acid) Bridged Gadolinium Metal-Organic Framework-Gold Nanoparticle Composites as Contrast Agents for Computed Tomography and Magnetic Resonance Bimodal Imaging.

    Science.gov (United States)

    Tian, Chixia; Zhu, Liping; Lin, Feng; Boyes, Stephen G

    2015-08-19

    Imaging contrast agents for magnetic resonance imaging (MRI) and computed tomography (CT) have received significant attention in the development of techniques for early stage cancer diagnosis. Gadolinium (Gd)(III), which has seven unpaired electrons and a large magnetic moment, can dramatically influence the water proton relaxation and hence exhibits excellent MRI contrast. On the other hand, gold (Au), which has a high atomic number and high X-ray attenuation coefficient, is an ideal contrast agent candidate for X-ray-based CT imaging. Gd metal-organic framework (MOF) nanoparticles with tunable size, high Gd(III) loading and multivalency can potentially overcome the limitations of clinically utilized Gd chelate contrast agents. In this work, we report for the first time the integration of GdMOF nanoparticles with gold nanoparticles (AuNPs) for the preparation of a MRI/CT bimodal imaging agent. Highly stable hybrid GdMOF/AuNPs composites have been prepared by using poly(acrylic acid) as a bridge between the GdMOF nanoparticles and AuNPs. The hybrid nanocomposites were then evaluated in MRI and CT imaging. The results revealed high longitudinal relaxivity in MRI and excellent CT imaging performance. Therefore, these GdMOF/AuNPs hybrid nanocomposites potentially provide a new platform for the development of multimodal imaging probes.

  14. Nanodiamond-Gadolinium(III) Aggregates for Tracking Cancer Growth In Vivo at High Field.

    Science.gov (United States)

    Rammohan, Nikhil; MacRenaris, Keith W; Moore, Laura K; Parigi, Giacomo; Mastarone, Daniel J; Manus, Lisa M; Lilley, Laura M; Preslar, Adam T; Waters, Emily A; Filicko, Abigail; Luchinat, Claudio; Ho, Dean; Meade, Thomas J

    2016-12-14

    The ability to track labeled cancer cells in vivo would allow researchers to study their distribution, growth, and metastatic potential within the intact organism. Magnetic resonance (MR) imaging is invaluable for tracking cancer cells in vivo as it benefits from high spatial resolution and the absence of ionizing radiation. However, many MR contrast agents (CAs) required to label cells either do not significantly accumulate in cells or are not biologically compatible for translational studies. We have developed carbon-based nanodiamond-gadolinium(III) aggregates (NDG) for MR imaging that demonstrated remarkable properties for cell tracking in vivo. First, NDG had high relaxivity independent of field strength, a finding unprecedented for gadolinium(III) [Gd(III)]-nanoparticle conjugates. Second, NDG demonstrated a 300-fold increase in the cellular delivery of Gd(III) compared to that of clinical Gd(III) chelates without sacrificing biocompatibility. Further, we were able to monitor the tumor growth of NDG-labeled flank tumors by T1- and T2-weighted MR imaging for 26 days in vivo, longer than was reported for other MR CAs or nuclear agents. Finally, by utilizing quantitative maps of relaxation times, we were able to describe tumor morphology and heterogeneity (corroborated by histological analysis), which would not be possible with competing molecular imaging modalities.

  15. A new selectophore for gadolinium selective sensor

    Energy Technology Data Exchange (ETDEWEB)

    Zamani, Hassan Ali, E-mail: haszamani@yahoo.com [Department of Applied Chemistry, Mashhad Branch, Islamic Azad University, Mashhad (Iran, Islamic Republic of); Faridbod, Farnoush; Ganjali, Mohammad Reza [Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran (Iran, Islamic Republic of); Biosensor Research Center, Endocrinology and Metabolism Molecular-Cellular Sciences Institute, Tehran University of Medical Sciences, Tehran (Iran, Islamic Republic of)

    2014-10-01

    Based on a selective complexation of N′-(2-oxo-1,2-di(pyridin-2-yl)ethylidene)furan-2-carbohydrazide (L) with Gd(III) ions, it was used as a selectophore in construction of a Gd(III) selective PVC membrane sensor. Different compositions for the membrane were tested. The o-nitrophenyloctyl ether (NPOE) was used as suitable plasticizer, and a mixture of sodium tetraphenyl borate (NaTPB) and oleic acid (OA) as anion excluders. The proposed sensor displayed a Nernstian behavior with the slope of 19.9 ± 0.6 mV decade{sup −1} in concentration range of 1.0 × 10{sup −6} to 1.0 × 10{sup −2} mol L{sup −1}. Detection limit was 4.2 × 10{sup −7} mol L{sup −1} and response time was ∼ 10 s. Applicable pH range of the electrode was 4.2–8.0. Lifetime of the sensor is at least 10 weeks. Analysis of certified reference materials confirmed the accuracy of the proposed electrode. - Highlights: • This work reports design of membrane sensor for monitoring of Gd3+ ions. • The novelty of this work is the high affinity of the ionophore toward the Gd3+ ions. • The sensor is superior to the formerly reported Gd3+ sensors in terms of selectivity.

  16. On the formation and structure of rare-earth element complexes in aqueous solutions under hydrothermal conditions with new data on gadolinium aqua and chloro complexes

    Science.gov (United States)

    Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

    2007-01-01

    Synchrotron X-ray spectroscopy experiments were made on the Gd(III) aqua and chloro complexes in low pH aqueous solutions at temperatures ranging from 25 to 500????C and at pressures up to 480??MPa using a hydrothermal diamond anvil cell. Analysis of fluorescence Gd L3-edge X-ray absorption fine structure (XAFS) spectra measured from a 0.006m Gd/0.16m HNO3 aqueous solution at temperatures up to 500????C and at pressures up to 260??MPa shows that the Gd-O distance of the Gd3+ aqua ion decreases steadily at a rate of ??? 0.007??A??/100????C whereas the number of coordinated H2O molecules decreases from 9.0 ?? 0.5 to 7.0 ?? 0.4. The loss of water molecules in the Gd3+ aqua ion inner hydration shell over this temperature range (a 22% reduction) is smaller than exhibited by the Yb3+ aqua ion (42% reduction) indicating that the former is significantly more stable than the later. We conjecture that the anomalous enrichment of Gd reported from measurement of REE concentrations in ocean waters may be attributed to the enhanced stability of the Gd3+ aqua ion relative to other REEs. Gd L3-edge XAFS measurements of 0.006m and 0.1m GdCl3 aqueous solutions at temperatures up to 500????C and pressures up to 480??MPa reveal that the onset of significant Gd3+-Cl- association occurs around 300????C. Partially-hydrated stepwise inner-sphere complexes most likely of the type Gd(H2O)??-nCln+3-n occur in the chloride solutions at higher temperatures, where ?? ??? 8 at 300????C decreasing slightly to an intermediate value between 7 and 8 upon approaching 500????C. This is the first direct evidence for the occurrence of partially-hydrated REE Gd (this study) and Yb [Mayanovic, R.A., Jayanetti, S., Anderson, A.J., Bassett, W.A., Chou, I-M., 2002a. The structure of Yb3+ aquo ion and chloro complexes in aqueous solutions at up to 500 ??C and 270 MPa. J. Phys. Chem. A 106, 6591-6599.] chloro complexes in hydrothermal solutions. The number of chlorides (n) of the partially-hydrated Gd(III

  17. Spectroscopic studies of neodymium (III) and praeseodymium (III) compounds in molten chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Lambert, H.; Sharrad, C. [School of Chemical Engineering and Analytical Science, University of Manchester, Oxford Road, Manchester M139PL (United Kingdom); Claux, B.; Soucek, P.; Malmbeck, R. [European Commission, JRC, Institute for Transuranium Elements, Postfach 2340, 76125 Karlsruhe (Germany)

    2016-07-01

    A novel spectroscopic furnace has been developed for the in situ acquisition of UV-visible absorption spectra in high temperature molten salts. The furnace has been used to obtain spectra of neodymium(III) and praseodymium(III) trichloride in LiCl-KCl eutectic at 450 Celsius degrees over various Ln(III) concentrations. The major absorption peaks for both for Nd(III) and Pr(III) in the UV-visible region of the spectrum have been identified and the molar absorbances quantified for each of these absorption maxima. The neodymium and praseodymium were then precipitated by adding respectively, Li{sub 2}CO{sub 3} and Li{sub 2}O to the salt and monitored using UV-visible spectroscopy. In both cases the precipitate has been identified as the relevant LnOCl by powder XRD. (authors)

  18. Synergistic extraction of trivalent lanthanoids with 3-phenyl-4-benzoyl-5-isoxazolone and various sulphoxides

    Energy Technology Data Exchange (ETDEWEB)

    Sahu, S.K.; Chakravortty, V. [Utkal Univ., Bhubaneswar (India). Dept. of Chemistry; Reddy, M.L.P.; Ramamohan, T.R. [Council of Scientific and Industrial Research, Trivandrum (India). Regional Research Lab.

    1999-07-01

    Synergistic extraction of trivalent lanthanoids Nd, Tb and Tm with mixtures of 3-phenyl-4-benzoyl-5-isoxazolone (HPBI) and dioctyl sulphoxide (DOSO), bis-2-ethylhexyl sulphoxide (B2EHSO) or diphenyl sulphoxide (DPhSO) in xylene from perchlorate solution was investigated. Lanthanoids were found to be extracted as Ln(PBI){sub 3} with HPBI alone. In the presence of sulphoxides, Nd(III) was found to be extracted as Nd(PBI){sub 3} . S and Nd(PBI){sub 3} . 2 S (where S = sulphoxide). On the other hand, Tb(III) and Tm(III) were extracted as Tb(PBI){sub 3} . S and Tm(PBI){sub 3} . S respectively. The equilibrium constants of the synergistic species were found to increase monotonically with decreasing ionic radii of these metal ions. The addition of a sulphoxide to the metal chelate system not only enhances the extraction efficiency but also improves the selectivities among these trivalent lanthanoids. (orig.)

  19. Computation of energy interaction parameters as well as electric dipole intensity parameters for the absorption spectral study of the interaction of Pr(III) with L-phenylalanine, L-glycine, L-alanine and L-aspartic acid in the presence and absence of Ca 2+ in organic solvents

    Science.gov (United States)

    Moaienla, T.; Singh, Th. David; Singh, N. Rajmuhon; Devi, M. Indira

    2009-10-01

    Studying the absorption difference and comparative absorption spectra of the interaction of Pr(III) and Nd(III) with L-phenylalanine, L-glycine, L-alanine and L-aspartic acid in the presence and absence of Ca 2+ in organic solvents, various energy interaction parameters like Slater-Condon ( FK), Racah ( Ek), Lande factor ( ξ4f), nephelauxetic ratio ( β), bonding ( b1/2), percentage-covalency ( δ) have been evaluated applying partial and multiple regression analysis. The values of oscillator strength ( P) and Judd-Ofelt electric dipole intensity parameter Tλ ( λ = 2, 4, 6) for different 4f-4f transitions have been computed. On analysis of the variation of the various energy interaction parameters as well as the changes in the oscillator strength ( P) and Tλ values reveal the mode of binding with different ligands.

  20. Sensitization of Eriochromeazurol-B in Presence of Cetyldimethylethylammonium Bromide for the Microdetermination of Some Lanthanides

    Directory of Open Access Journals (Sweden)

    Anil B. Zade

    2012-01-01

    Full Text Available Cetyldimethylethylammonium bromide, a cationic surfactant has been used to decolorize eriochromeazurol B, an anionic triphenylmethane type of dye. Addition of specific lanthanide metal ion to this decolorized solution resulted into intense colored stable ternary complex with large bathochromic shift from 540 nm (binary complex to 650 nm (ternary complex with increase in absorbance values at shifted wavelength. CDMEAB thus decreases the color intensity of ECAB and increases the absorbance value of ternary complexes. This two fold advantage resulted into enhancement in molar absorptivities and sensitivities at shifted wavelength of ternary complexes with stoichiometric composition 1:(1:32, [Ln : (R:S] for all lanthanides understudy namely yttrium, neodymium, europium, terbium and ytterbium. The ternary complexes at pH 6.0 exhibited absorption maxima at 650 nm with molar absorptivities 69000 L.mol-1.cm-2 for Y(III, 66000 L.mol-1.cm-2 for Nd(III, 69000 L.mol-1.cm-2 for Eu(III, 64000 L.mol-1.cm-2 for Tb(III, 70000 L.mol-1.cm-2 for Yb(III. Beer's law were obeyed in concentration range 0.11-0.94, 0.19-1.53, 0.2-1.41, 0.21-1.69 and 0.23-1.11 ppm for Y(III, Nd(III, Eu(III, Tb(III and Yb(III respectively. Conditional formation constants and various analytical parameters have been evaluated and compared the results of newly formed ternary complexes with binary complexes. Finally newly suggested modified method have been recommended for the microdetermination of lanthanides understudy.

  1. Recovery of rare earth elements from the sulfothermophilic red alga Galdieria sulphuraria using aqueous acid.

    Science.gov (United States)

    Minoda, Ayumi; Sawada, Hitomi; Suzuki, Sonoe; Miyashita, Shin-ichi; Inagaki, Kazumi; Yamamoto, Takaiku; Tsuzuki, Mikio

    2015-02-01

    The demand for rare earth elements has increased dramatically in recent years because of their numerous industrial applications, and considerable research efforts have consequently been directed toward recycling these materials. The accumulation of metals in microorganisms is a low-cost and environmentally friendly method for the recovery of metals present in the environment at low levels. Numerous metals, including rare earth elements, can be readily dissolved in aqueous acid, but the efficiency of metal biosorption is usually decreased under the acidic conditions. In this report, we have investigated the use of the sulfothermophilic red alga Galdieria sulphuraria for the recovery of metals, with particular emphasis on the recovery of rare earth metals. Of the five different growth conditions investigated where G. sulphuraria could undergo an adaptation process, Nd(III), Dy(III), and Cu(II) were efficiently recovered from a solution containing a mixture of different metals under semi-anaerobic heterotrophic condition at a pH of 2.5. G. sulphuraria also recovered Nd(III), Dy(III), La(III), and Cu(II) with greater than 90% efficiency at a concentration of 0.5 ppm. The efficiency remained unchanged at pH values in the range of 1.5-2.5. Furthermore, at pH values in the range of 1.0-1.5, the lanthanoid ions were collected much more efficiently into the cell fractions than Cu(II) and therefore successfully separated from the Cu(II) dissolved in the aqueous acid. Microscope observation of the cells using alizarin red suggested that the metals were accumulating inside of the cells. Experiments using dead cells suggested that this phenomenon was a biological process involving specific activities within the cells.

  2. Calix[4]azacrowns as novel molecular scaffolds for the generation of visible and near-infrared lanthanide luminescence.

    Science.gov (United States)

    Oueslati, Issam; Sa Ferreira, Rute A; Carlos, Luís D; Baleizão, Carlos; Berberan-Santos, Mario N; de Castro, Baltazar; Vicens, Jacques; Pischel, Uwe

    2006-03-20

    Two calix[4]azacrowns, capped with two aminopolyamide bridges, were used as ligands for the complexation of lanthanide ions [Eu(III), Tb(III), Nd(III), Er(III), La(III)]. The formation of 1:2 and 1:1 complexes was observed, and stability constants, determined by UV absorption and fluorescence spectroscopy, were found to be generally on the order of log beta(11) approximately 5-6 and log beta(12) approximately 10. The structural changes of the ligands upon La(III) complexation were probed by 1H NMR spectroscopy. The two ligands were observed to have opposite fluorescence behaviors, namely, fluorescence enhancement (via blocking of photoinduced electron transfer from amine groups) or quenching (via lanthanide-chromophore interactions) upon metal ion complexation. Long-lived lanthanide luminescence was sensitized by excitation in the pi,pi band of the aromatic moieties of the ligands. The direct involvement of the antenna triplet state was demonstrated via quenching of the ligand phosphorescence by Tb(III). Generally, Eu(III) luminescence was weak (Phi(lum) Nd(III) was also generated by energy-transfer sensitization.

  3. Synthesis and Evaluation of new Polyfunctional Molecules for Group Actinide Extraction; Synthese et evaluation de Nouvelles Molecules Polyfonctionnelles pour la Separation Groupee des Actinides

    Energy Technology Data Exchange (ETDEWEB)

    Marie, C.

    2009-10-15

    The aim of this project is to design new extracting molecules for spent nuclear fuel reprocessing. In order to minimize the long-term residual radiotoxicity of the waste, the GANEX process is an option based on homogeneous recycling of actinides. All actinides (U, Np, Pu, Am, Cm), present in a highly acidic aqueous solution, would be extracted together and separated from fission products (especially from lanthanides) using liquid-liquid extraction. In this context, twenty new bi-topic ligands constituted of a nitrogen poly-aromatic unit functionalized by amide groups were synthesized. Liquid-liquid extraction tests with these ligands dissolved alone in the organic phase show that N, N, N', N'-tetra-alkyl-6, 6''(2, 2':6', 2''-terpyridine)-diamides are able to selectively extract actinides at different oxidation states (Np(V et VI), U(VI), Pu(IV), Am(III), Cm(III)) from an aqueous solution 3M HNO{sub 3}. Nevertheless, actinides(III) are poorly extracted. According to crystallographic structures of complexes with Nd(III) and U(VI) determined by X-rays diffraction, these ligands are penta-dentate. In solution (methanol), complexes stoichiometries (1:1) of Nd(III), U(VI) and Pu(IV) were determined by electro-spray ionization mass spectrometry. Stability constants, evaluated by UV-visible spectrophotometry in MeOH/H{sub 2}O solutions, confirm the selectivity of ligands toward actinides(III) with respect to lanthanides(III). Associate to nuclear magnetic resonance experiments and DFT calculations (Density Functional Theory), a better knowledge of their coordination mode was achieved. (author)

  4. Selectivity of the highly preorganized tetradentate ligand 2,9-di(pyrid-2-yl)-1,10-phenanthroline for metal ions in aqueous solution, including lanthanide(III) ions and the uranyl(VI) cation.

    Science.gov (United States)

    Carolan, Ashley N; Cockrell, Gregory M; Williams, Neil J; Zhang, Gang; VanDerveer, Donald G; Lee, Hee-Seung; Thummel, Randolph P; Hancock, Robert D

    2013-01-01

    Some metal ion complexing properties of DPP (2,9-Di(pyrid-2-yl)-1,10-phenanthroline) are reported with a variety of Ln(III) (Lanthanide(III)) ions and alkali earth metal ions, as well as the uranyl(VI) cation. The intense π-π* transitions in the absorption spectra of aqueous solutions of 10(-5) M DPP were monitored as a function of pH and metal ion concentration to determine formation constants of the alkali-earth metal ions and Ln(III) (Ln = lanthanide) ions. It was found that log K(1)(DPP) for the Ln(III) ions has a peak at Ln(III) = Sm(III) in a plot of log K(1) versus 1/r(+) (r(+) = ionic radius for 8-coordination). For Ln(III) ions larger than Sm(III), there is a steady rise in log K(1) from La(III) to Sm(III), while for Ln(III) ions smaller than Sm(III), log K(1) decreases slightly to the smallest Ln(III) ion, Lu(III). This pattern of variation of log K(1) with varying size of Ln(III) ion was analyzed using MM (molecular mechanics) and DFT (density functional theory) calculations. Values of strain energy (∑U) were calculated for the [Ln(DPP)(H(2)O)(5)](3+) and [Ln(qpy)(H(2)O)(5)](3+) (qpy = quaterpyrdine) complexes of all the Ln(III) ions. The ideal M-N bond lengths used for the Ln(III) ions were the average of those found in the CSD (Cambridge Structural Database) for the complexes of each of the Ln(III) ions with polypyridyl ligands. Similarly, the ideal M-O bond lengths were those for complexes of the Ln(III) ions with coordinated aqua ligands in the CSD. The MM calculations suggested that in a plot of ∑U versus ideal M-N length, a minimum in ∑U occurred at Pm(III), adjacent in the series to Sm(III). The significance of this result is that (1) MM calculations suggest that a similar metal ion size preference will occur for all polypyridyl-type ligands, including those containing triazine groups, that are being developed as solvent extractants in the separation of Am(III) and Ln(III) ions in the treatment of nuclear waste, and (2) Am(III) is very

  5. Fluorescent dialdehyde ligand for the encapsulation of dinuclear luminescent lanthanide complexes.

    Science.gov (United States)

    Lin, Po-Heng; Leclère, Mathieu; Long, Jérôme; Burchell, Tara J; Korobkov, Ilia; Clérac, Rodolphe; Murugesu, Muralee

    2010-06-28

    Five dinuclear lanthanide complexes [Ln(III)(2)(hpd)(6)].solvent, Ln(III) = Eu(III) (1.2MeCN), Gd(III) (2.2MeCN), Tb(III) (3.MeCN.MeOH), Dy(III) (4.2MeCN), Ho(III) (5.2MeCN) and Hhpd (2-Hydroxyisophthaldehyde) were synthesised and structurally and magnetically characterised. X-Ray structural analysis shows all complexes are isostructural and crystallise in the triclinic P1 space group. The dinuclear complexes are composed of eight-coordinate lanthanide ions linked by two phenoxide bridges from two hpd(-) ligands. Complex 1 exhibits characteristic fluorescence in the visible region.

  6. Steric hindrances create a discrete linear Dy4 complex exhibiting SMM behaviour.

    Science.gov (United States)

    Lin, Shuang-Yan; Zhao, Lang; Ke, Hongshan; Guo, Yun-Nan; Tang, Jinkui; Guo, Yang; Dou, Jianmin

    2012-03-21

    Two linear tetranuclear lanthanide complexes of general formula [Ln(4)(L)(2)(C(6)H(5)COO)(12)(MeOH)(4)], where HL = 2,6-bis((furan-2-ylmethylimino)methyl)-4-methylphenol, () and Ln(III) = Dy(III) (1) and Gd(III) (2), have been synthesized and characterized. The crystal structural analysis demonstrates that two Schiff-base ligands inhibit the growth of benzoate bridged 1D chains, leading to the isolation of discrete tetranuclear complexes due to their steric hindrances. Every Ln(III) ion is coordinated by eight donor atoms in a distorted bicapped trigonal-prismatic arrangement. Alternating current (ac) susceptibility measurements of complex 1 reveal a frequency- and temperature-dependent out-of-phase signal under zero dc field, typical of single-molecule magnet (SMM) behaviour with an anisotropic barrier Δ(eff) = 17.2 K.

  7. Transmetallation of Gd-DTPA by Fe3+, Cu2+ and Zn2+ in water: batch experiments and coagulation-flocculation simulations.

    Science.gov (United States)

    Rabiet, Marion; Letouzet, Marine; Hassanzadeh, Sepideh; Simon, Stéphane

    2014-01-01

    The study investigates the stability of gadolinium-DTPA complex in presence of competing metallic ions, Fe(3+), Cu(2+) and Zn(2+) using batch experiments and coagulation-flocculation simulations. High performance liquid chromatography with fluorescence detection was used for simultaneous analysis of chelate gadolinium (Gd-DTPA) and free Gd(III) ion in water. It was shown that Cu(2+) has a strong affinity for DTPA and could lead to a complete release of Gd(3+). Fe(3+) appeared also to compete strongly with Gd(3+) for DTPA binding since up to 80% of Gd-complex was dissociated under iron excess condition. Finally, zinc had a lower influence on Gd speciation: only 15% of Gd(3+) was released with addition of a 5-fold excess of Zn(2+). During coagulation-flocculation simulation, Fe(3+) was able to displace about 27% of Gd-DTPA, and no adsorption was observed onto flocs.

  8. Gd-Complexes of New Arylpiperazinyl Conjugates of DTPA-Bis(amides): Synthesis, Characterization and Magnetic Relaxation Properties.

    Science.gov (United States)

    Ba-Salem, Abdullah O; Ullah, Nisar; Shaikh, M Nasiruzzaman; Faiz, Mohamed; Ul-Haq, Zaheer

    2015-04-29

    Two new DTPA-bis(amide) based ligands conjugated with the arylpiperazinyl moiety were synthesized and subsequently transformed into their corresponding Gd(III) complexes 1 and 2 of the type [Gd(L)H2O]·nH2O. The relaxivity (R1) of these complexes was measured, which turned out to be comparable with that of Omniscan®, a commercially available MRI contrast agent. The cytotoxicity studies of these complexes indicated that they are non-toxic, which reveals their potential and physiological suitability as MRI contrast agents. All the synthesized ligands and complexes were characterized with the aid of analytical and spectroscopic methods, including elemental analysis, 1H-NMR, FT-IR, XPS and fast atom bombardment (FAB) mass spectrometry.

  9. Gd-Complexes of New Arylpiperazinyl Conjugates of DTPA-Bis(amides: Synthesis, Characterization and Magnetic Relaxation Properties

    Directory of Open Access Journals (Sweden)

    Abdullah O. Ba-Salem

    2015-04-01

    Full Text Available Two new DTPA-bis(amide based ligands conjugated with the arylpiperazinyl moiety were synthesized and subsequently transformed into their corresponding Gd(III complexes 1 and 2 of the type [Gd(LH2O]·nH2O. The relaxivity (R1 of these complexes was measured, which turned out to be comparable with that of Omniscan®, a commercially available MRI contrast agent. The cytotoxicity studies of these complexes indicated that they are non-toxic, which reveals their potential and physiological suitability as MRI contrast agents. All the synthesized ligands and complexes were characterized with the aid of analytical and spectroscopic methods, including elemental analysis, 1H-NMR, FT-IR, XPS and fast atom bombardment (FAB mass spectrometry.

  10. A Eu(II)-Containing Cryptate as a Redox Sensor in Magnetic Resonance Imaging of Living Tissue.

    Science.gov (United States)

    Ekanger, Levi A; Polin, Lisa A; Shen, Yimin; Haacke, E Mark; Martin, Philip D; Allen, Matthew J

    2015-11-23

    The Eu(II) ion rivals Gd(III) in its ability to enhance contrast in magnetic resonance imaging. However, all reported Eu(II)-based complexes have been studied in vitro largely because the tendency of Eu(II) to oxidize to Eu(III) has been viewed as a major obstacle to in vivo imaging. Herein, we present solid- and solution-phase characterization of a Eu(II)-containing cryptate and the first in vivo use of Eu(II) to provide contrast enhancement. The results indicate that between one and two water molecules are coordinated to the Eu(II) core upon dissolution. We also demonstrate that Eu(II)-based contrast enhancement can be observed for hours in a mouse.

  11. Separation process for lanthanides based on solvation properties of non ionic surfactants

    Energy Technology Data Exchange (ETDEWEB)

    Draye, M.; Favre-Reguillon, A.; Foos, J.; Cote, G

    2004-07-01

    In the present study, cloud-point extraction is used with a lipophilic chelating agent (8-hydroxyquinoline) to extract and separate lanthanum (III) and gadolinium (III) from an aqueous solution. The methodology used is based on the formation of lanthanide (III) organic complexes that are soluble in a micellar phase of non-ionic surfactant. The lanthanide (III) complexes are then extracted into the surfactant-rich phase at a temperature above the cloud-point temperature. The cloud-point temperature, the structure of the lipophilic part of the nonionic surfactant and the chelating agent - metal molar ratio are identified as factors determining the extraction efficiency and selectivity. With Triton X-114, high selectivity and decontamination factor for Gd(III) is observed indicating that micelle mediated extraction involving cloud-point extraction is promising for the specific separation of actinide ions from nuclear waste solution. (authors)

  12. Modeling rare earth complexes: Sparkle/AM1 parameters for thulium (III)

    Science.gov (United States)

    Freire, Ricardo O.; Rocha, Gerd B.; Simas, Alfredo M.

    2005-08-01

    The Sparkle/AM1 model, recently defined for Eu(III), Gd(III) and Tb(III) [R.O. Freire, G.B. Rocha, A.M., Simas, Inorg. Chem. 44 (2005) 3299], is extended to Tm(III). A set of 15 structures of high crystallographic quality from the Cambridge Crystallographic Database, with ligands chosen to be representative of all complexes with nitrogen or oxygen directly bonded to the Tm(III) ion, was used as a training set. For the 15 complexes, the Sparkle/AM1 unsigned mean error, for all interatomic distances between the Tm(III) ion and the oxygen or nitrogen ligand atoms of the first sphere of coordination, is 0.07 Å, a level of accuracy useful for luminescent complex design.

  13. Enhancement of optical Faraday effect of nonanuclear Tb(III) complexes.

    Science.gov (United States)

    Nakanishi, Takayuki; Suzuki, Yuki; Doi, Yoshihiro; Seki, Tomohiro; Koizumi, Hitoshi; Fushimi, Koji; Fujita, Koji; Hinatsu, Yukio; Ito, Hajime; Tanaka, Katsuhisa; Hasegawa, Yasuchika

    2014-07-21

    The effective magneto-optical properties of novel nonanuclear Tb(III) complexes with Tb-O lattice (specifically, [Tb9(sal-R)16(μ-OH)10](+)NO3(-), where sal-R = alkyl salicylate (R = -CH3 (Me), -C2H5 (Et), -C3H7 (Pr), or -C4H9 (Bu)) are reported. The geometrical structures of these nonanuclear Tb(III) complexes were characterized using X-ray single-crystal analysis and shape-measure calculation. Optical Faraday rotation was observed in nonanuclear Tb(III) complexes in the visible region. The Verdet constant per Tb(III) ion of the Tb9(sal-Me) complex is 150 times larger than that of general Tb(III) oxide glass. To understand their large Faraday rotation, electron paramagnetic resonance measurements of Gd(III) complexes were carried out. In this Report, the magneto-optical relation to the coordination geometry of Tb ions is discussed.

  14. Rare earth(III) complexes for the development of new magnetic and luminescent probes; Complexes de lanthanides(III) pour le developpement de nouvelles sondes magnetiques et luminescentes

    Energy Technology Data Exchange (ETDEWEB)

    Nonat, A

    2007-10-15

    The simultaneous optimisation of the molecular parameters determining the relaxivity (number of coordinated water molecules, water-exchange, rotation dynamics of the whole complex, electronic relaxation, Gd(III)-proton distance) is essential to prepare efficient contrast agents. The aim of this work is on the one hand to design and study complexes with a high number of bound water molecules and to understand the influence of the coordination sphere on the stability and on the electronic relaxation and on the other hand, to use the ligand as a chromophore for the development of luminescent probes for biomedical imaging. We present the structure, the stability and the relaxivity of Gd(III) complexes of two series of tripodal ligands containing picolinate units based either on the 1,4,7-tri-aza-cyclononane ring or on a tertiary amine. These complexes show high relaxivity in water and in serum and can establish a non covalent interaction with serum albumin. The interpretation of the water proton relaxivity with the help of new relaxometric methods based on an auxiliary probe solute has allowed us to show that both the presence of the picolinate groups and the 1,4,7-tri-aza-cyclononane framework can lead to Gd(III) complexes with favourable electronic relaxation properties. This ligands have also been used for Eu(III) and Tb(III) complexation leading to strong luminescence in visible light. Other complexes derived from 8-hydroxyquinoline unit which display a very high luminescence in infrared are also studied. (author)

  15. Effect of the medium and the formation of nanostructures on deexcitation of electronic excitation of Eu(III) and Tb(III) chelates

    Science.gov (United States)

    Sveshnikova, E. B.; Dudar, S. S.; Shablya, A. V.; Ermolaev, V. L.

    2006-10-01

    The intensity I lum and lifetime τlum of the luminescence of complexes of Eu(III) and Tb(III) ions with β-diketones and o-phenanthroline in water-ethanol solutions of these ligands have been analyzed as functions of the concentrations of ligand, luminescing lanthanide ions, and added ions causing columinescence and of the solvent deuteration. It is shown that the formation of nanostructures from Ln complexes and their coarsening leads to an increase in τlum of Eu(III) and Tb(III) and that this increase is due to the suppression of both photochemical deexcitation of these ions and transfer of their electronic excitation energy to OH vibrations of water molecules. The disappearance of the dependence of I lum of Eu(III) on deuteration of water-ethanol solutions of n-methoxybenzoyltrifluoracetone + o-phenanthroline caused by adding Gd(III) ions is explained by the shift of the equilibrium of formation of complexes of Ln chelates to neutral hydrophoblic forms corresponding to the formation of nanostructures of these chelates in the solution. The differences in effect of La(III) and Gd(III) ions on I lum and τlum of Eu(III) and Tb(III) complexes are explained. It is shown that the widely discussed effect of columinescence not only results from the energy migration in mixed structures of Eu or Tb complexes and Gd complexes but is also due to a large extent to the decrease in τlum of Eu(III) or Tb(III) caused by their incorporation into nanostructures.

  16. Chelating DTPA amphiphiles: ion-tunable self-assembly structures and gadolinium complexes.

    Science.gov (United States)

    Moghaddam, Minoo J; de Campo, Liliana; Kirby, Nigel; Drummond, Calum J

    2012-10-05

    A series of chelating amphiphiles and their gadolinium (Gd(III)) metal complexes have been synthesized and studied with respect to their neat and lyotropic liquid crystalline phase behavior. These amphiphiles have the ability to form ion-tunable self-assembly nanostructures and their associated Gd(III) complexes have potential as magnetic resonance imaging (MRI) contrast enhancement agents. The amphiphiles are composed of diethylenetriaminepentaacetic acid (DTPA) chelates conjugated to one or two oleyl chain(s) (DTPA-MO and DTPA-BO), or isoprenoid-type chain(s) of phytanyl (DTPA-MP and DTPA-BP). The thermal phase behavior of the neat amphiphiles was examined by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and cross polarizing optical microscopy (POM). Self-assembly of neat amphiphiles and their associated Gd complexes, as well as their lyotropic phase behavior in water and sodium acetate solutions of different ionic strengths, were examined by POM and small and wide angle X-ray scattering (SWAXS). All neat amphiphiles exhibited lamellar structures. The non-complexed amphiphiles showed a variety of lyotropic phases depending on the number and nature of the hydrophobic chain in addition to the ionic state of the hydration. Upon hydration with increased Na-acetate concentration and the subtle changes in the effective headgroup size, the interfacial curvature of the amphiphile increased, altering the lyotropic liquid crystalline structures towards higher order mesophases such as the gyroid (Ia3d) bicontinuous cubic phase. The chelation of Gd with the DTPA amphiphiles resulted in lamellar crystalline structures for all the neat amphiphiles. Upon hydration with water, the Gd-complexed mono-conjugates formed micellar or vesicular self-assemblies, whilst the bis-conjugates transformed only partially into lyotropic liquid crystalline mesophases.

  17. Fabrication and evaluation of tumor-targeted positive MRI contrast agent based on ultrasmall MnO nanoparticles.

    Science.gov (United States)

    Huang, Haitao; Yue, Tao; Xu, Ke; Golzarian, Jafar; Yu, Jiahui; Huang, Jin

    2015-07-01

    Gd(III) chelate is currently used as positive magnetic resonance imaging (MRI) contrast agent in clinical diagnosis, but generally induces the risk of nephrogenic systemic fibrosis (NSF) due to the dissociated Gd(3+) from Gd(III) chelates. To develop a novel positive MRI contrast agent with low toxicity and high sensitivity, ultrasmall MnO nanoparticles were PEGylated via catechol-Mn chelation and conjugated with cRGD as active targeting function to tumor. Particularly, the MnO nanoparticles with a size of ca. 5nm were modified by α,β-poly(aspartic acid)-based graft polymer containing PEG and DOPA moieties and, meanwhile, conjugated with cRGD to produce the contrast agent with a size of ca. 100nm and a longitudinal relaxivity (r1) of 10.2mM(-1)S(-1). Such nanoscaled contrast agent integrated passive- and active-targeting function to tumor, and its efficient accumulation behavior in tumor was verified by in vivo distribution study. At the same time, the PEG moiety played a role of hydrophilic coating to improve the biocompatibility and stability under storing and physiological conditions, and especially might guarantee enough circulation time in blood. Moreover, in vivo MRI revealed a good and long-term effect of enhancing MRI signal for as-fabricated contrast agent while cell viability assay proved its acceptable cytotoxicity for MRI application. On the whole, the as-fabricated PEGylated and cRGD-functionalized contrast agent based on ultrasmall MnO nanoparticles showed a great potential to the T1-weighted MRI diagnosis of tumor.

  18. Chemistry of paramagnetic and diamagnetic contrast agents for Magnetic Resonance Imaging and Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Mayoral, Elena [Laboratorio de Sintesis Organica e Imagen Molecular por Resonancia Magnetica, Facultad de Ciencias, UNED, Paseo Senda del Rey 9, E-28040 Madrid (Spain); Departamento de Quimica Inorganica y Quimica Tecnica, Facultad de Ciencias, UNED, Paseo Senda del Rey 9, E-28040 Madrid (Spain); Negri, Viviana; Soler-Padros, Jordi [Laboratorio de Sintesis Organica e Imagen Molecular por Resonancia Magnetica, Facultad de Ciencias, UNED, Paseo Senda del Rey 9, E-28040 Madrid (Spain); Cerdan, Sebastian [Laboratorio de Imagen Espectroscopica por Resonancia Magnetica (LIERM), Instituto de Investigaciones Biomedicas ' Alberto Sols' , CSIC/UAM, c/Arturo Duperier 4, E-28029 Madrid (Spain); Ballesteros, Paloma [Laboratorio de Sintesis Organica e Imagen Molecular por Resonancia Magnetica, Facultad de Ciencias, UNED, Paseo Senda del Rey 9, E-28040 Madrid (Spain)], E-mail: pballesteros@ccia.uned.es

    2008-09-15

    We provide a brief overview of the chemistry and most relevant properties of paramagnetic and diamagnetic contrast agents (CAs) for Magnetic Resonance Imaging and Magnetic Resonance Spectroscopic Imaging. Paramagnetic CAs for MRI consist mainly of Gd(III) complexes from linear or macrocyclic polyaminopolycarboxylates. These agents reduce, the relaxation times T{sub 1} and T{sub 2} of the water protons in a concentration dependent manner, increasing selectively MRI contrast in those regions in which they accumulate. In most instances they provide anatomical information on the localization of lesions and in some specific cases they may allow to estimate some physiological properties of tissues including mainly vascular performance. Because of its ability to discriminate easily between normal and diseased tissue, extracellular pH (pH{sub e}) has been added recently, to the battery of variables amenable to MRI investigation. A variety of Gd(III) containing macrocycles sensitive to pH, endogenous or exogenous polypeptides or even liposomes have been investigated for this purpose, using the pH dependence of their relaxivity or magnetization transfer rate constant (chemical exchange saturation transfer, CEST). Many environmental circumstances in addition to pH affect, however, relaxivity or magnetization transfer rate constants of these agents, making the results of pH measurements by MRI difficult to interpret. To overcome these limitations, our laboratory synthesized and developed a novel series of diamagnetic CAs for Magnetic Resonance Spectroscopic Imaging, a new family of monomeric and dimeric imidazolic derivatives able to provide unambiguous measurements of pH{sub e}, independent of water relaxivity, diffusion or exchange.

  19. Stimuli-Responsive Biodegradable Hyperbranched Polymer-Gadolinium Conjugates as Efficient and Biocompatible Nanoscale Magnetic Resonance Imaging Contrast Agents.

    Science.gov (United States)

    Sun, Ling; Li, Xue; Wei, Xiaoli; Luo, Qiang; Guan, Pujun; Wu, Min; Zhu, Hongyan; Luo, Kui; Gong, Qiyong

    2016-04-27

    The efficacy and biocompatibility of nanoscale magnetic resonance imaging (MRI) contrast agents depend on optimal molecular structures and compositions. Gadolinium [Gd(III)] based dendritic macromolecules with well-defined and tunable nanoscale sizes are excellent candidates as multivalent MRI contrast agents. Here, we propose a novel alternate preparation of biodegradable hyperbranched polymer-gadolinium conjugates via a simple strategy and report potentially efficient and biocompatible nanoscale MRI contrast agents for cancer diagnosis. The enzyme-responsive hyperbranched poly(oligo-(ethylene glycol) methacrylate)-gadolinium conjugate (HB-POEGMA-Gd) was prepared via one-step reversible addition-fragmentation chain transfer (RAFT) polymerization and Gd(III) chelating, and the cRGDyK functionalized polymer (HB-POEGMA-cRGD-Gd) was obtained via click chemistry. By using an enzyme similar to lysosomal cathepsin B, hyperbranched conjugates of high molecular weights (MW) (180 and 210 kDa) and nanoscale sizes (38 and 42 nm) were degraded into low MW (25 and 30 kDa) and smaller products (4.8 and 5.2 nm) below the renal threshold. Conjugate-based nanoscale systems had three-fold more T1 relaxivity compared to clinical agent diethylenediaminepentaacetic acid (DTPA)-Gd. Animal studies with the nanoscale system offered greater tumor accumulation and enhanced signal intensity (SI) in mouse U87 tumors of which the greatest activity was conferred by the cRGDyK moiety functionalized hyperbranched conjugate. In vitro cytotoxicity, hemocompatibility and in vivo toxicity studies confirmed no adverse events. This design strategy for multifunctional Gd(III)-labeled biodegradable dendritic macromolecules may have significant potential as future efficient, biocompatible polymeric nanoscale MRI diagnostic contrast agents for cancer.

  20. Extraction mechanism of Gd{sup 3+} by BTMPPA

    Energy Technology Data Exchange (ETDEWEB)

    Bari, Md. Fazlul [School of Materials Engineering, Northern Malaysia University College of Engineering, KUKUM, Taman Muhibbah 02600, Arau, Perlis (Malaysia)]. E-mail: fazlul@kukum.edu.my; Saad, Bahruddin [School of Chemical Sciences, Universiti Sains Malaysia, 11800 Minden, Penang (Malaysia); Rahman, Ismail Abdur [School of Chemical Sciences, Universiti Sains Malaysia, 11800 Minden, Penang (Malaysia); Saleh, Muhammad Idiris [School of Chemical Sciences, Universiti Sains Malaysia, 11800 Minden, Penang (Malaysia)

    2007-06-14

    The extraction behavior of Gd(III) from acidic nitrate-acetato medium by bis(2,4,4-trimethylpentyl)phosphinic acid (BTMPPA, H{sub 2}A{sub 2}) in toluene either alone or in combination with trioctylphospine oxide (TOPO, B) has been investigated as a function of contact time, concentrations of Gd{sup 3+}, H{sup +}, NO{sub 3} {sup -} and Ac{sup -} (acetate) in the aqueous phase, the concentration of H{sub 2}A{sub 2} and TOPO in the organic phase and temperature. Dependencies of H{sup +}, BTMPPA, TOPO and Ac{sup -} concentrations on extraction ratio suggest that the extracted species are [Gd(Ac)(HA{sub 2}){sub 2}.H{sub 2}A{sub 2}] and [Gd(Ac)A{sub 2}.HA.2B] for without and with TOPO, respectively at lower loading, while GdA{sub 3} is extracted at higher loading in both cases. The synergistic effect of TOPO is observed only at higher TOPO concentrations region. The equilibrium constants are evaluated to be 10{sup -0.63} and 10{sup -2.79} for the system without and with TOPO, respectively. The La(III)/Gd(III) separation factors are found to be 348 and 393 for the system without and with TOPO, respectively. The temperature dependence of the extraction data from acidic nitrate-acetato gives the enthalpy of extraction, 56 kJ/mol. The loading capacity for 100 g BTMPPA is found to be 17.89 g Gd(III)

  1. Poly[tetradecaaquatetrakis(μ3-1H-imidazole-4,5-dicarboxylatotetra-μ3-sulfato-cobalt(IIhexagadolinium(III

    Directory of Open Access Journals (Sweden)

    Li-Cai Zhu

    2011-08-01

    Full Text Available The asymmetric unit of the title compound, [CoGd6(C5H2N2O44(SO46(H2O14]n, contains a CoII ion (site symmetry overline1, three GdIII ions, two imidazole-4,5-dicarboxylate ligands, three SO42− anions, and seven coordinated water molecules. The CoII ion is six-coordinated by two O atoms from water molecules, two O atoms and two N atoms from two imidazole-4,5-dicarboxylate ligands, giving a slightly distorted octahedral geometry. The GdIII ions exhibit three types of coordination environments. One Gd ion is eight-coordinated in a bicapped trigonal–prismatic geometry by four O atoms from two imidazole-4,5-dicarboxylate ligands, two O atoms from two SO42− anions and two coordinated water molecules. The other Gd ions are nine-coordinated in a tricapped trigonal–prismatic geometry; one of these Gd ions is bonded to four O atoms from two imidazole-4,5-dicarboxylate ligands, three O atoms from three SO42− anions and two water O atoms and the other Gd ion is coordinated by one O atom and one N atom from one imidazole-4, 5-dicarboxylate ligand, five O atoms from three SO42− anions as well as two coordinated water molecules. These metal coordination units are connected by bridging imidazole-4,5-dicarboxylate and sulfate ligands, generating a three-dimensional network. The crystal structure is further stabilized by N—H...O, O—H...O, and C—H...O hydrogen-bonding interactions between water molecules, SO42− anions, and imidazole-4,5-dicarboxylate ligands.

  2. Physicochemical Properties of Near-Linear Lanthanide(II) Bis(silylamide) Complexes (Ln = Sm, Eu, Tm, Yb).

    Science.gov (United States)

    Goodwin, Conrad A P; Chilton, Nicholas F; Vettese, Gianni F; Moreno Pineda, Eufemio; Crowe, Iain F; Ziller, Joseph W; Winpenny, Richard E P; Evans, William J; Mills, David P

    2016-10-17

    Following our report of the first near-linear lanthanide (Ln) complex, [Sm(N(††))2] (1), herein we present the synthesis of [Ln(N(††))2] [N(††) = {N(Si(i)Pr3)2}; Ln = Eu (2), Tm (3), Yb (4)], thus achieving approximate uniaxial geometries for a series of "traditional" Ln(II) ions. Experimental evidence, together with calculations performed on a model of 4, indicates that dispersion forces are important for stabilization of the near-linear geometries of 1-4. The isolation of 3 under a dinitrogen atmosphere is noteworthy, given that "[Tm(N″)(μ-N″)]2" (N″ = {N(SiMe3)2}) has not previously been structurally authenticated and reacts rapidly with N2(g) to give [{Tm(N″)2}2(μ-η(2):η(2)-N2)]. Complexes 1-4 have been characterized as appropriate by single-crystal X-ray diffraction, magnetic measurements, electrochemistry, multinuclear NMR, electron paramagnetic resonance (EPR), and electronic spectroscopy, along with computational methods for 3 and 4. The remarkable geometries of monomeric 1-4 lead to interesting physical properties, which complement and contrast with comparatively well understood dimeric [Ln(N″)(μ-N″)]2 complexes. EPR spectroscopy of 3 shows that the near-linear geometry stabilizes mJ states with oblate spheroid electron density distributions, validating our previous suggestions. Cyclic voltammetry experiments carried out on 1-4 did not yield Ln(II) reduction potentials, so a reactivity study of 1 was performed with selected substrates in order to benchmark the Sm(III) → Sm(II) couple. The separate reactions of 1 with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), azobenzene, and benzophenone gave crystals of [Sm(N(††))2(TEMPO)] (5), [Sm(N(††))2(N2Ph2)] (6), and [Sm(N(††)){μ-OPhC(C6H5)CPh2O-κO,O'}]2 (7), respectively. The isolation of 5-7 shows that the Sm(II) center in 1 is still accessible despite having two bulky N(††) moieties and that the N-donor atoms are able to deviate further from linearity or ligand

  3. Effect of complexation with lanthanide metal ions on the photochromism of (1,3,3-trimethyl- 5 ′ -hydroxy- 6 ′ -formyl- indoline-spiro2,2 ′ -[2h]chromene in different media

    Directory of Open Access Journals (Sweden)

    2006-01-01

    Full Text Available Complexation of lanthanide ions {Ln(III ions [Tb(III, Eu(III, or Sm(III]} with the spiropyran-derived merocyanine obtained in dark and under steady irradiation of indoline spiropyran (1,3,3-trimethyl- 5 ′ -hydroxy- 6 ′ -formyl-indoline-spiro-2,2 ′ -[2H]chromene induces a noticeable hypsochromic shift of about 10–110 nm of its visible absorption band concomitant with hypochromic effect and influences its thermal bleaching in the dark. The effect of lanthanide ions and medium on photochromic, spectral-and-kinetic, and luminescence properties of the spiropyran and its complexes in solution and polymer matrix of polymethylmethacrylate (PMMA is studied. Efficient energy transfer from the spiropyran moiety results in efficient typical luminescence from the Ln(III ion that becomes more pronounced in polar nonalcoholic solvents and PMMA solid matrix. Moreover, luminescence mappings for pattern recognition analysis have been obtained from which the nature of the solvent and/or the ligand is clearly identified.

  4. Crystal structure of a mixed-ligand terbium(III coordination polymer containing oxalate and formate ligands, having a three-dimensional fcu topology

    Directory of Open Access Journals (Sweden)

    Chainok Kittipong

    2016-01-01

    Full Text Available The title compound, poly[(μ3-formato(μ4-oxalatoterbium(III], [Tb(CHO2(C2O4]n, is a three-dimensional coordination polymer, and is isotypic with the LaIII, CeIII and SmIII analogues. The asymmetric unit contains one TbIII ion, one formate anion (CHO2− and half of an oxalate anion (C2O42−, the latter being completed by application of inversion symmetry. The TbIII ion is nine-coordinated in a distorted tricapped trigonal–prismatic manner by two chelating carboxylate groups from two C2O42− ligands, two carboxylate oxygen atoms from another two C2O42− ligands and three oxygen atoms from three CHO2− ligands, with the Tb—O bond lengths and the O—Tb—O bond angles ranging from 2.4165 (19 to 2.478 (3 Å and 64.53 (6 to 144.49 (4°, respectively. The CHO2− and C2O42− anions adopt μ3-bridging and μ4-chelating-bridging coordination modes, respectively, linking adjacent TbIII ions into a three-dimensional 12-connected fcu topology with point symbol (324.436.56. The title compound exhibits thermal stability up to 623 K, and also displays strong green photoluminescence in the solid state at room temperature.

  5. Efficient formation of luminescent lanthanide(III) complexes by solid-phase synthesis and on-resin screening.

    Science.gov (United States)

    Nakamura, Tatsuya; Mizukami, Shin; Tanaka, Miho; Kikuchi, Kazuya

    2013-11-01

    Time-resolved luminescence measurements of luminescent lanthanide complexes have advantages in biological assays and high-throughput screening, owing to their high sensitivity. In spite of the recent advances in their energy-transfer mechanism and molecular-orbital-based computational molecular design, it is still difficult to estimate the quantum yields of new luminescent lanthanide complexes. Herein, solid-phase libraries of luminescent lanthanide complexes were prepared through amide-condensation and Pd-catalyzed coupling reactions and their luminescent properties were screened with a microplate reader. Good correlation was observed between the time-resolved luminescence intensities of the solid-phase libraries and those of the corresponding complexes that were synthesized by using liquid-phase chemistry. This method enabled the rapid and efficient development of new sensitizers for Sm(III), Eu(III), and Tb(III) luminescence. Thus, solid-phase combinatorial synthesis combined with on-resin screening led to the discovery of a wide variety of luminescent sensitizers.

  6. Recovery of molybdenum using alumina microspheres and precipitation with selective organic reagents

    Energy Technology Data Exchange (ETDEWEB)

    Carvalho, Fatima Maria Sequeira de; Abrao, Alcidio [Instituto de Pesquisas Energeticas e Nucleares (IPEN), Sao Paulo, SP (Brazil). Dept. de Engenharia Quimica e Ambiental]. E-mail: fatimamc@net.ipen.br; aabrao@net.ipen.br

    1998-07-01

    In this paper is presented a study for the optimization of dissolution of the UAL{sub x} plates used for irradiation and production of radiomolybdenum. The alloy is dissolved in nitric acid with mercury as catalyst. The separation and concentration of the molybdenum was achieved using a chromatographic grade alumina microspheres column. the purified eluted molybdenum is finally precipitated using one of the selective reagents: alizarine blue, {alpha},{alpha}'- bipyridine and 1,10-phenanthroline. Any one of the obtained precipitate can be fired to the molybdenum trioxide. The interference of the following elements was studied: Re(VII), U(VI), Cr(VI), W(VI), V(V), Te(IV), Ti(IV), Zr(IV), Th(IV), Fe(III), Au(III), Ru(III), Al(III), Bi(III), Sb(III), Ce(IV), Pr(III), Sc(III), Y(III), Sm(III), Ba(II), Sr(II), Ni(II), Co(II), Cs(I). The molybdenum precipitates were characterized by gravimetric, CHN, TG, DTG, IR and X-ray diffraction analyses. (author)

  7. Preparation of Sm–Ru bimetallic alloy films on Ru(0001) surface by vapour-deposition and annealing

    Indian Academy of Sciences (India)

    G Ranga Rao; H Nozoye

    2001-12-01

    Sm–Ru intermetallic surface alloy films were prepared by vacuum deposition and annealing of rare earth Sm on single crystal Ru(0001) surface. The Ru 3 and Sm 3 core level spectra clearly show the formation of surface alloy layers. XPS measurements on surface alloy film revealed an induced peak in the Ru3 region at lower binding energy by 1 eV compared to the bulk Ru (elemental) suggesting an electronic effect of alloying and Sm–Ru bond formation. The Sm 35/2 photoemission peak of Sm film consists of strong features characteristic of Sm(II) with electron configuration 46 (5\\ 6)2 and Sm(III) with electron configuration 46 (5\\ 6)3. It is observed that the Sm(II) feature decreases in intensity upon alloy formation with surface Ru atoms. Oxidation of these films with carbon monoxide indicates alloy breakdown due to the oxidation of Sm atoms selectively. Alloy oxidation also shows a clear shift of Sm 35/2 feature.

  8. Unsymmetrical Schiff base (ON) ligand on complexation with some transition metal ions: Synthesis, spectral characterization, antibacterial, fluorescence and thermal studies

    Science.gov (United States)

    Ali, Omyma A. M.; El-Medani, Samir M.; Abu Serea, Maha R.; Sayed, Abeer S. S.

    2015-02-01

    A series of eight metal Schiff base complexes were synthesized by the thermal reaction of Cu(II), Ni(II), Fe(III), Co(II), Zn(II), Hg(II), La(III) or Sm(III) with a Schiff base "L" produced by the condensation of furfuraldehyde and 1,2-diaminobenzene. These compounds were characterized by elemental analysis, UV-Vis, FT-IR, molar conductance, mass spectrometry, thermal and fluorescence studies. The studies suggested the coordination of the ligand L to metal through azomethine imine nitrogen and furan oxygen atoms of Schiff base moiety. Thermogravimetric (TG/DTG) analyses data were studied and indicated high stability for all complexes and suggested the presence of lattice and/or coordinated water molecules in the complexes. Coats-Redfern method has been used to calculate the kinetic and thermodynamic parameters of the metal complexes. The spectral and thermal analysis reveal that all complexes have octahedral geometry except Cu(II) and Ni(II) complexes which can attain a square planner arrangements. The ligand and its complexes exhibited intraligand (π-π∗) fluorescence and can potentially serve as photoactive materials. Both the ligand and its complexes have been screened for antibacterial activities.

  9. Synthesis, structure, infrared and fluorescence spectra of new rare earth complexes with 6-hydroxy chromone-3-carbaldehyde benzoyl hydrazone

    Science.gov (United States)

    Wang, Bao-Dui; Yang, Zheng-Yin; Zhang, Ding-Wa; Wang, Yan

    2006-01-01

    A novel 6-hydroxy chromone-3-carbaldehyde benzoyl hydrazone ligand and its four complexes, [LnL2(NO3)2]NO3 [Ln = Eu(1), Sm(2), Tb(3), Dy(4)], were synthesized. The complexes were characterized by the elemental analyses, molar conductivity and IR spectra. The crystal and molecular structure of Sm(III) complex was determined by single-crystal X-ray diffraction: crystallized in the triclinic system, space group P-1, Z = 1, a = 11.037(4) Å, b = 14.770(5) Å, c = 15.032(7) Å, α = 60.583(4), β = 75.528(7), γ = 88.999(4), R1 = 0.0349. The fluorescence properties of complexes in the solid state and in the organic solvent were studied in detail, respectively. Under the excitation of ultraviolet light, strong red fluorescence of solid europium complex was observed. But the green fluorescence of solid terbium complex was not observed. These observations show that the ligand favor energy transfers to the emitting energy level of Eu3+. Some factors that influence the fluorescent intensity were also discussed.

  10. Synthesis and luminescent spectroscopy of lanthanide complexes with dimethylpyridine-2,6-dicarboxylate (dmpc)

    Energy Technology Data Exchange (ETDEWEB)

    Taha, Ziyad A., E-mail: tahaz33@just.edu.jo [Department of Applied Chemical Sciences, Faculty of Arts and Sciences, Jordan University of Science and Technology, Irbid 22110 (Jordan); Ajlouni, Abdulaziz M.; Hijazi, Ahmed K. [Department of Applied Chemical Sciences, Faculty of Arts and Sciences, Jordan University of Science and Technology, Irbid 22110 (Jordan); Al-Rawashdeh, Nathir A. [Department of Applied Chemical Sciences, Faculty of Arts and Sciences, Jordan University of Science and Technology, Irbid 22110 (Jordan); Department of Chemistry, United Arab Emirates University, Al Ain 15551 (United Arab Emirates); Al-Hassan, Khader A.; Al-Haj, Yaser A. [Department of Chemistry, Faculty of Science, Yarmouk University, 1163 Irbid (Jordan); Ebqa' ai, Mohammad A. [Al-Qunfudah Center For Scientific Research, Umm Al-Qura University, College in Al-Qunfudah, Makkah (Saudi Arabia); Altalafha, Ammar Y. [Department of Chemistry, Faculty of Science, Yarmouk University, 1163 Irbid (Jordan)

    2015-05-15

    A series of lanthanide complexes with the general formulae [Ln(dmpc)(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}]NO{sub 3} (Ln=Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Er) and [La(dmpc)(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}]NO{sub 3} were prepared by direct reaction between hydrated lanthanide(III) nitrate and dimethylpyridine-2,6-dicarboxylate (dmpc) in a 1:1 M ratio in ethylacetate–chloroform mixture. The luminescence properties of the dmpc and its Ln(III) complexes were investigated in solid state and in methanol, DMF and DMSO solutions. The Tb–dmpc, Eu–dmpc, Sm–dmpc and Dy–dmpc complexes exhibit characteristic luminescence of Tb(III), Eu(III), Sm(III) and Dy(III) ions indicating energy transfer from the dmpc to the Ln(III) ions. Scavenging activities of the dmpc and its Ln(III) complexes on DPPH{sup •} free radical were investigated in DMSO solution at a different concentrations ranges. - Highlights: • Nine new lanthanide complexes with dmpc ligand are prepared and characterized. • Ln–dmpc {Ln=Eu, Tb, Sm, Dy} complexes exhibit characteristic emissions of Ln ions. • The solvent effect on the luminescence intensity is investigated. • The antioxidant activity of the dmpc is enhanced upon complexation with lanthanide.

  11. Synthesis, spectroscopic, thermal and antimicrobial studies of neodymium(III) and samarium(III) complexes derived from tetradentate ligands containing N and S donor atoms.

    Science.gov (United States)

    Ain, Qurratul; Pandey, S K; Pandey, O P; Sengupta, S K

    2015-04-05

    Trivalent lanthanide complexes of the type [Ln(L)Cl(H2O)2] (where Ln=Nd(III) or Sm(III) and LH2=Schiff bases derived by the condensation of 3-(phenyl/substitutedphenyl)-4-amino-5-mercapto-1,2,4-triazole with diacetyl/benzil) have been synthesized by the reactions of anhydrous lanthanide(III) chloride with Schiff bases in methanol. The structures of the complexes have been proposed on the basis of elemental analysis, electrical conductance, magnetic moment, spectroscopic measurements (IR, 1H, 13C NMR and UV-vis spectra) and X-ray diffraction studies. The spectral data reveal that the Schiff base ligands behave as dibasic tetradentate chelating agents having coordination sites at two thiol sulfur atoms and two azomethine nitrogen atoms. The presence of coordinated water in metal complexes was confirmed by thermal and IR data of the complexes. All the Schiff bases and their metal complexes have also been screened for their antibacterial activity against Bacillus subtilis, Staphylococcus aureus and antifungal activities against Aspergillus niger, Curvularia pallescens and Colletotrichum capsici.

  12. Unsymmetrical Schiff base (ON) ligand on complexation with some transition metal ions: synthesis, spectral characterization, antibacterial, fluorescence and thermal studies.

    Science.gov (United States)

    Ali, Omyma A M; El-Medani, Samir M; Abu Serea, Maha R; Sayed, Abeer S S

    2015-02-05

    A series of eight metal Schiff base complexes were synthesized by the thermal reaction of Cu(II), Ni(II), Fe(III), Co(II), Zn(II), Hg(II), La(III) or Sm(III) with a Schiff base "L" produced by the condensation of furfuraldehyde and 1,2-diaminobenzene. These compounds were characterized by elemental analysis, UV-Vis, FT-IR, molar conductance, mass spectrometry, thermal and fluorescence studies. The studies suggested the coordination of the ligand L to metal through azomethine imine nitrogen and furan oxygen atoms of Schiff base moiety. Thermogravimetric (TG/DTG) analyses data were studied and indicated high stability for all complexes and suggested the presence of lattice and/or coordinated water molecules in the complexes. Coats-Redfern method has been used to calculate the kinetic and thermodynamic parameters of the metal complexes. The spectral and thermal analysis reveal that all complexes have octahedral geometry except Cu(II) and Ni(II) complexes which can attain a square planner arrangements. The ligand and its complexes exhibited intraligand (π-π(∗)) fluorescence and can potentially serve as photoactive materials. Both the ligand and its complexes have been screened for antibacterial activities.

  13. Tris[6-methoxy-2-(phenyliminiomethylphenolato]-κ4O,O′;κO1-tris(thiocyanato-κNsamarium(III

    Directory of Open Access Journals (Sweden)

    Guo-Di Ge

    2011-06-01

    Full Text Available In the crystal structure of title compound, [Sm(NCS3(C14H13NO23], two of the zwitterionic Schiff base 6-methoxy-2-(phenyliminiomethylphenolate ligands coordinate to the SmIII atom in a bidentate fashion via the phenolate and methoxy O atoms. The third Schiff base ligand is monodentate, binding only through the phenolate O atom. The coordination sphere of the eight-coordinate Sm atom is completed by the three independent thiocyanate ions binding through their N atoms, affording a square-antiprismatic geometry. An S atom of one of the thiocyanate anions is disordered over two sites in a 0.85:0.15 ratio. In the phenolate ligands, the proton of the phenolic hydroxy group transfers to the imine N atom. This proton is also involved in an intramolecular N—H...O hydrogen bond that imposes a nearly planar conformation on each ligand, with dihedral angles of 1.75 (4, 3.68 (5 and 3.86 (4° between the aromatic rings of each ligand.

  14. Radionuclide-Chelating Agent Complexes in Low-Level Radioactive Decontamination Waste; Stability, Adsorption and Transport Potential

    Energy Technology Data Exchange (ETDEWEB)

    Serne, R. Jeffrey; Cantrell, Cantrell J.; Lindenmeier, Clark W.; Owen, Antionette T.; Kutnyakov, Igor V.; Orr, Robert D.; Felmy, Andrew R.

    2002-02-01

    Speciation calculations were done to determine whether organic complexants facilitate transport of radionuclides leached from waste buried in soils. EDTA readily mobilizes divalent transition metals and moderately impacts trivalent actinides. Picolinate readily mobilizes only Ni2+ and Co2+. These speciation predictions ignore the influence of soil adsorption and biodegradation that break apart the complexes. In adsorption studies, picolinate concentrations have to be >10-4 M to lower the adsorption of Ni and Co. For Sm(III), Th(IV), Np(V), U(VI), and Pu, the picolinate concentration must be >10-3 M before adsorption decreases. EDTA forms strong complexes with divalent transition metals and can stop adsorption of Ni and Co when EDTA solution concentrations are 10-5 M. EDTA complexes with Np(V), U(VI), and Pu are much weaker; EDTA concentrations would have to be >10-3 M to adversely effects non-transition metal/radionuclide adsorption. Most picolinate and ETDA-metal complexes appear to readily dissociate during interactions with soils. The enhanced migration of radionuclide-organic complexes may be limited to a few unique conditions. We recommend that mixtures of metal/radionuclides and EDTA should not be solidified or co-disposed with high pH materials such as cement. For weaker binding organic complexants, such as picolinate, citrate and oxalate, co-disposal of decontamination wastes and concrete should be acceptable.

  15. Synthesis, characterization, biological activities and luminescent properties of lanthanide complexes with [2-thiophenecarboxylic acid, 2-(2- pyridinylmethylene)hydrazide] Schiff bases ligand

    Institute of Scientific and Technical Information of China (English)

    Abdulaziz M Ajlouni; Qutaiba Abu-Salem; Ziyad A Taha; Ahmed K Hijazi; Waleed Al Momani

    2016-01-01

    A Schiff baseL[2-thiophenecarboxylic acid, 2-(2-pyridinylmethylene)hydrazide] with its lanthanide metal complexeswas synthesized. These complexes were characterized by elemental analysis, molar conductivity measurements, spectral analysis (NMR, FT-IR, and UV-Vis), luminescence and thermal gravimetric analysis. The Schiff base ligandwas a tridentate chelate and coordinates to the central lanthanide ion with 1:2 metal:ligand ratio. The conductivity data showeda1:1 electrolytic nature with a general formula [LnL2(NO3)2]NO3. The luminescence emission properties for Sm,Tb, and Eu complexeswere observed and showedthat the ligandL couldabsorb and transfer energy to Sm(III), Tb(III) and Eu(III)ions. The complexes possesseda good antibacterial activity against different bacterial strains. In addition,the scavenging activity of the Ln(III) complexes on DPPHwas concentration dependant and the complexeswere significantly more efficient in quenching DPPH than the free Schiff base ligand.

  16. [N,N'-Bis(2,6-diisopropyl-phen-yl)methanimidamidato][η-1,4-bis-(tri-methyl-sil-yl)cyclo-octa-tetra-enyl](tetra-hydro-furan)-samarium(III) toluene monosolvate.

    Science.gov (United States)

    Edelmann, Anja; Hrib, Cristian G; Hilfert, Liane; Blaurock, Steffen; Edelmann, Frank T

    2010-11-27

    The title compound, [Sm(C(25)H(35)N(2))(C(14)H(24)Si(2))(C(4)H(8)O)]·C(7)H(8), was prepared by treatment of anhydrous samarium trichloride with a 1:1 mixture of in situ-prepared Li(DippForm) [DippFormH = N,N'-bis-(2,6-diisopropyl-phen-yl)methanimidamide] and Li(2)(COT'') [COT'' = 1,4-bis-(trimethyl-sil-yl)cyclo-octa-tetra-enyl] in tetra-hydro-furan (THF). Despite the presence of two very bulky ligands (COT'' and DippForm), the mol-ecule still contains one coordinated THF ligand. The overall coordination geometry around the Sm(III) atom resembles a three-legged piano-stool with the COT'' ligand being η(8)-coordinated and the DippForm(-) anion acting as an N,N'-chelating ligand [Sm-N = 2.5555 (15) and 2.4699 (15) Å]. The asymmetric unit also contains a disordered mol-ecule of toluene, the refined ratio of the two components being 0.80 (4):0.20 (4).

  17. [N,N′-Bis(2,6-diisopropylphenylmethanimidamidato][η8-1,4-bis(trimethylsilylcyclooctatetraenyl](tetrahydrofuransamarium(III toluene monosolvate

    Directory of Open Access Journals (Sweden)

    Anja Edelmann

    2010-12-01

    Full Text Available The title compound, [Sm(C25H35N2(C14H24Si2(C4H8O]·C7H8, was prepared by treatment of anhydrous samarium trichloride with a 1:1 mixture of in situ-prepared Li(DippForm [DippFormH = N,N′-bis(2,6-diisopropylphenylmethanimidamide] and Li2(COT′′ [COT′′ = 1,4-bis(trimethylsilylcyclooctatetraenyl] in tetrahydrofuran (THF. Despite the presence of two very bulky ligands (COT′′ and DippForm, the molecule still contains one coordinated THF ligand. The overall coordination geometry around the SmIII atom resembles a three-legged piano-stool with the COT′′ ligand being η8-coordinated and the DippForm− anion acting as an N,N′-chelating ligand [Sm—N = 2.5555 (15 and 2.4699 (15 Å]. The asymmetric unit also contains a disordered molecule of toluene, the refined ratio of the two components being 0.80 (4:0.20 (4.

  18. Hybrid conducting polymer materials incorporating poly-oxo-metalates for extraction of actinides; Materiaux polymeres conducteurs hybrides incorporant des polyoxometallates pour l'extraction d'actinides

    Energy Technology Data Exchange (ETDEWEB)

    Racimor, D

    2003-09-15

    The preparation and characterization of hybrid conducting polymers incorporating poly-oxo-metalates for extracting actinides is discussed. A study of the coordination of various lanthanide cations (Ce(III), Ce(IV), Nd(III)) by the mono-vacant poly-oxo-metalate {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} showed significant differences according to the cation.. Various {alpha}-A-[PW{sub 9}O{sub 34}(RPO){sub 2}]{sup 5-} hybrids were synthesized and their affinity for actinides or lanthanides was demonstrated through complexation. The first hybrid poly-oxo-metallic lanthanide complexes were then synthesized, as was the first hybrid functionalized with a pyrrole group. The electro-polymerization conditions of this pyrrole remain still to be optimized. Poly-pyrrole materials incorporating {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} or its neodymium or cerium complexes as doping agents proved to be the first conducting polymer incorporating poly-oxo-metalates capable of extracting plutonium from nitric acid. (author)

  19. Determination of Nd3+ Ions in Solution Samples by a Coated Wire Ion-Selective Sensor

    Directory of Open Access Journals (Sweden)

    Hassan Ali Zamani

    2012-01-01

    Full Text Available A new coated wire electrode (CWE using 5-(methylsulfanyl-3-phenyl-1H-1,2,4-triazole (MPT as an ionophore has been developed as a neodymium ion-selective sensor. The sensor exhibits Nernstian response for the Nd3+ ions in the concentration range of 1.0×10−6-1.0×10−2 M with detection limit of 3.7×10−7 M. It displays a Nernstian slope of 20.2±0.2 mV/decade in the pH range of 2.7–8.1. The proposed sensor also exhibits a fast response time of ∼5 s. The sensor revealed high selectivity with respect to all common alkali, alkaline earth, transition and heavy metal ions, including members of the lanthanide family other than Nd3+. The electrode was used as an indicator electrode in the potentiometric titration of Nd(III ions with EDTA. The electrode was also employed for the determination of the Nd3+ ions concentration in water solution samples.

  20. Electrochemistry and the mechanisms of nucleation and growth of neodymium during electroreduction from LiCl–KCl eutectic salts on Mo substrate

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Hao [Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); Department of Chemical and Materials Engineering, University of Idaho, Moscow, ID 83844 (United States); Pesic, Batric, E-mail: pesic@uidaho.edu [Department of Chemical and Materials Engineering, University of Idaho, Moscow, ID 83844 (United States)

    2015-03-15

    The electrochemical behavior of NdCl{sub 3} was studied on a Mo electrode in molten LiCl–KCl eutectic salts. The electroreduction of Nd(III)/Nd(0) involved two reaction steps, as confirmed by three different electrochemical techniques. In the first reaction step, Nd(III) is converted into soluble Nd(II), which undergoes further reduction into metallic Nd(0) in the second reaction step. The standard reaction rate constants for each reaction step were determined by Nicholson method. The rate constant values were used in Matsuda-Ayabe’s criteria for testing the electrochemical reversibility. Accordingly, both reaction steps were quasi-reversible redox reactions. The nucleation mechanisms of neodymium metal deposited on a Mo substrate were predicted by using Scharifker–Hill model, and tested for the first time by scanning electron microscopy (SEM) studies of the electrode surface. The SEM studies confirmed that for the low initial concentration of NdCl{sub 3}, neodymium nucleates and grows progressively, while for higher NdCl{sub 3} concentrations, the related mechanism is instantaneous. Both are governed by the aggregative growth mechanisms based on surface mobility of formed nanoclusters.

  1. Prediction of dissolved actinide concentrations in concentrated electrolyte solutions: a conceptual model and model results for the Waste Isolation Pilot Plant (WIPP)

    Energy Technology Data Exchange (ETDEWEB)

    Novak, C.F.; Moore, R.C. [Sandia National Labs., Albuquerque, NM (United States); Bynum, R.V. [Science Applications International Corp., Albuquerque, NM (United States)

    1996-10-25

    The conceptual model for WIPP dissolved concentrations is a description of the complex natural and artificial chemical conditions expected to influence dissolved actinide concentrations in the repository. By a set of physical and chemical assumptions regarding chemical kinetics, sorption substrates, and waste-brine interactions, the system was simplified to be amenable to mathematical description. The analysis indicated that an equilibrium thermodynamic model for describing actinide solubilities in brines would be tractable and scientifically supportable. This paper summarizes the conceptualization and modeling approach and the computational results as used in the WIPP application for certification of compliance with relevant regulations for nuclear waste repositories. The WIPP site contains complex natural brines ranging from sea water to 10x more concentrated than sea water. Data bases for predicting solubility of Am(III) (as well as Pu(III) and Nd(III)), Th(IV), and Np(V) in these brines under potential repository conditions have been developed, focusing on chemical interactions with Na, K, Mg, Cl, SO{sub 4}, and CO{sub 3} ions, and the organic acid anions acetate, citrate, EDTA, and oxalate. The laboratory and modeling effort augmented the Harvie et al. parameterization of the Pitzer activity coefficient model so that it could be applied to the actinides and oxidation states important to the WIPP system.

  2. Study of extraction kinetics of lanthanides(III) and actinides(III) nitrates by the molecule N, N'-dimethyl-N, N'-dibutyl, tetradecylmalonamide; Etude des cinetiques d'extraction des nitrates de lanthanides (III) et d'actinides (III) par le malonamide N, N'-dimethyl-N, N'-dibutyl, tetradecylmalonamide

    Energy Technology Data Exchange (ETDEWEB)

    Daldon, M

    1999-07-01

    The kinetics of extraction of lanthanides (III) and actinides (III) nitrates by the molecule N, N'-dimethyl - N, N'-dibutyl tetra-decyl malonamide has been investigated. This study was realised with a new constant interfacial-area-stirred cell. During the qualification step of the device it appears that the reduction of the device can lead to hydrolytic perturbations. The main conclusions are: - after the determination of conditions which provide kinetics regime (diffusion of species neglectable), partial orders of the kinetics law have been obtained and lead to the establishment of the law J = k [Nd{sup 3+}] [NO{sub 3}{sup -}]{sup 3} [diamide]{sup 1}, - interfacial tension measurements and kinetics study in presence of surface-active compounds proved that the chemical limiting reaction for Nd(III) is interfacial, - the results allow to propose an adsorption-desorption reaction mechanism, - a comprehensive study of the extraction kinetics of the lanthanides(III) series and also Am(III) and Cm(III) nitrates has been realised. The lighter lanthanides (La, Ce and Pr) exhibit higher kinetics rate of extraction than the others, which differs from the tendency observed with distribution coefficients which exhibit tetrad effect. The kinetics rate of extraction of Am(III) and Cm(III) is closed to the value of Eu(III). (author)

  3. Sequential separation of lanthanides, thorium and uranium using novel solid phase extraction method from high acidic nuclear wastes.

    Science.gov (United States)

    Kesava Raju, Ch Siva; Subramanian, M S

    2007-06-25

    A novel grafted polymer for selective extraction and sequential separation of lanthanides, thorium and uranium from high acidic wastes has been developed by grafting Merrifield chloromethylated (MCM) resin with octyl(phenyl)-N,N-diisobutylcarbamoyl-methylphosphine oxide (CMPO) (MCM-CMPO). The grafting process is well characterized using FT-IR spectroscopy, (31)P and (13)C CPMAS (cross-polarized magic angle spin) NMR spectroscopy and CHNPS elemental analysis. The influence of various physico-chemical parameters during metal ion extraction by the resin phase are studied and optimized by both static and dynamic methods. The resin shows very high sorption capacity values of 0.960mmolg(-1) for U(VI), 0.984mmolg(-1) for Th(IV), 0.488mmolg(-1) for La(III) and 0.502mmolg(-1) for Nd(III) under optimum HNO(3) medium, respectively. The grafted polymer shows faster rate exchange kinetics (extraction) and greater preconcentration ability, with reusability exceeding 20 cycles. During desorption process, sequential separation of the analytes is possible with varying eluting agents. The developed grafted resin has been successfully applied in extracting Th(IV) from high matrix monazite sand, U(VI) and Th(IV) from simulated nuclear spent fuel mixtures. All the analytical data is based on triplicate analysis and measurements are within 3.5% rsd reflecting the reproducibility and reliability of the developed method.

  4. Enhanced extraction and separation of trivalent lanthanoids with 4,4,4-trifluoro-1-phenyl-1,3-butanedione and crown ether

    Energy Technology Data Exchange (ETDEWEB)

    Reddy, M.L.P.; Luxmi Varma, R.; Ramamohan, T.R. [Regional Research Lab. (CSIR), Trivandrum (India)

    1998-08-01

    Synergistic extraction of the trivalent lanthanoids Nd, Eu and Tm with mixtures of 4,4,4-trifluoro-1-phenyl-1,3-butanedione (Hbtfa) and 18-crown-6, dicyclohexano-18-crown-6 or dibenzo-18-crown-6 (CE) in 1,2-dichloroethane from perchlorate solutions was investigated. Characteristic ion-pair extraction of the Nd(III) or Eu(III) was observed with 1,2-dichloroethane containing Hbtfa and crown ether, in which the cationic complex, Ln(btfa){sub 2}.CE{sup +}, was formed and extracted. On the other hand, the heavier lanthanoid, Tm(III), was extracted as Tm(btfa){sub 3}.CE. The addition of a crown ether to the metal chelate system not only enhances the extraction efficiency of these trivalent metal ions but also improves the selectivities significantly among the lighter and middle lanthanoids. Hence, such a system would be of practical value in the mutual or group separation of trivalent lanthanoids. (orig.)

  5. Crown ethers as synergists in the extraction of trivalent lanthanoids with 3-phenyl-4-(4-fluorobenzoyl)-5-isoxazolone

    Energy Technology Data Exchange (ETDEWEB)

    Pavithran, R.; Reddy, M.L.P. [Separation Science and Technology Group, Regional Research Lab. (CSIR), Thiruvananthapuram (India)

    2004-07-01

    This paper highlights the results of investigations carried out on the extraction of lanthanoids such as Nd(III), Eu(III) and Tm(III) from nitrate solutions into chloroform with 3-phenyl-4-(4-fluorobenzoyl)-5-isoxazolone (HFBPI) in the presence and absence of various crown ethers (CE); 18-crown-6 (18C6), dicyclohexano-18-crown-6 (DC18C6), benzo-18-crown-6 (B18C6) and dibenzo-18-crown-6 (DB18C6). The results demonstrated that these trivalent metal ions were extracted into chloroform as Ln(FBPI){sub 3} with HFBPI alone and as Ln(FBPI){sub 3}.CE in the presence of a CE. The equilibrium constants of the above extracted complexes deduced by a non-linear regression analysis were found to increase monotonically with a decrease in ionic radii of these metal ions. The addition of a CE to the metal chelate system significantly improves the extraction efficiency of these metal ions. The complexation strength of trivalent lanthanoids with various CEs follows the order: DC18C6 > 18C6 > B18C6 > DB18C6. Solid complexes of Eu(III) with HFBPI alone and with mixtures of HFBPI and various crown ethers have been isolated and characterised by IR and {sup 1}H NMR spectral data to further clarify the nature of the extracted complexes. (orig.)

  6. Synergistic extraction of rare earths with bis(2,4,4-trimethyl pentyl) dithiophosphinic acid and trialkyl phosphine oxide.

    Science.gov (United States)

    Reddy, M L; Bosco Bharathi, J R; Peter, S; Ramamohan, T R

    1999-08-23

    Synergistic extraction of trivalent rare earths from nitrate solutions using mixtures of bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex 301=HX) and trialkyl phosphine oxide (Cyanex 923=TRPO) in xylene has been investigated. The results demonstrate that these trivalent metal ions are extracted into xylene as MX(3).3HX with Cyanex 301 alone. In the presence of Cyanex 923, La(III) and Nd(III) are found to be extracted as MX(2).NO(3).TRPO. On the other hand, Eu(III), Y(III) and heavier rare earths are found to be extracted as MX(3).HX.2TRPO. The addition of a trialkylphosphine oxide to the metal extraction system not only enhances the extraction efficiency of these metal ions but also improves the selectivities significantly, especially between yttrium and heavier lanthanides. The separation factors between these metal ions were calculated and compared with that of commercially important extraction systems like di-2-ethylhexyl phosphoric acid.

  7. Uranium (III) precipitation in molten chloride by wet argon sparging

    Energy Technology Data Exchange (ETDEWEB)

    Vigier, Jean-François, E-mail: jean-francois.vigier@ec.europa.eu [CEA, Nuclear Energy Division, Radiochemistry & Processes Department, F-30207 Bagnols sur Cèze (France); Unité de Catalyse et de Chimie du Solide, UCCS UMR CNRS 8181, Univ. Lille Nord de France, ENSCL-USTL, B.P. 90108, 59652 Villeneuve d' Ascq Cedex (France); Laplace, Annabelle [CEA, Nuclear Energy Division, Radiochemistry & Processes Department, F-30207 Bagnols sur Cèze (France); Renard, Catherine [Unité de Catalyse et de Chimie du Solide, UCCS UMR CNRS 8181, Univ. Lille Nord de France, ENSCL-USTL, B.P. 90108, 59652 Villeneuve d' Ascq Cedex (France); Miguirditchian, Manuel [CEA, Nuclear Energy Division, Radiochemistry & Processes Department, F-30207 Bagnols sur Cèze (France); Abraham, Francis [Unité de Catalyse et de Chimie du Solide, UCCS UMR CNRS 8181, Univ. Lille Nord de France, ENSCL-USTL, B.P. 90108, 59652 Villeneuve d' Ascq Cedex (France)

    2016-06-15

    In the context of pyrochemical processes for nuclear fuel treatment, the precipitation of uranium (III) in molten salt LiCl-CaCl{sub 2} (30–70 mol%) at 705 °C is studied. First, this molten chloride is characterized with the determination of the water dissociation constant. With a value of 10{sup −4.0}, the salt has oxoacid properties. Then, the uranium (III) precipitation using wet argon sparging is studied. The salt is prepared using UCl{sub 3} precursor. At the end of the precipitation, the salt is totally free of solubilized uranium. The main part is converted into UO{sub 2} powder but some uranium is lost during the process due to the volatility of uranium chloride. The main impurity of the resulting powder is calcium. The consequences of oxidative and reductive conditions on precipitation are studied. Finally, coprecipitation of uranium (III) and neodymium (III) is studied, showing a higher sensitivity of uranium (III) than neodymium (III) to precipitation. - Highlights: • Precipitation of Uranium (III) is quantitative in molten salt LiCl-CaCl{sub 2} (30–70 mol%). • The salt is oxoacid with a water dissociation constant of 10{sup −4.0} at 705 °C. • Volatility of uranium chloride is strongly reduced in reductive conditions. • Coprecipitation of U(III) and Nd(III) leads to a consecutive precipitation of the two elements.

  8. Fluorescence Resonance Energy Transfer of the Tb(III)-Nd(III) Binary System in Molten LiCl-KCl Eutectic Salt

    Energy Technology Data Exchange (ETDEWEB)

    Kim, B. Y. [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Yun, J. I. [KAIST, Daejeon (Korea, Republic of)

    2015-05-15

    The lanthanides act as a neutron poison in nuclear reactor with large neutron absorption cross section. For that reason, very low amount of lanthanides is required in the recovered U/TRU ingot product from pyrochemical process. In view of that, the investigation of thermodynamic properties and chemical behaviors of lanthanides in molten chloride salt are necessary to estimate the performance efficiency of pyrochemical process. However, there are uncertainties about knowledge and understanding of basic mechanisms in pyrochemical process, such as chemical speciation and redox behaviors due to the lack of in-situ monitoring methods for high temperature molten salt. The spectroscopic analysis is one of the probable techniques for in-situ qualitative and quantitative analysis. Recently, a few fluorescence spectroscopic measurements on single lanthanide element in molten LiCl-KCl eutectic have been investigated. The fluorescence intensity and the fluorescence lifetime of Tb(III) were decreased as increasing the concentration of Nd(III), demonstrating collisional quenching between donor ions and acceptor ions. The Forster distance (..0) of Tb(III)-Nd(III) binary system in molten LiCl-KCl eutectic was determined in the specific range of .... (0.1-1.0) and .. (1.387-1.496)

  9. Controls on Soluble Pu Concentrations in PuO2/Magnetite Suspensions

    Energy Technology Data Exchange (ETDEWEB)

    Felmy, Andrew R.; Moore, Dean A.; Pearce, Carolyn I.; Conradson, Steven D.; Qafoku, Odeta; Buck, Edgar C.; Rosso, Kevin M.; Ilton, Eugene S.

    2012-11-06

    Time-dependent reduction of PuO2(am) was studied over a range of pH values in the presence of aqueous Fe(II) and magnetite (Fe3O4) nanoparticles. At early time frames (up to 56 days) very little aqueous Pu was mobilized from PuO2(am), even though measured pH and redox potentials, coupled to equilibrium thermodynamic modeling indicated the potential for significant reduction of PuO2(am) to relatively soluble Pu(III). Introduction of Eu(III) or Nd(III) to the suspensions as competitive cations to displace possible sorbed Pu(III) resulted in the release of significant concentrations of aqueous Pu. However, the similarity of aqueous Pu concentrations that resulted from the introduction of Eu(III)/Nd(III) to suspensions with and without magnetite indicated that the Pu was displaced from the PuO2(am), not from magnetite. The fact that soluble forms of Pu can be displaced from the surface of PuO2(am) represents a potential, but previously unidentified, source of Pu to aqueous solution or subsurface groundwaters.

  10. Study of Neodymium Extraction in Molten Fluorides by Electrochemical Co-Reduction with Aluminium

    Energy Technology Data Exchange (ETDEWEB)

    Gibilaro, M.; Massot, L.; Chamelot, P.; Taxil, P. [Laboratoire de Genie Chimique UMR 5503, Departement Procedes Electrochimiques, Universite de Toulouse, 31062 Toulouse Cedex 9 (France)

    2008-07-01

    This work concerns the co-deposition process of Al-Nd alloys in LiF-CaF{sub 2} medium (79-21% mol.) on tungsten electrode at 860 deg. C using electrochemical techniques: cyclic and square wave voltammetries and potentiostatic electrolysis. Specific peaks of Al-Nd alloys formation were observed in cyclic voltammograms between the reduction waves of Nd(III) and Al(III), in a fluoride melt containing neodymium and aluminium ions. The difference of potential measured between solvent reduction and the alloys formation allows expecting an extraction efficiency of 99.99% by the use of the co-reduction process. The intermetallic compounds (Al{sub 11}Nd{sub 3}, Al{sub 3}Nd, AlNd{sub 2} and AlNd{sub 3}) were obtained and characterised by Scanning Electron Microscopy with EDS probe. The validity of the process was tested by carrying neodymium extraction in the form of Al-Nd alloy; the extraction efficiency was more than 95%. (authors)

  11. Three-dimensional magnetic and abundance mapping of the cool Ap star HD 24712 II. Two-dimensional Magnetic Doppler Imaging in all four Stokes parameters

    CERN Document Server

    Rusomarov, N; Ryabchikova, T; Piskunov, N

    2014-01-01

    Aims: We present a magnetic Doppler imaging study from all Stokes parameters of the cool, chemically peculiar star HD 24712. This is the very first such analysis performed at a resolving power exceeding 10^5. Methods: The analysis is performed on the basis of phase-resolved observations of line profiles in all four Stokes parameters obtained with the HARPSpol instrument attached at the 3.6-m ESO telescope. We use the magnetic Doppler imaging code, INVERS10, which allows us to derive the magnetic field geometry and surface chemical abundance distributions simultaneously. Results: We report magnetic maps of HD 24712 recovered from a selection of FeI, FeII, NdIII, and NaI lines with strong polarization signals in all Stokes parameters. Our magnetic maps successfully reproduce most of the details available from our observation data. We used these magnetic field maps to produce abundance distribution map of Ca. This new analysis shows that the surface magnetic field of HD 24712 has a dominant dipolar component wit...

  12. Influences of different environmental parameters on the sorption of trivalent metal ions on bentonite: batch sorption, fluorescence, EXAFS and EPR studies.

    Science.gov (United States)

    Verma, P K; Pathak, P N; Mohapatra, P K; Godbole, S V; Kadam, R M; Veligzhanin, A A; Zubavichus, Y V; Kalmykov, S N

    2014-04-01

    The presence of long-lived radionuclides in natural aquatic systems is of great environmental concern in view of their possible migration into biospheres of mankind. Trivalent actinides such as (241/243)Am can contribute a great deal to radioactivity for several thousand years. This migration is significantly influenced by various factors such as pH, complexing ions present in aquatic environments, and the sorption of species involving radionuclides by sediments around water bodies. Clay minerals such as bentonite are known to be highly efficient in radionuclide retention and hence are suitable candidates for backfill materials. This study presents experimental results on the interaction of Eu(iii) and Gd(iii) (chemical analogs of Am(iii) and Cm(iii)) with bentonite clay under varying experimental conditions of contact time, pH, and the presence of complexing anions such as humic acid (HA) and citric acid (cit). The sorption of HA on bentonite decreased with increasing the pH from 2 to 8, which was attributed to electrostatic interactions between HA and the bentonite surfaces. The sorption of Eu(iii) on bentonite colloids showed marginal variation with pH (>95%). However, a decrease in Eu(iii) sorption was observed in the presence of HA beyond pH 5 due to the increased aqueous complexation of Eu(iii) with deprotonated HA in the aqueous phase. The complexation of Eu(iii) with citrate ions was studied using Time Resolved Laser induced Fluorescence Spectroscopy (TRLFS) to explain the sorption data. Extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance (EPR) investigations were carried out to understand the local chemical environment surrounding Eu(iii) and Gd(iii) (EPR probe) sorbed on bentonite under different experimental conditions. Surface complexation modelling shows the predominant formation of ≡XOEu(+2) (silanol) up to pH < 7, and beyond which ≡YOEu(OH)(+) (aluminol) is responsible for the quantitative sorption of Eu(iii) onto

  13. Photo-induced DNA cleavage activity and remarkable photocytotoxicity of lanthanide(III) complexes of a polypyridyl ligand.

    Science.gov (United States)

    Hussain, Akhtar; Gadadhar, Sudarshan; Goswami, Tridib K; Karande, Anjali A; Chakravarty, Akhil R

    2012-01-21

    Lanthanide(III) complexes [Ln(pyphen)(acac)(2)(NO(3))] (1, 2), [Ln(pydppz)(acac)(2)(NO(3))] (3, 4) and [La(pydppz)(anacac)(2)(NO(3))] (5), where Ln is La(III) (in 1, 3, 5) and Gd(III) (in 2, 4), pyphen is 6-(2-pyridyl)-1,10-phenanthroline, pydppz is 6-(2-pyridyl)-dipyrido[3,2-a:2',3'-c]phenazine, anacac is anthracenylacetylacetonate and acac is acetylacetonate, were prepared, characterized and their DNA photocleavage activity and photocytotoxicity studied. The crystal structure of complex 2 displays a GdO(6)N(3) coordination. The pydppz complexes 3-5 show an electronic spectral band at ~390 nm in DMF. The La(III) complexes are diamagnetic, while the Gd(III) complexes are paramagnetic with seven unpaired electrons. The molar conductivity data suggest 1 : 1 electrolytic nature of the complexes in aqueous DMF. They are avid binders to calf thymus DNA giving K(b) in the range of 5.4 × 10(4)-1.2 × 10(6) M(-1). Complexes 3-5 efficiently cleave supercoiled DNA to its nicked circular form in UV-A light of 365 nm via formation of singlet oxygen ((1)O(2)) and hydroxyl radical (HO˙) species. Complexes 3-5 also exhibit significant photocytotoxic effect in HeLa cancer cells giving respective IC(50) value of 0.16(±0.01), 0.15(±0.01) and 0.26±(0.02) μM in UV-A light of 365 nm, while they are less toxic in dark with an IC(50) value of >3 μM. The presence of an additional pyridyl group makes the pydppz complexes more photocytotoxic than their dppz analogues. FACS analysis of the HeLa cells treated with complex 4 shows apoptosis as the major pathway of cell death. Nuclear localization of complex 5 having an anthracenyl moiety as a fluorophore is evidenced from the confocal microscopic studies.

  14. Structure and Dynamics of a Trinuclear Gadolinium(III) Complex: The Effect of Intramolecular Electron Spin Relaxation on Its Proton Relaxivity(1).

    Science.gov (United States)

    Tóth É, Éva; Helm, Lothar; Merbach, André E.; Hedinger, Roman; Hegetschweiler, Kaspar; Jánossy, András

    1998-08-10

    The trinuclear [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) complex has been characterized in aqueous solution as a model compound from the point of view of MRI: the parameters that affect proton relaxivity have been determined in a combined variable temperature, pressure, and multiple-field (17)O NMR, EPR, and NMRD study. The solution structure of the complex was found to be the same as in solid state: the total coordination number of the lanthanide(III) ion is 8 with two inner-sphere water molecules. EPR measurements proved a strong intramolecular dipole-dipole interaction between Gd(III) electron spins. This mechanism dominates electron spin relaxation at high magnetic fields (B > 5 T). Its proportion to the overall relaxation decreases with decreasing magnetic field and becomes a minor term at fields used in MRI. Consequently, it cannot increase the electronic relaxation rates to such an extent that they limit proton relaxivity. [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) undergoes a relatively slow water exchange (k(ex)(298) = (1.1 +/- 0.2) x 10(7) s(-1)) compared to the Gd(III) aqua ion, while the mechanism is much more associatively activated as shown by the activation volume (DeltaV () = (-12.7 +/- 1.5) cm(3) mol(-)(1)). The lower exchange rate, as compared to [Gd(H(2)O)(8)](3+) and [Gd(PDTA)(H(2)O)(2)](-), can be explained with the higher rigidity of the [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) which considerably slows down the transition from the eight-coordinate reactant to the nine-coordinate transition state. The unexpectedly low rotational correlation time of the complex is interpreted in terms of a spherical structure with a large hydrophobic surface avoiding the formation of a substantial hydration sphere around [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+).

  15. Synthesis, complexation and water exchange properties of Gd(III)-TTDA-mono and bis(amide) derivatives and their binding affinity to human serum albumin.

    Science.gov (United States)

    Ou, Ming-Hung; Chen, Yi-Ming; Chang, Ya-Hui; Lu, Wen-Kuei; Liu, Gin-Chung; Wang, Yun-Ming

    2007-07-14

    With the objective of tuning the lipophilicity of ligands and maintaining the neutrality and stability of Gd(III) chelate, we designed and synthesized two bis(amide) derivatives of TTDA, TTDA-BMA and TTDA-BBA, and a mono(amide) derivative, TTDA-N-MOBA. The ligand protonation constants and complex stability constants for various metal ions were determined in this study. The identification of the microscopic sites of protonation of the amide ligand by 1H NMR titrations show that the first protonation site occurs on the central nitrogen atom. The values of the stability constant of TTDA-mono and bis(amide) complex are significantly lower than those of TTDA and DTPA, but the selectivity constants of these ligands for Gd(III) over Zn(II) and Cu(II) are slightly higher than those of TTDA and DTPA. On the basis of the water-exchange rate values available for [Gd(TTDA-BMA)(H2O)], [Gd(TTDA-BBA)(H2O)] and [Gd(TTDA-N-MOBA)(H2O)]-, we can state that, in general, the replacement of one carboxylate group by an amide group decreases the water-exchange rate of the gadolinium(III) complexes by a factor of about three to five. The decrease in the exchange rate is explained in terms of a decreased steric crowding and charge effect around the metal ion when carboxylates are replaced by an amide group. In addition, to support the HSA protein binding studies of lipophilic [Gd(TTDA-N-MOBA)(H2O)]- and [Gd(TTDA-BBA)(H2O)] complexes, further protein-complex binding was studied by ultrafiltration and relaxivity studies. The binding constants (KA) of [Gd(TTDA-N-MOBA)(H2O)]- and [Gd(TTDA-BBA)(H2O)] are 8.6 x 10(2) and 1.0 x 10(4) dm3 mol(-1), respectively. The bound relaxivities (r1(b)) are 51.8 and 52 dm3 mmol(-1) s(-1), respectively. The KA value of [Gd(TTDA-BBA)(H2O)] is similar to that of MS-325 and indicates a stronger interaction of [Gd(TTDA-BBA)(H2O)] with HSA.

  16. Seven 3d-4f coordination polymers of macrocyclic oxamide with polycarboxylates: Syntheses, crystal structures and magnetic properties

    Science.gov (United States)

    Xin, Na; Sun, Ya-Qiu; Zheng, Yan-Feng; Xu, Yan-Yan; Gao, Dong-Zhao; Zhang, Guo-Ying

    2016-11-01

    Seven new 3d-4f heterometallic coordination polymers, [Ln(CuL)2(Hbtca)(btca)(H2O)]·2H2O (Ln = TbIII1, PrIII2, SmIII3, EuIII4, YbIII5), [Nd(NiL)(nip)(Rnip)]·0·25H2O·0.25CH3OH (R= 0.6CH3, 0.4H) 6 and [Nd2(NiL)(nip)3(H2O)]·2H2O 7(CuL or NiL, H2L = 2, 3-dioxo-5, 6, 14, 15-dibenzo-1, 4, 8, 12-tetraazacyclo-pentadeca-7, 13-dien; H2btca = benzotriazole-5-carboxylic acid; H2nip = 5-nitroisophthalic acid) have been synthesized by a solvothermal method and characterized by single-crystal X-ray diffraction. Complexes 1-5 exhibit a double-strand meso-helical chain structures formed by [LnIIICuII2] units via the oxamide and benzotriazole-5-carboxylate bridges, while complex 6 exhibits a four-strand meso-helical chain formed by NdNi unit via the oxamide and 5-nitroisophthalate bridges. Complex 7 consists of a 2D layer framework formed by four-strand meso-helical chain via the nip2- bridges. Moreover, the magnetic properties of them were investigated, and the best-fit analysis of χMT versus T show that the anisotropic contribution of Ln(III) ions (arising from the spin-orbit coupling or the crystal field perturbation) dominates (weak exchange limit) in these complexes(for 3, λ = 214.6 cm-1, zj' = -0.33 cm-1, gav = 1.94; for 5, Δ = 6.98 cm-1, zj' = 1.53 cm-1, gav = 1.85).

  17. Gd-DTPA-Dopamine-Bisphytanyl Amphiphile: Synthesis, Characterisation and Relaxation Parameters of the Nanoassemblies and Their Potential as MRI Contrast Agents.

    Science.gov (United States)

    Gupta, Abhishek; Willis, Scott A; Waddington, Lynne J; Stait-Gardner, Tim; de Campo, Liliana; Hwang, Dennis W; Kirby, Nigel; Price, William S; Moghaddam, Minoo J

    2015-09-28

    Here, a new amphiphilic magnetic resonance imaging (MRI) contrast agent, a Gd(III)-chelated diethylenetriaminepentaacetic acid conjugated to two branched alkyl chains via a dopamine spacer, Gd-DTPA-dopamine-bisphytanyl (Gd-DTPA-Dop-Phy), which is readily capable of self-assembling into liposomal nanoassemblies upon dispersion in an aqueous solution, is reported. In vitro relaxivities of the dispersions were found to be much higher than Magnevist, a commercially available contrast agent, at 0.47 T but comparable at 9.40 T. Analysis of variable temperature (17)O NMR transverse relaxation measurements revealed the water exchange of the nanoassemblies to be faster than that previously reported for paramagnetic liposomes. Molecular reorientation dynamics were probed by (1)H NMRD profiles using a classical inner and outer sphere relaxation model and a Lipari-Szabo "model-free" approach. High payloads of Gd(III) ions in the liposomal nanoassemblies made solely from the Gd-DTPA-Dop-Phy amphiphiles, in combination with slow molecular reorientation and fast water exchange makes this novel amphiphile a suitable candidate to be investigated as an advanced MRI contrast agent.

  18. Separation of Gd-humic complexes and Gd-based magnetic resonance imaging contrast agent in river water with QAE-Sephadex A-25 for the fractionation analysis.

    Science.gov (United States)

    Matsumiya, Hiroaki; Inoue, Hiroto; Hiraide, Masataka

    2014-10-01

    Gadolinium complexed with naturally occurring, negatively charged humic substances (humic and fulvic acids) was collected from 500 mL of sample solution onto a column packed with 150 mg of a strongly basic anion-exchanger (QAE-Sephadex A-25). A Gd-based magnetic resonance imaging contrast agent (diethylenetriamine-N,N,N',N″,N″-pentaacetato aquo gadolinium(III), Gd-DTPA(2-)) was simultaneously collected on the same column. The Gd-DTPA complex was desorbed by anion-exchange with 50mM tetramethylammonium sulfate, leaving the Gd-humic complexes on the column. The Gd-humic complexes were subsequently dissociated with 1M nitric acid to desorb the humic fraction of Gd. The two-step desorption with small volumes of the eluting agents allowed the 100-fold preconcentration for the fractionation analysis of Gd at low ng L(-1) levels by inductively coupled plasma-mass spectrometry (ICP-MS). On the other hand, Gd(III) neither complexed with humic substances nor DTPA, i.e., free species, was not sorbed on the column. The free Gd in the effluent was preconcentrated 100-fold by a conventional solid-phase extraction with an iminodiacetic acid-type chelating resin and determined by ICP-MS. The proposed analytical fractionation method was applied to river water samples.

  19. Poly[[tetraaquatetrakis[μ3-5-(pyridine-4-carboxamidoisophthalato]cobalt(IIdigadolinium(III] tetrahydrate

    Directory of Open Access Journals (Sweden)

    Dai-Zhi Kuang

    2011-10-01

    Full Text Available In the centrosymmetric polymeric title compound, {[CoGd2(C14H8N2O54(H2O4]·4H2O}n, the GdIII cation is coordinated by one water molecule and four pyridine-4-carboxamidoisophthalate (L anions in a distorted square-antiprismatic arrangement, while the CoII cation, located on an inversion center, is coordinated by two pyridyl-N atoms, two carboxylate-O atoms and two water molecules in a distorted octahedral geometry. The asymmetric unit contains two anionic L ligands: one bridges two Gd cations and one Co cation through two carboxyl groups and one pyridine-N atom; the other bridges two Gd cations and one Co cation through two carboxyl groups and the uncoordinated pyridine-N atom is hydrogen-bonded to the adjacent coordinated water molecule. Extensive O—H...O and N—H...O hydrogen bonds are present in the crystal structure.

  20. Synthesis and Characterization of Heteronuclear Copper(II-Lanthanide(III Complexes of N,N′-1,3-Propylenebis(Salicylaldiminato Where Lanthanide(III = Gd or Eu

    Directory of Open Access Journals (Sweden)

    Longjam Jaideva Singh

    2013-01-01

    Full Text Available Three complexes, namely, [Cu(salbn] (1, [Cu(salbnGd(NO33·H2O] (2, and [Cu(salbnEu(NO33·H2O] (3 where salbn = N,N′-1,3-propylenebis (salicylaldiminato have been synthesized and characterized by elemental analyses, ICP-AES, IR, UV, NMR, MS, EDX, powder XRD, and EPR spectroscopies. The EDX results suggest the presence of two different metal ions in heteronuclear complexes (2 and (3. The ligand(salbn, complex (1, and complex (3 crystallize in triclinic system while complex (2 crystallizes in monoclinic system. The EPR studies suggest that [Cu(salbn] complex is tetragonally coordinated monomeric copper(II complex with unpaired electron in the dx2-y2 orbital and spectral features that are the characteristics of axial symmetry while complex (2 in DMF solution at liquid nitrogen temperature exhibits an anisotropic broad signal around g ~ 2.03 which may suggest a weak magnetic spin-exchange interaction between Gd(III and Cu(II ions. The fluorescence intensity of Eu(III decreased markedly in the complex (3.

  1. On the Use of Molecular Weight Cutoff Cassettes to Measure Dynamic Relaxivity of Novel Gadolinium Contrast Agents: Example Using Hyaluronic Acid Polymer Complexes in Phosphate-Buffered Saline

    Directory of Open Access Journals (Sweden)

    Nima Kasraie

    2011-01-01

    Full Text Available The aims of this study were to determine whether standard extracellular contrast agents of Gd(III ions in combination with a polymeric entity susceptible to hydrolytic degradation over a finite period of time, such as Hyaluronic Acid (HA, have sufficient vascular residence time to obtain comparable vascular imaging to current conventional compounds and to obtain sufficient data to show proof of concept that HA with Gd-DTPA ligands could be useful as vascular imaging agents. We assessed the dynamic relaxivity of the HA bound DTPA compounds using a custom-made phantom, as well as relaxation rates at 10.72 MHz with concentrations ranging between 0.09 and 7.96 mM in phosphate-buffered saline. Linear dependences of static longitudinal relaxation rate (R1 on concentration were found for most measured samples, and the HA samples continued to produce high signal strength after 24 hours after injection into a dialysis cassette at 3T, showing superior dynamic relaxivity values compared to conventional contrast media such as Gd-DTPA-BMA.

  2. Mechanical downsizing of a gadolinium(III)-based metal-organic framework for anticancer drug delivery.

    Science.gov (United States)

    Kundu, Tanay; Mitra, Shouvik; Patra, Prasun; Goswami, Arunava; Díaz Díaz, David; Banerjee, Rahul

    2014-08-11

    A Gd(III) -based porous metal-organic framework (MOF), Gd-pDBI, has been synthesized using fluorescent linker pDBI (pDBI=(1,4-bis(5-carboxy-1H-benzimidazole-2-yl)benzene)), resulting in a three-dimensional interpenetrated structure with a one-dimensional open channel (1.9×1.2 nm) filled with hydrogen-bonded water assemblies. Gd-pDBI exhibits high thermal stability, porosity, excellent water stability, along with organic-solvent and mild acid and base stability with retention of crystallinity. Gd-pDBI was transformed to the nanoscale regime (ca. 140 nm) by mechanical grinding to yield MG-Gd-pDBI with excellent water dispersibility (>90 min), maintaining its porosity and crystallinity. In vitro and in vivo studies on MG-Gd-pDBI revealed its low blood toxicity and highest drug loading (12 wt %) of anticancer drug doxorubicin in MOFs reported to date with pH-responsive cancer-cell-specific drug release.

  3. Theoretical studies on polynuclear {Cu(II)5Gd(III)n} clusters (n = 4, 2): towards understanding their large magnetocaloric effect.

    Science.gov (United States)

    Rajeshkumar, Thayalan; Annadata, Harshini V; Evangelisti, Marco; Langley, Stuart K; Chilton, Nicholas F; Murray, Keith S; Rajaraman, Gopalan

    2015-02-16

    Density functional theory (DFT) studies on two polynuclear clusters, [Cu(II)5Gd(III)4O2(OMe)4(teaH)4(O2CC(CH3)3)2(NO3)4] (1) and [Cu5Gd2(OH)4(Br)2-(H2L)2(H3L)2(NO3)2(OH2)4] (2), have been carried out to probe the origin of the large magnetocaloric effect (MCE). The magnetic exchange interactions for 1 and 2 via multiple pathways are estimated using DFT calculations. While the calculated exchange parameters deviate from previous experimental estimates obtained by fitting the magnetic data, the DFT parameter set is found to offer a striking match to the magnetic data for both complexes, highlighting the problem of overparameterization. Magnetostructural correlations for {Cu-Gd} pairs have been developed where both the Cu-O-Gd angles and Cu-O-Gd-O dihedral angles are found to significantly influence the magnitude and sign of the exchange constants. The magnitude of the MCE has been examined as a function of the exchange interactions, and clues on how the effect can be enhanced are discussed.

  4. [Applications of metal ions and their complexes in medicine I].

    Science.gov (United States)

    Nagy, László; Csintalan, Gabriella; Kálmán, Eszter; Sipos, Pál; Szvetnik, Attila

    2003-01-01

    The "inorganic medical chemistry" is a rapidly developing field with enormous potential for applications, which offers new possibilities to the pharmaceutical industry. For example, the titanocene dichloride is already in clinical use, and antimetastatic activity of a range of Ru(III) complexes is also well established. There are ways to minimize the toxicity of Gd(III) complexes and therefore they can be safely injected as MRI contrast agents. The so called "ligand design" allows paramagnetic ions to be targeted to specific organs. Such designed ligands also enable the targeting of radiodiagnostic (99mTc) and radiotherapeutic (186Re) isotopes. There is a significant progress in understanding the coordination chemistry and biochemistry of metal ion(s) containing complexes such as Au antiarthritic and Bi antiulcer drugs. Further, currently developing areas include Mn (SOD mimics), V (insulin mimics), Ru (NO scavengers), Ln-based photosensitizers, metal-targeted organic agents and the Fe overload. The expanding knowledge of the role of metals in biochemistry is expected to provide scope for the design of new drugs in many other areas too, for example neuropharmaceutical and antiaffective agents. Progress in coordination chemistry is strongly dependent on understanding not only the thermodynamics of reactions, but also the kinetics of metal complexes under biologically relevant conditions.

  5. Lanthanide complexes of tritopic bis(hydrazone) ligands: single-molecule magnet behavior in a linear Dy(III)3 complex.

    Science.gov (United States)

    Anwar, Muhammad U; Tandon, Santokh S; Dawe, Louise N; Habib, Fatemah; Murugesu, Muralee; Thompson, Laurence K

    2012-01-16

    Tritopic pyridinebis(hydrazone)-based ligands typically produce square M(9) [3 × 3] grid complexes with first-row transition-metal ions (e.g., M = Mn, Fe, Co, Cu, Zn), but with larger lanthanide ions, such coordination motifs are not produced, and instead linear trinuclear complexes appear to be a preferred option. The reaction of 2pomp [derived from pyridine-2,6-bis(hydrazone) and 2-acetylpyridine] with La(III), Gd(III), and Dy(III) salts produces helical linear trinuclear [Ln(3)(2pomp)(2)]-based complexes, where each metal ion occupies one of the three tridentate ligand pockets. Two ligands encompass the three metal ions, and internal connections between metal ions occur through μ-O(hydrazone) bridges. Coligands include benzoate, nitrate, and N,N-dimethylformamide. The linear Dy(III)(3) complex exhibits single-molecule magnet behavior, demonstrated through alternating-current susceptibility measurements. Slow thermal magnetic relaxation was detected in an external field of 1800 Oe, where quantum-tunneling effects were suppressed (U(eff) = 14 K).

  6. Single-molecule magnet behavior for an antiferromagnetically superexchange-coupled dinuclear dysprosium(III) complex.

    Science.gov (United States)

    Long, Jérôme; Habib, Fatemah; Lin, Po-Heng; Korobkov, Ilia; Enright, Gary; Ungur, Liviu; Wernsdorfer, Wolfgang; Chibotaru, Liviu F; Murugesu, Muralee

    2011-04-13

    A family of five dinuclear lanthanide complexes has been synthesized with general formula [Ln(III)(2)(valdien)(2)(NO(3))(2)] where (H(2)valdien = N1,N3-bis(3-methoxysalicylidene)diethylenetriamine) and Ln(III) = Eu(III)1, Gd(III)2, Tb(III)3, Dy(III)4, and Ho(III)5. The magnetic investigations reveal that 4 exhibits single-molecule magnet (SMM) behavior with an anisotropic barrier U(eff) = 76 K. The step-like features in the hysteresis loops observed for 4 reveal an antiferromagnetic exchange coupling between the two dysprosium ions. Ab initio calculations confirm the weak antiferromagnetic interaction with an exchange constant J(Dy-Dy) = -0.21 cm(-1). The observed steps in the hysteresis loops correspond to a weakly coupled system similar to exchange-biased SMMs. The Dy(2) complex is an ideal candidate for the elucidation of slow relaxation of the magnetization mechanism seen in lanthanide systems.

  7. pH-Responsive Relaxometric Behaviour of Coordination Polymer Nanoparticles Made of a Stable Macrocyclic Gadolinium Chelate.

    Science.gov (United States)

    Aríñez-Soriano, Javier; Albalad, Jorge; Carné-Sánchez, Arnau; Bonnet, Célia S; Busqué, Félix; Lorenzo, Julia; Juanhuix, Jordi; Terban, Maxwell W; Imaz, Inhar; Tóth, Éva; Maspoch, Daniel

    2016-09-01

    Lanthanide-containing nanoscale particles have been widely explored for various biomedical purposes, however, they are often prone to metal leaching. Here we have created a new coordination polymer (CP) by applying, for the first time, a stable Gd(III) chelate as building block in order to prevent any fortuitous release of free lanthanide(III) ion. The use of the Gd-DOTA-4AmP complex as a design element in the CP allows not only for enhanced relaxometric properties (maximum r1 =16.4 mm(-1)  s(-1) at 10 MHz), but also for a pH responsiveness (Δr1 =108 % between pH 4 and 6.5), beyond the values obtained for the low molecular weight Gd-DOTA-4AmP itself. The CP can be miniaturised to the nanoscale to form colloids that are stable in physiological saline solution and in cell culture media and does not show cytotoxicity.

  8. Multifunctional Magnetic Gd(3+) -Based Coordination Polymer Nanoparticles: Combination of Magnetic Resonance and Multispectral Optoacoustic Detections for Tumor-Targeted Imaging in vivo.

    Science.gov (United States)

    An, Qiao; Liu, Jing; Yu, Meng; Wan, Jiaxun; Li, Dian; Wang, Changchun; Chen, Chunying; Guo, Jia

    2015-11-11

    To overcome traditional barriers in optical imaging and microscopy, optoacoustic-imaging has been changed to combine the accuracy of spectroscopy with the depth resolution of ultrasound, achieving a novel modality with powerful in vivo imaging. However, magnetic resonance imaging provides better spatial and anatomical resolution. Thus, a single hybrid nanoprobe that allows for simultaneous multimodal imaging is significant not only for cutting edge research in imaging science, but also for accurate clinical diagnosis. A core-shell-structured coordination polymer composite microsphere has been designed for in vivo multimodality imaging. It consists of a Fe3 O4 nanocluster core, a carbon sandwiched layer, and a carbocyanine-Gd(III) (Cy-Gd(III) ) coordination polymer outer shell (Fe3 O4 @C@Cy-Gd(III) ). Folic acid-conjugated poly(ethylene glycol) chains are embedded within the coordination polymer shell to achieve extended circulation and targeted delivery of probe particles in vivo. Control of Fe3 O4 core grain sizes results in optimal r2 relaxivity (224.5 × 10(-3) m(-1) s(-1) ) for T2 -weighted magnetic resonance imaging. Cy-Gd(III) coordination polymers are also regulated to obtain a maximum 25.1% of Cy ligands and 5.2% of Gd(III) ions for near-infrared fluorescence and T1 -weighted magnetic resonance imaging, respectively. The results demonstrate their impressive abilities for targeted, multimodal, and reliable imaging.

  9. Single-molecule magnet behavior in 2,2’-bipyrimidine-bridged dilanthanide complexes

    Directory of Open Access Journals (Sweden)

    Wen Yu

    2016-01-01

    Full Text Available A series of 2,2’-bipyrimidine-bridged dinuclear lanthanide complexes with the general formula [Ln(tmhd3]2bpm (tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionate, bpm = 2,2’-bipyrimidine, Ln = Gd(III, 1; Tb(III, 2; Dy(III, 3; Ho(III, 4 and Er(III, 5 has been synthesized and characterized. Sublimation of [Tb(tmhd3]2bpm onto a Au(111 surface leads to the formation of a homogeneous film with hexagonal pattern, which was studied by scanning tunneling microscopy (STM. The bulk magnetic properties of all complexes have been studied comprehensively. The dynamic magnetic behavior of the Dy(III and Er(III compounds clearly exhibits single molecule magnet (SMM characteristics with an energy barrier of 97 and 25 K, respectively. Moreover, micro-SQUID measurements on single crystals confirm their SMM behavior with the presence of hysteresis loops.

  10. 1,2-hydroxypyridonates as contrast agents for magnetic resonance imaging: TREN-1,2-HOPO.

    Science.gov (United States)

    Jocher, Christoph J; Moore, Evan G; Xu, Jide; Avedano, Stefano; Botta, Mauro; Aime, Silvio; Raymond, Kenneth N

    2007-10-29

    1,2-Hydroxypyridinones (1,2-HOPO) form very stable lanthanide complexes that may be useful as contrast agents for magnetic resonance imaging (MRI). X-ray diffraction of single crystals established that the solid-state structures of the Eu(III) and the previously reported [Inorg. Chem. 2004, 43, 5452] Gd(III) complex are identical. The recently discovered sensitizing properties of 1,2-HOPO chelates for Eu(III) luminescence [J. Am. Chem. Soc. 2006, 128, 10 067] allow for direct measurement of the number of water molecules coordinated to the metal center. Fluorescence measurements of the Eu(III) complex corroborate that, in solution, two water molecules coordinate the lanthanide (q = 2) as proposed from the analysis of NMRD profiles. In addition, fluorescence measurements have verified the anion binding interactions of lanthanide TREN-1,2-HOPO complexes in solution, studied by relaxivity, revealing only very weak oxalate binding (KA = 82.7 +/- 6.5 M-1). Solution thermodynamic studies of the metal complex and free ligand have been carried out using potentiometry, spectrophotometry, and fluorescence spectroscopy. The metal ion selectivity of TREN-1,2-HOPO supports the feasibility of using 1,2-HOPO ligands for selective lanthanide binding [pGd = 19.3 (2), pZn = 15.2 (2), pCa = 8.8 (3)].

  11. Poly[[diaquabis(μ3-isonicotinato-κ3N:O:O′bis(μ2-isonicotinato-κ2N:Ogadolinium(IIIdisiliver(I] nitrate monohydrate

    Directory of Open Access Journals (Sweden)

    Ji-Huai Wu

    2010-10-01

    Full Text Available In the title compound, {[Ag2Gd(C6H4NO24(H2O2]NO3·H2O}n, the GdIII ion is coordinated by eight O atoms from six isonicotinate ligands and two water molecules in a distorted square antiprismatic geometry. Two AgI ions are each bonded to two N atoms from two isonicotinate ligands in a linear or bow-like fashion [N—Ag—N angles = 178.6 (2 and 147.1 (2°]. These metal ions are connected by the isonicotinate ligands into a layer parallel to (010. O—H...O hydrogen bonds donated by the coordinated and uncoordinated water molecules and intralayer π–π stacking interactions between the pyridine rings [centroid–centroid distances = 3.551 (4 and 3.555 (4 Å] are observed. The layers interact with each other by interlayer Ag...O(aqua contacts [2.731 (4 Å] and π–π stacking interactions between the pyridine rings [centroid–centroid distances = 3.466 (3 and 3.516 (3 Å], resulting in the formation of a three-dimensional supramolecular structure.

  12. Comparison of MRI properties between derivatized DTPA and DOTA gadolinium-dendrimer conjugates

    Science.gov (United States)

    Nwe, K.; Bernardo, M; Regino, C. A. S.; Williams, M; Brechbiel, M. W.

    2010-01-01

    In this report we directly compare the in vivo and in vitro MRI properties of gadolinium-dendrimer conjugates of derivatized acyclic diethylenetriamine-N,N’,N’,N’’, N’’-pentaacetic acid (1B4M-DTPA) and macrocyclic 1,4,7,10-tetraazacyclododecane-N,N’,N’’,N’’’-tetraacetic acid (C-DOTA). The metal-ligand chelates were pre-formed in alcohol prior to conjugation to the generation 4 PAMAM dendrimer (G4D), and the dendrimer-based agents were purified by Sephadex® G-25 column. The analysis and SE-HPLC data indicated chelate to dendrimer ratios of 30:1 and 28:1 respectively. Molar relaxivity measured at pH 7.4, 22°C, and 3T are comparable (29.5 vs. 26.9 mM−1s−1), and both conjugates are equally viable as MRI contrast agents based on the images obtained. The macrocyclic agent however exhibits a faster rate of clearance in vivo (t1/2 = 16 vs. 29 min.). Our conclusion is that the macrocyclic-based agent is the more suitable agent for in vivo use for these reasons combined with kinetic inertness associated with the Gd(III) DOTA complex stability properties. PMID:20663676

  13. Biodegradable human serum albumin nanoparticles as contrast agents for the detection of hepatocellular carcinoma by magnetic resonance imaging.

    Science.gov (United States)

    Watcharin, Waralee; Schmithals, Christian; Pleli, Thomas; Köberle, Verena; Korkusuz, Hüdayi; Huebner, Frank; Zeuzem, Stefan; Korf, Hans W; Vogl, Thomas J; Rittmeyer, Claudia; Terfort, Andreas; Piiper, Albrecht; Gelperina, Svetlana; Kreuter, Jörg

    2014-05-01

    Tumor visualization by magnetic resonance imaging (MRI) and nanoparticle-based contrast agents may improve the imaging of solid tumors such as hepatocellular carcinoma (HCC). In particular, human serum albumin (HSA) nanoparticles appear to be a suitable carrier due to their safety and feasibility of functionalization. In the present study HSA nanoparticles were conjugated with gadolinium diethylenetriaminepentaacetic acid (Gd-DTPA) using carbodiimide chemistry. The nanoparticles had a uniform spherical shape and a diameter of 235±19nm. For better optical visualization in vitro and in vivo, the HSA-Gd nanoparticles were additionally labeled with rhodamine 123. As shown by confocal microscopy and flow cytometry analysis, the fluorescent nanoparticles were readily taken up by Huh-7 hepatocellular carcinoma cells. After 24h incubation in blood serum, less than 5% of the Gd(III) was released from the particles, which suggests that this nanoparticulate system may be stable in vivo and, therefore, may serve as potentially safe T1 MRI contrast agent for MRI of hepatocellular carcinoma.

  14. Self-assembled polymeric nanoparticles as new, smart contrast agents for cancer early detection using magnetic resonance imaging.

    Science.gov (United States)

    Mouffouk, Fouzi; Simão, Teresa; Dornelles, Daniel F; Lopes, André D; Sau, Pablo; Martins, Jorge; Abu-Salah, Khalid M; Alrokayan, Salman A; Rosa da Costa, Ana M; dos Santos, Nuno R

    2015-01-01

    Early cancer detection is a major factor in the reduction of mortality and cancer management cost. Here we developed a smart and targeted micelle-based contrast agent for magnetic resonance imaging (MRI), able to turn on its imaging capability in the presence of acidic cancer tissues. This smart contrast agent consists of pH-sensitive polymeric micelles formed by self-assembly of a diblock copolymer (poly(ethyleneglycol-b-trimethylsilyl methacrylate)), loaded with a gadolinium hydrophobic complex ((t)BuBipyGd) and exploits the acidic pH in cancer tissues. In vitro MRI experiments showed that (t)BuBipyGd-loaded micelles were pH-sensitive, as they turned on their imaging capability only in an acidic microenvironment. The micelle-targeting ability toward cancer cells was enhanced by conjugation with an antibody against the MUC1 protein. The ability of our antibody-decorated micelles to be switched on in acidic microenvironments and to target cancer cells expressing specific antigens, together with its high Gd(III) content and its small size (35-40 nm) reveals their potential use for early cancer detection by MRI.

  15. The addition of a second lanthanide ion to increase the luminescence of europium(III) macrocyclic complexes

    Energy Technology Data Exchange (ETDEWEB)

    Bromm, A.J. Jr.; Vallarino, L.M. [Virginia Commonwealth Univ., Richmond, VA (United States). Dept. of Chemistry; Leif, R.C. [Newport Instruments, San Diego, CA (United States); Quagliano, J.R. [Los Alamos National Lab., NM (United States)

    1998-12-29

    At present, the microscopic visualization of luminescent labels containing lanthanide(III) ions, primarily europium(III), as light-emitting centers is best performed with time-gated instrumentation, which by virtually eliminating the background fluorescence results in an improved signal to noise ratio. However, the use of the europium(III) macrocycle, Quantum Dye{trademark}, in conjunction with the strong luminescence enhancing effect (cofluorescence) of yttrium(III) or gadolinium(III), can eliminate the need for such specialized instrumentation. In the presence of Gd(III), the luminescence of the Eu(III)-macrocycles can be conveniently observed with conventional fluorescence instrumentation at previously unattainable low levels. The Eu(III) {sup 5}D{sub 0} {r_arrow} {sup 7}F{sub 2} emission of the Eu(III)-macrocycles was observed as an extremely sharp band with a maximum at 619 nm and a clearly resolved characteristic pattern. At very low Eu(III)-macrocycle concentrations, another sharp emission was detected at 614 nm, arising from traces of Eu(III) present in even the purest commercially available gadolinium products. Discrimination of the resolved emissions of the Eu(III)-macrocycle and Eu(III) contaminant should provide a means to further lower the limit of detection of the Eu(III)-macrocycle.

  16. Cell-permeable Ln(III) chelate-functionalized InP quantum dots as multimodal imaging agents.

    Science.gov (United States)

    Stasiuk, Graeme J; Tamang, Sudarsan; Imbert, Daniel; Poillot, Cathy; Giardiello, Marco; Tisseyre, Céline; Barbier, Emmanuel L; Fries, Pascal Henry; de Waard, Michel; Reiss, Peter; Mazzanti, Marinella

    2011-10-25

    Quantum dots (QDs) are ideal scaffolds for the development of multimodal imaging agents, but their application in clinical diagnostics is limited by the toxicity of classical CdSe QDs. A new bimodal MRI/optical nanosized contrast agent with high gadolinium payload has been prepared through direct covalent attachment of up to 80 Gd(III) chelates on fluorescent nontoxic InP/ZnS QDs. It shows a high relaxivity of 900 mM(-1) s(-1) (13 mM(-1 )s(-1) per Gd ion) at 35 MHz (0.81 T) and 298 K, while the bright luminescence of the QDs is preserved. Eu(III) and Tb(III) chelates were also successfully grafted to the InP/ZnS QDs. The absence of energy transfer between the QD and lanthanide emitting centers results in a multicolor system. Using this convenient direct grafting strategy additional targeting ligands can be included on the QD. Here a cell-penetrating peptide has been co-grafted in a one-pot reaction to afford a cell-permeable multimodal multimeric MRI contrast agent that reports cellular localization by fluorescence and provides high relaxivity and increased tissue retention with respect to commercial contrast agents.

  17. Quantitative Imaging of Cell-Permeable Magnetic Resonance Contrast Agents Using X-Ray Fluorescence

    Directory of Open Access Journals (Sweden)

    Paul J. Endres

    2006-10-01

    Full Text Available The inability to transduce cellular membranes is a limitation of current magnetic resonance imaging probes used in biologic and clinical settings. This constraint confines contrast agents to extracellular and vascular regions of the body, drastically reducing their viability for investigating processes and cycles in developmental biology. Conversely, a contrast agent with the ability to permeate cell membranes could be used in visualizing cell patterning, cell fate mapping, gene therapy, and, eventually, noninvasive cancer diagnosis. Therefore, we describe the synthesis and quantitative imaging of four contrast agents with the capability to cross cell membranes in sufficient quantity for detection. Each agent is based on the conjugation of a Gd(III chelator with a cellular transduction moiety. Specifically, we coupled Gd(III–diethylenetriaminepentaacetic acid DTPA and Gd(III–1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid with an 8–amino acid polyarginine oligomer and an amphipathic stilbene molecule, 4-amino-4'-(N,N-dimethylaminostilbene. The imaging modality that provided the best sensitivity and spatial resolution for direct detection of the contrast agents is synchrotron radiation x-ray fluorescence (SR-XRF. Unlike optical microscopy, SR-XRF provides two-dimensional images with resolution 103 better than 153Gd gamma counting, without altering the agent by organic fluorophore conjugation. The transduction efficiency of the intracellular agents was evaluated by T1 analysis and inductively coupled plasma mass spectrometry to determine the efficacy of each chelate-transporter combination.

  18. Direct measurement of the Mn(II) hydration state in metal complexes and metalloproteins through 17O NMR line widths.

    Science.gov (United States)

    Gale, Eric M; Zhu, Jiang; Caravan, Peter

    2013-12-11

    Here we describe a simple method to estimate the inner-sphere hydration state of the Mn(II) ion in coordination complexes and metalloproteins. The line width of bulk H2(17)O is measured in the presence and absence of Mn(II) as a function of temperature, and transverse (17)O relaxivities are calculated. It is demonstrated that the maximum (17)O relaxivity is directly proportional to the number of inner-sphere water ligands (q). Using a combination of literature data and experimental data for 12 Mn(II) complexes, we show that this method provides accurate estimates of q with an uncertainty of ±0.2 water molecules. The method can be implemented on commercial NMR spectrometers working at fields of 7 T and higher. The hydration number can be obtained for micromolar Mn(II) concentrations. We show that the technique can be extended to metalloproteins or complex:protein interactions. For example, Mn(II) binds to the multimetal binding site A on human serum albumin with two inner-sphere water ligands that undergo rapid exchange (1.06 × 10(8) s(-1) at 37 °C). The possibility of extending this technique to other metal ions such as Gd(III) is discussed.

  19. Visualization of Fluoride Ions In Vivo Using a Gadolinium(III)-Coumarin Complex-Based Fluorescence/MRI Dual-Modal Probe.

    Science.gov (United States)

    Wang, Yue; Song, Renfeng; Feng, Huan; Guo, Ke; Meng, Qingtao; Chi, Haijun; Zhang, Run; Zhang, Zhiqiang

    2016-12-16

    A new Gadolinium(III)-coumarin complex, DO3A-Gd-CA, was designed and prepared as a dual-modal probe for simultaneous fluorescence and relaxivity responses to fluoride ions (F(-)) in aqueous media and mice. DO3A-Gd-CA was designed by using Gd(III) center as an MRI signal output unit and fluoride binding site, and the 4-(diethylamino)-coumarin-3-carboxylic acid (CA) as a fluorescence reporter. Upon the addition of fluoride ions to the solution of DO3A-Gd-CA, the liberation of the coordinated CA ligand led to a 5.7-fold fluorescence enhancement and a 75% increase in the longitudinal relaxivity (r₁). The fluorescent detection limit for fluoride ions was determined to be 8 μM based on a 3σ/slope. The desirable features of the proposed DO3A-Gd-CA, such as high sensitivity and specificity, reliability at physiological pH and low cytotoxicity enable its application in visualization of fluoride ion in mice. The successful in vivo imaging indicates that DO3A-Gd-CA could be potentially used in biomedical diagnosis fields.

  20. Synthesis, structures,thermal and magnetic properties of a series of lanthanide [Ln=Sm, Gd, Er, Yb] complexes with 4-quinolineacarboxylate

    Institute of Scientific and Technical Information of China (English)

    GAO Qian; XIE Yabo; ZHANG Chong; SUN Jihong

    2009-01-01

    A series of lanthanide binuclear complexes, [Ln2(L)6(H2O)4]·2H2O (Ln=Sm(III), Gd(III), Er(III), Yb(III), HL=4-quinolineacarboxylic acid, were synthesized by reactions of corresponding rare earth salts with 4-quinolineacarboxylic acid at room temperature and were characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. X-ray diffraction analyses showed that they exhibited the same binuclear architecture and crystallized in monoclinic system and P21/c space group. In four complexes, each metal center adopted nine-coordinated mode coordinated by nine O atoms from two H2O molecules and three carboxyls of three ligands, and HL showed three different coordination modes. The variable-temperature magnetic susceptibility showed that complex [Gd2(L)6(H2O)4]·2H2O performed very weak antiferromagnetic property at low temperature and exchange was almost paramagnetic at high temperature. Complexes [Er2(L)6(H2O)4]·2H2O and [Yb2(L)6(H2O)4]·2H2O performed dominating antiferromagnetic coupling.

  1. Spectrophotometric Study of Ternary Complex Forming Systems of Some Lanthanide Metal Ions with Eriochrome Cyanine R in Presence of Cetylpyridinium Bromide for Microdetermination

    Directory of Open Access Journals (Sweden)

    A. S. Dhepe

    2011-01-01

    Full Text Available Study of coordination compounds of lanthanide elements has received a great attention due to growing applications in science and technology. Number of chromogenic reagents form water soluble colored complexes with lanthanides. Eriochrome cyanine R (ECR a member of triphenylmethane type of dye has been reported to form green colored complexes with lanthanides and has been used for microdetermination of these metal ions. Addition of cationic surfactant, Cetylpyridinium bromide (CPB, a cationic surfactant sensitizes the color reactions of Gd(III, Tb(III, Dy(III, Ho(III and Lu(III with ECR. Formation of water soluble, highly colored ternary complexes with a considerable bathochromic shift of about 50 nm in presence of surfactant has been observed. Optimum reaction conditions and other analytical parameters were also evaluated. Stoichiometric ratio 1:3:3 of Ln: ECR: CPB are responsible for the observed rise in molar absorptivity and sensitivity. Beer’s law was obeyed between 0.50 to 13.00 ppm. Effective photometric range and molar absorptivity of these ternary complexes have been calculated. Effect of some common interfering ions on determination of these lanthanide metal ions was studied. A simple, rapid and highly sensitive spectrophotometeric method has been proposed for the determination of metal ions understudy.

  2. Gd(III)-DOTA-modified sonosensitive liposomes for ultrasound-triggered release and MR imaging

    Science.gov (United States)

    Jung, Suk Hyun; Na, Kyunga; Lee, Seul A.; Cho, Sun Hang; Seong, Hasoo; Shin, Byung Cheol

    2012-08-01

    Ultrasound-sensitive (sonosensitive) liposomes for tumor targeting have been studied in order to increase the antitumor efficacy of drugs and decrease the associated severe side effects. Liposomal contrast agents having Gd(III) are known as a nano-contrast agent system for the efficient and selective delivery of contrast agents into pathological sites. The objective of this study was to prepare Gd(III)-DOTA-modified sonosensitive liposomes (GdSL), which could deliver a model drug, doxorubicin (DOX), to a specific site and, at the same time, be capable of magnetic resonance (MR) imaging. The GdSL was prepared using synthesized Gd(III)-DOTA-1,2-distearoyl- sn-glycero-3-phosphoethanolamine lipid. Sonosensitivity of GdSL to 20-kHz ultrasound induced 33% to 40% of DOX release. The relaxivities ( r 1) of GdSL were 6.6 to 7.8 mM-1 s-1, which were higher than that of MR-bester®. Intracellular uptake properties of GdSL were evaluated according to the intensity of ultrasound. Intracellular uptake of DOX for ultrasound-triggered GdSL was higher than that for non-ultrasound-triggered GdSL. The results of our study suggest that the paramagnetic and sonosensitive liposomes, GdSL, may provide a versatile platform for molecular imaging and targeted drug delivery.

  3. Solution chemistry of 1,15-bis(N,N-dimethyl)-5,11-dioxo-8-(N-benzyl)-1,4,8,12,15-pentaazapentadecane with metal ions of biological interest-Insights toward active metal ion containing therapeutics and diagnostic agents.

    Science.gov (United States)

    Nomkoko, Thembelani E; Jackson, Graham E; Nakani, Bandile S; Hunter, Roger

    2006-09-01

    The equilibrium constants of Cu(II), Zn(II), Ca(II) and Gd(III) with 1,15-bis(N,N-dimethyl)-5,11-dioxo-8-(N-benzyl)-1,4,8,12,15-pentaazapentadecane (La) have been studied at 25 degrees C and an ionic strength of 0.15 mol dm-3. Copper forms more stable complexes with La than the other metal ions investigated. This is probably due to the ease with which Cu(II) deprotonates the nitrogen donor atoms of the amide groups. UV/Vis spectrophotometric data indicate tetradentate binding of the ligand towards copper in [CuLaH-1] and pentadentate binding in [CuLaH-2]. Octanol-water partition coefficients of Cu(II)-La complexes indicate that although these species are largely hydrophilic, approximately 5.62% of the [CuLaH-1] complex goes into the organic phase. This percentage may promote dermal absorption of copper with a calculated penetration rate of 3.75x10(-4) mm h-1. The [CuLaH-1] species which predominates at pH 7.4 is a poor mimic of native copper-zinc superoxide dismutase. Blood-plasma simulation studies predict that La is unable to increase the low molecular mass copper fraction in vivo. This has been confirmed by biodistribution patterns, which are similar to those of 64CuCl2.

  4. High performance magneto-fluorescent nanoparticles assembled from terbium and gadolinium 1,3-diketones

    Science.gov (United States)

    Zairov, Rustem; Mustafina, Asiya; Shamsutdinova, Nataliya; Nizameev, Irek; Moreira, Beatriz; Sudakova, Svetlana; Podyachev, Sergey; Fattakhova, Alfia; Safina, Gulnara; Lundstrom, Ingemar; Gubaidullin, Aidar; Vomiero, Alberto

    2017-01-01

    Polyelectrolyte-coated nanoparticles consisting of terbium and gadolinium complexes with calix[4]arene tetra-diketone ligand were first synthesized. The antenna effect of the ligand on Tb(III) green luminescence and the presence of water molecules in the coordination sphere of Gd(III) bring strong luminescent and magnetic performance to the core-shell nanoparticles. The size and the core-shell morphology of the colloids were studied using transmission electron microscopy and dynamic light scattering. The correlation between photophysical and magnetic properties of the nanoparticles and their core composition was highlighted. The core composition was optimized for the longitudinal relaxivity to be greater than that of the commercial magnetic resonance imaging (MRI) contrast agents together with high level of Tb(III)-centered luminescence. The tuning of both magnetic and luminescent output of nanoparticles is obtained via the simple variation of lanthanide chelates concentrations in the initial synthetic solution. The exposure of the pheochromocytoma 12 (PC 12) tumor cells and periphery human blood lymphocytes to nanoparticles results in negligible effect on cell viability, decreased platelet aggregation and bright coloring, indicating the nanoparticles as promising candidates for dual magneto-fluorescent bioimaging.

  5. Dendritic surface functionalization of nanomaterials: controlling properties and functions for biomedical applications

    Directory of Open Access Journals (Sweden)

    Ali Nazemi

    2013-01-01

    Full Text Available A wide variety of nanomaterials have demonstrated promise in medical applications such as drug delivery and imaging. In these applications, the surface chemistry of the materials is critical as it plays an important role in determining the toxicity and biodistribution behavior of the material. We review here the functionalization of nanomaterials with dendrons as an efficient method to alter the surface chemistry of the materials, introducing new properties and functions. Described here is the functionalization of superparamagnetic iron oxide nanoparticles (SPIO with dendritic guanidines to enhance their transport into cells for magnetic resonance imaging applications. The introduction of dendrons bearing peripheral hydroxyls, amines, guanidines, carbohydrates and Gd(III chelates to polymer vesicles (polymersomes is also described. These dendritic moieties allow for modulation of toxicity, cell uptake, protein binding, and contrast agent efficiency, while at the same time allowing the stabilities of the polymersomes to be maintained. Thus, this approach holds promise for the development of a wide range of multifunctional materials for pharmaceutical applications.

  6. Americium/Lanthanide Separations in Alkaline Solutions for Advanced Nuclear Fuel Cycles

    Energy Technology Data Exchange (ETDEWEB)

    Goff, George S. [Los Alamos National Laboratory; Long, Kristy Marie [Los Alamos National Laboratory; Reilly, Sean D. [Los Alamos National Laboratory; Jarvinen, Gordon D. [Los Alamos National Laboratory; Runde, Wolfgang H. [Los Alamos National Laboratory

    2012-06-11

    Project goals: Can used nuclear fuel be partitioned by dissolution in alkaline aqueous solution to give a solution of uranium, neptunium, plutonium, americium and curium and a filterable solid containing nearly all of the lanthanide fission products and certain other fission products? What is the chemistry of Am/Cm/Ln in oxidative carbonate solutions? Can higher oxidation states of Am be stabilized and exploited? Conclusions: Am(VI) is kinetically stable in 0.5-2.0 M carbonate solutions for hours. Aliquat 336 in toluene has been successfully shown to extract U(VI) and Pu(VI) from carbonate solutions. (Stepanov et al 2011). Higher carbonate concentration gives lower D, SF{sub U/Eu} for = 4 in 1 M K{sub 2}CO{sub 3}. Experiments with Am(VI) were unsuccessful due to reduction by the organics. Multiple sources of reducing organics...more optimization. Reduction experiments of Am(VI) in dodecane/octanol/Aliquat 336 show that after 5 minutes of contact, only 30-40% of the Am(VI) has been reduced. Long enough to perform an extraction. Shorter contact times, lower T, and lower Aliquat 336 concentration still did not result in any significant extraction of Am. Anion exchange experiments using a strong base anion exchanger show uptake of U(VI) with minimal uptake of Nd(III). Experiments with Am(VI) indicate Am sorption with a Kd of 9 (10 minute contact) but sorption mechanism is not yet understood. SF{sub U/Nd} for = 7 and SF{sub U/Eu} for = 19 after 24 hours in 1 M K{sub 2}CO{sub 3}.

  7. Supramolecular coordination chemistry in aqueous solution: lanthanide ion-induced triple helix formation.

    Science.gov (United States)

    Lessmann, J J; Horrocks, W D

    2000-07-24

    The self-assembly of dinuclear triple helical lanthanide ion complexes (helicates), in aqueous solution, is investigated utilizing laser-induced, lanthanide luminescence spectroscopy. A series of dinuclear lanthanide (III) helicates (Ln(III)) based on 2,6-pyridinedicarboxylic acid (dipicolinic acid, dpa) coordinating units was synthesized by linking two dpa moieties using the organic diamines (1R,2R)-diaminocyclohexane (chxn-R,R) and 4,4'-diaminodiphenylmethane (dpm). Luminescence excitation spectroscopy of the Eu3+ 7F0-->5D0 transition shows the apparent cooperative formation of neutral triple helical complexes in aqueous solution, with a [Eu2L3] stoichiometry. Eu3+ excitation peak wavelengths and excited-state lifetimes correspond to those of the [Eu(dpa)3]3- model complex. CD studies of the Nd(III) helicate Nd2(dpa-chxn-R,R)3 reveal optical activity of the f-f transitions, indicating that the chiral linking group induces a stable chirality at the metal ion center. Molecular mechanics calculations using CHARMm suggest that the delta delta configuration at the Nd3+ ion centers is induced by the chxn-R,R linker. Stability constants were determined for both ligands with Eu3+, yielding identical results: log K = 31.6 +/- 0.2 (K in units of M-4). Metal-metal distances calculated from Eu3+-->Nd3+ energy-transfer experiments show that the complexes have metal-metal distances close to those calculated by molecular modeling. The fine structure in the Tb3+ emission bands is consistent with the approximate D3 symmetry as anticipated for helicates.

  8. Hypersensitivity in the 4f-4f absorption spectra of tris (acetylacetonato) neodymium(III) complexes with imidazole and pyrazole in non-aqueous solutions. Effect of environment on hypersensitive transitions

    Energy Technology Data Exchange (ETDEWEB)

    Ansari, Anees A.; Ilmi, Rashid [Department of Chemistry, Jamia Millia Islamia, New Delhi 110025 (India); Iftikhar, K., E-mail: kiftikhar.ch@jmi.ac.in [Department of Chemistry, Jamia Millia Islamia, New Delhi 110025 (India)

    2012-01-15

    The optical absorption spectra of [Nd(acac){sub 3}(H{sub 2}O){sub 2}].H{sub 2}O, [Nd(acac){sub 3}(im){sub 2}] and [Nd(acac){sub 3}(pz){sub 2}] (where acac is the anion of acetylacetone, im is imidazole and pz is pyrazole) complexes in the visible region have been analyzed. The transition {sup 4}G{sub 5/2} <- {sup 4}I{sub 9/2} located near the middle of the visible region (17,500 cm{sup -1}) is hypersensitive. Its behavior is in sharp contrast to many other typically weak and consistently unvaried, normal 4f-4f transitions. It is overlapped by a less intense transition {sup 2}G{sub 7/2} <- {sup 4}I{sub 9/2}. The band shapes of the hypersensitive transition show remarkable changes on passing from aqueous solution to various non-aqueous solutions, which is the result of changes in the environment about the Nd(III) ion in the various solutions and suggests coordination of a solvent molecules. Pyridine has been found especially effective in promoting 4f-4f electric-dipole intensity. The DMSO invades the complexes and replaces the water molecules and heterocyclic amines from the coordination sphere. Two DMSO molecules coordinate and the complexes acquire similar structure, [Nd(acac){sub 3}(DMSO){sub 2}] in solution. The oscillator strength and the band shape of the hypersensitive transition of all the complexes remains the same in this solvent. The IR spectra and the NMR spectra of the complexes have also discussed. - Highlights: > Structurally similar eight-coordinate complexes of neodymium are synthesized. > The 4f-4f absorption spectra are investigated in non-aqueous solvents. > Methanol, isopropanol and acetonitrile are coordinating solvents. > Pyridine and DMSO are coordinating solvents by replacing the ancillary ligands. > Pyridine is most effective in promoting the 4f-4f intensity.

  9. New unsymmetrical digycolamide ligands for trivalent actinide separation

    Energy Technology Data Exchange (ETDEWEB)

    Ravi, Jammu; Venkatesan, K.A.; Antony, M.P.; Srinivasan, T.G.; Rao, P.R. Vasudeva [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Fuel Chemistry Div.

    2014-10-01

    New unsymmetrical diglycolamides (UDGAs), N,N-di-butyl-N',N'-di-dodecyl-3-oxapentane-1,5-diamide (C{sub 12}-C{sub 4}), N,N-di-dodecyl-N',N'-di-hexyl-3-oxapentane-1,5-diamide (C{sub 12}-C{sub 6}), N,N-di-decyl-N',N'-di-dodecyl-3-oxapentane-1,5-diamide (C{sub 12}-C{sub 10}) have been synthesized, and evaluated for the separation of americium(III) and europium(III) from nitric acid medium. The extraction behavior of Am(III), Eu(III), and Sr(II) in a solution of these UDGAs in n-dodecane was studied as a function of concentration of nitric acid in the aqueous phase. The distribution ratio of Am(III) and Eu(III) increased with increase in the concentration of nitric acid. The third phase formation behavior of nitric acid and neodymium(III) in 0.1 M UDGA/n-dodecane was studied. The third phase formation was not observed in all these UDGAs in n-dodecane (0.1 M), when the concentration of Nd(III) was ∝ 500 mM in 3-4M nitric acid. The stoichiometry of Am(III)-UDGA was determined from the slope analysis of the extraction data, which indicated the formation of 1:3 complex in all cases. Our studies revealed that the UDGA ligands with dodecyl group attached to one amidic nitrogen atom is inevitable for preventing third phase formation and the alkyl group at the other amidic nitrogen can be varied from butyl to decyl group for obtaining efficient extraction of trivalent actinides from high-level nuclear waste. (orig.)

  10. T1-Weighted MR imaging of liver tumor by gadolinium-encapsulated glycol chitosan nanoparticles without non-specific toxicity in normal tissues

    Science.gov (United States)

    Na, Jin Hee; Lee, Sangmin; Koo, Heebeom; Han, Hyounkoo; Lee, Kyung Eun; Han, Seung Jin; Choi, Seung Hong; Kim, Hyuncheol; Lee, Seulki; Kwon, Ick Chan; Choi, Kuiwon; Kim, Kwangmeyung

    2016-05-01

    Herein, we have synthesized Gd(iii)-encapsulated glycol chitosan nanoparticles (Gd(iii)-CNPs) for tumor-targeted T1-weighted magnetic resonance (MR) imaging. The T1 contrast agent, Gd(iii), was successfully encapsulated into 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA)-modified CNPs to form stable Gd(iii)-encapsulated CNPs (Gd(iii)-CNPs) with an average particle size of approximately 280 nm. The stable nanoparticle structure of Gd(iii)-CNPs is beneficial for liver tumor accumulation by the enhanced permeation and retention (EPR) effect. Moreover, the amine groups on the surface of Gd(iii)-CNPs could be protonated and could induce fast cellular uptake at acidic pH in tumor tissue. To assay the tumor-targeting ability of Cy5.5-labeled Gd(iii)-CNPs, near-infrared fluorescence (NIRF) imaging and MR imaging were used in a liver tumor model as well as a subcutaneous tumor model. Cy5.5-labeled Gd(iii)-CNPs generated highly intense fluorescence and T1 MR signals in tumor tissues after intravenous injection, while DOTAREM®, the commercialized control MR contrast agent, showed very low tumor-targeting efficiency on MR images. Furthermore, damaged tissues were found in the livers and kidneys of mice injected with DOTAREM®, but there were no obvious adverse effects with Gd(iii)-CNPs. Taken together, these results demonstrate the superiority of Gd(iii)-CNPs as a tumor-targeting T1 MR agent.Herein, we have synthesized Gd(iii)-encapsulated glycol chitosan nanoparticles (Gd(iii)-CNPs) for tumor-targeted T1-weighted magnetic resonance (MR) imaging. The T1 contrast agent, Gd(iii), was successfully encapsulated into 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA)-modified CNPs to form stable Gd(iii)-encapsulated CNPs (Gd(iii)-CNPs) with an average particle size of approximately 280 nm. The stable nanoparticle structure of Gd(iii)-CNPs is beneficial for liver tumor accumulation by the enhanced permeation and retention (EPR) effect. Moreover, the

  11. Self-Assembly of Peptide Amphiphiles Designed as Imaging Probes for 19F and Relaxation-Enhanced 1H imaging

    Science.gov (United States)

    Preslar, Adam Truett

    This work incorporates whole-body imaging functionality into peptide amphiphile (PA) nanostructures used for regenerative medicine to facilitate magnetic resonance imaging (MRI). Two strategies were employed: 1. Conjugation of gadolinium chelates to peptide nanostructures to monitor biomaterial degradation in vivo with MRI and inductively-coupled plasma-mass spectroscopy (ICP-MS) 2. Synthesis of perfluorinated moiety-bearing peptide amphiphiles for 19F-MRI. The Gd(III) chelate gadoteridol was conjugated by copper-catalyzed "click" chemistry to a series of PAs known to form cylindrical nanostructures. By fitting nuclear magnetic resonance dispersion (NMRD) profiles to the Solomon-Bloembergen-Morgan (SBM) equations, it was observed that the water exchange parameter (tauM) depended on thermal annealing or calcium ion cross-linking. The sequence C16V 3A3E3G(Gd) exhibited an acceleration of nearly 100 ns after thermal annealing and calcium addition. These gadolinium-labeled PAs were used to track in vivo degradation of gels within the tibialis anterior muscle in a murine model. The half-life of biomaterial degradation was determined to be 13.5 days by inductively coupled plasma mass spectrometry (ICP-MS) of Gd(III). Gel implants could be monitored by MRI for eight days before the signal dispersed due to implant degradation and dilution. Additionally, nanostructures incorporating highly fluorinated domains were investigated for use as MRI contrast agents. Short, perfluoroalkyane tails of seven or eight carbon atoms in length were grafted to PA sequences containing a V2A2 beta-sheet forming sequence. The V2A2 sequence is known to drive 1D nanostructure assembly. It was found that the sequences C7F13V2A 2E2 and C7F13V2A 2K3 formed 1D assemblies in water which transition from ribbon-like to cylindrical shape as pH increases from 4.5 to 8.0. Ribbon-like nanostructures had reduced magnetic resonance signal by T 2 relaxation quenching, whereas their cylindrical counterparts

  12. Mononuclear and polynuclear complexes ligated by an iminodiacetic acid derivative: synthesis, structure, solution studies and magnetic properties.

    Science.gov (United States)

    Puentes, Roberto; Torres, Julia; Kremer, Carlos; Cano, Joan; Lloret, Francesc; Capucci, Davide; Bacchi, Alessia

    2016-03-28

    Two novel families of coordination polymers, [Ln(bzlida)(Hbzlida)]·H2O (Ln = La, Nd) and [Ln2(bzlida)3]·3H2O (Ln = Nd, Sm, Eu, Gd) were prepared by hydrothermal reaction of Ln2O3 with benzyliminodiacetic acid (H2bzlida). The conditions of synthesis, in particular the pH value, were selected on the basis of previous speciation studies reported in this work. The first type of complex consists of 1D chains built by a fully deprotonated ligand bridging two lanthanide ions and protonated Hbzlida(-) ligands connecting three cations. The second type is formed by [Ln2(bzlida)3] bimetallic units in which the ligand has a tridentate NOO coordination mode. This is expanded to a 2D network through carboxylate linkers. Under similar synthetic conditions but including copper acetate in the reaction mixture, a new compound was also obtained and characterized: [Cu(bzlida)2{Er(AcO)(H2O)5}2][Cu(bzlida)2]·6H2O (AcO = acetate). This salt is made up of the [Cu(bzlida)2{Er(AcO)(H2O)5}2](2+) heterotrimetallic complex cation containing an acetato bridge, and the [Cu(bzlida)2](2-) anion. The same reaction produces the monomeric [Cu(Hbzlida)2]·4H2O whose structure was also elucidated. Magnetic properties of the Gd(iii) derivative were studied and analyzed experimentally and theoretically. The results are compared and discussed with respect to those reported in the literature and a magnetostructural correlation is suggested.

  13. Relaxometric studies of gadolinium-functionalized perfluorocarbon nanoparticles for MR imaging.

    Science.gov (United States)

    de Vries, Anke; Moonen, Rik; Yildirim, Muhammed; Langereis, Sander; Lamerichs, Rolf; Pikkemaat, Jeroen A; Baroni, Simona; Terreno, Enzo; Nicolay, Klaas; Strijkers, Gustav J; Grüll, Holger

    2014-01-01

    Fluorine MRI ((19) F MRI) is receiving an increasing attention as a viable alternative to proton-based MRI ((1) H MRI) for dedicated application in molecular imaging. The (19) F nucleus has a high gyromagnetic ratio, a 100% natural abundance and is furthermore hardly present in human tissues allowing for hot spot MR imaging. The applicability of (19) F MRI as a molecular and cellular imaging technique has been exploited, ranging from cell tracking to detection and imaging of tumors in preclinical studies. In addition to applications, developing new contrast materials with improved relaxation properties has also been a core research topic in the field, since the inherently low longitudinal relaxation rates of perfluorocarbon compounds result in relatively low imaging efficiency. Borrowed from (1) H MRI, the incorporation of lanthanides, specifically Gd(III) complexes, as signal modulating ingredients in the nanoparticle formulation has emerged as a promising approach to improvement of the fluorine signal. Three different perfluorocarbon emulsions were investigated at five different magnetic field strengths. Perfluoro-15-crown-5-ether was used as the core material and Gd(III)DOTA-DSPE, Gd(III)DOTA-C6-DSPE and Gd(III)DTPA-BSA as the relaxation altering components. While Gd(III)DOTA-DSPE and Gd(III)DOTA-C6-DSPE were favorable constructs for (1) H NMR, Gd(III)DTPA-BSA showed the strongest increase in (19F) R(1). These results show the potential of the use of paramagnetic lipids to increase (19F) R(1) at clinical field strengths (1.5-3 T). At higher field strengths (6.3-14 T), gadolinium does not lead to an increase in (19F) R(1) compared with emulsions without gadolinium, but leads to an significant increase in (19F) R(2). Our data therefore suggest that the most favorable situation for fluorine measurements is at high magnetic fields without the inclusion of gadolinium constructs.

  14. Three isostructural one-dimensional Ln(III) chains with distorted cubane motifs showing dual fluorescence and slow magnetic relaxation/magnetocaloric effect.

    Science.gov (United States)

    Li, Yan; Yu, Jia-Wen; Liu, Zhong-Yi; Yang, En-Cui; Zhao, Xiao-Jun

    2015-01-05

    Three new homometallic lanthanide complexes with mixed carboxylate-modified rigid ligands, [Ln(μ3-OH)(na)(pyzc)]n (na(-) = 1-naphtholate, pyzc(-) = 2-pyrazinecarboxylate, Ln = Dy (1), Yb (2), and Gd (3)), were solvothermally synthesized, and their structures and magnetic as well as photophysical properties were completely investigated. Complexes 1-3 are crystallographically isostructural, exhibiting linear chains with four bidentate bridging μ-COO(-) moieties encapsulated cubic {Ln4(μ3-OH)4}(8+) clusters repeatedly extended by 4-fold chelating-bridging-pyzc(-) connectors. Magnetically, the former two complexes with highly anisotropic Dy(III) and weak anisotropic Yb(III) ions in the distorted NO7 triangular dodecahedron coordination environment display field-induced slow relaxation of magnetization. Fitting the dynamic magnetic data to the Arrhenius law gives energy barrier ΔE/kB = 39.6 K and pre-exponential factor τo = 1.52 × 10(-8) s for 1 and ΔE/kB = 14.1 K and τo = 2.13 × 10(-7) s for 2. By contrast, complex 3 with isotropic Gd(III) ion and weak intracluster antiferromagnetic coupling shows a significant cryogenic magnetocaloric effect, with a maximum -ΔSm value of 30.0 J kg(-1) K(-1) at 2.5 K and 70 kOe. Additionally, the chromophoric na(-) and pyzc(-) ligands can serve as antenna groups, selectively sensitizing the Dy(III)- and Yb(III)-based luminescence of 1 and 2 in the UV-visible region by an intramolecular energy transfer process. Thus, complexes 1-3, incorporating field-induced slow magnetic magnetization and interesting luminescence together, can be used as composite magneto-optical materials. More importantly, these interesting results further demonstrate that the mixed-ligand system with rigid carboxylate-functionalized chromophores can be excellent candidates for the preparations of new bifunctional magneto-optical materials.

  15. Magnetic and magnetocaloric properties of an unusual family of carbonate-panelled [Ln(III)(6)Zn(III)(2)] cages.

    Science.gov (United States)

    Sethi, Waqas; Sanz, Sergio; Pedersen, Kasper S; Sørensen, Mikkel A; Nichol, Gary S; Lorusso, Giulia; Evangelisti, Marco; Brechin, Euan K; Piligkos, Stergios

    2015-06-14

    The reaction of the pro-ligand H4L, which combines the complementary phenolic oxime and diethanolamine moieties within the same organic framework, with Zn(NO3)2·6H2O and Ln(NO3)3·6H2O in a basic methanolic solution generates a family of isostructural heterometallic coordination compounds of general formula [Ln6Zn2(CO3)5(OH)(H2L)4(H3L)2(H4L)]NO3·xMeOH [Ln = Gd, x = 30 (), Ln = Dy, x = 32 (), Ln = Sm, x = 31 (), Ln = Eu, x = 29 (), Ln = Tb, x = 30 ()]. The octametallic skeleton of the cage describes a heavily distorted [Gd] octahedron capped on two faces by Zn(II) ions. The metal core is stabilised by a series of μ3- and μ4-CO3(2-) ions, originating from the serendipitous fixation of atmospheric CO2. The magnetic properties of all family members were examined via SQUID magnetometry, with the χMT product and VTVB data of the Gd analogue () being independently fitted by numerical diagonalisation to afford the same best-fit parameter JGd-Gd = -0.004 cm(-1). The MCE of complex was elucidated from specific heat data, with the magnetic entropy change reaching a value of 22.6 J kg(-1) K(-1) at T = 1.7 K, close to the maximum entropy value per mole expected from six Gd(III) spins (SGd = 7/2), 23.7 J kg(-1) K(-1).

  16. Self-assembly synthesis, structural features, and photophysical properties of dilanthanide complexes derived from a novel amide type ligand: energy transfer from Tb(III) to Eu(III) in a heterodinuclear derivative.

    Science.gov (United States)

    Gao, Cunji; Kirillov, Alexander M; Dou, Wei; Tang, Xiaoliang; Liu, Liangliang; Yan, Xuhuan; Xie, Yujie; Zang, Peixian; Liu, Weisheng; Tang, Yu

    2014-01-21

    A novel amide type ligand benzyl-N,N-bis[(2'-furfurylaminoformyl)phenoxyl)ethyl]-amine (L) has been designed and applied for the self-assembly generation of homodinuclear lanthanide coordination compounds [Ln2(μ2-L)2(NO3)6(EtOH)2] [Ln = Eu (1), Tb (2), and Gd (3)] and a heterodinuclear derivative [EuTb(μ2-L)2(NO3)6(EtOH)2] (4). All the complexes have been characterized by the X-ray single-crystal diffraction analyses. They are isostructural, crystallize in a monoclinic space group P21/c, and form [2 + 2] rectangular macrocycle structures. Compound 4 is the first example of a [2 + 2] rectangular macrocycle heterodinuclear EuTb complex assembled from an amide type ligand. In 4, the discrete 0D dimeric [EuTb(μ2-L)2(NO3)6(EtOH)2] units are extended, via the multiple N-H···O hydrogen bonds, into a 2D supramolecular network that has been topologically classified as a uninodal 4-connected underlying net with the sql [Shubnikov tetragonal plane net] topology. The triplet state ((3)ππ*) of L studied by the Gd(III) complex 3 demonstrated that the ligand beautifully populates Tb(III) emission (Φ = 52%), whereas the corresponding Eu(III) derivative 1 shows weak luminescence efficiency (Φ = 0.7%) because the triplet state of L has a poor match with (5)D1 energy level of Eu(III). Furthermore, the photoluminescent properties of heterodinuclear complex 4 have been compared with those of the analogous homodinuclear compounds. The quantum yield and lifetime measurements prove that energy transfer from Tb(III) to Eu(III) is being achieved, namely, that the Tb(III) center is also acting to sensitize the Eu(III) and enhancing Eu(III) emission in 4.

  17. DNA-gadolinium-gold nanoparticles for in vivo T1 MR imaging of transplanted human neural stem cells.

    Science.gov (United States)

    Nicholls, Francesca J; Rotz, Matthew W; Ghuman, Harmanvir; MacRenaris, Keith W; Meade, Thomas J; Modo, Michel

    2016-01-01

    The unambiguous imaging of transplanted cells remains a major challenge to understand their biological function and therapeutic efficacy. In vivo imaging of implanted cells is reliant on tagging these to differentiate them from host tissue, such as the brain. We here characterize a gold nanoparticle conjugate that is functionalized with modified deoxythymidine oligonucleotides bearing Gd(III) chelates and a red fluorescent Cy3 moiety to visualize in vivo transplanted human neural stem cells. This DNA-Gd@Au nanoparticle (DNA-Gd@AuNP) exhibits an improved T1 relaxivity and excellent cell uptake. No significant effects of cell uptake have been found on essential cell functions. Although T1 relaxivity is attenuated within cells, it is sufficiently preserved to afford the in vivo detection of transplanted cells using an optimized voxel size. In vivo MR images were corroborated by a post-mortem histological verification of DNA-Gd@AuNPs in transplanted cells. With 70% of cells being correctly identified using the DNA-Gd-AuNPs indicates an overall reliable detection. Less than 1% of cells were false positive for DNA-Gd@AuNPs, but a significant number of 30% false negatives reveals a dramatic underestimation of transplanted cells using this approach. DNA-Gd@AuNPs therefore offer new opportunities to visualize transplanted cells unequivocally using T1 contrast and use cellular MRI as a tool to derive biologically relevant information that allows us to understand how the survival and location of implanted cells determines therapeutic efficacy.

  18. Importance of outer-sphere and aggregation phenomena in the relaxation properties of phosphonated gadolinium complexes with potential applications as MRI contrast agents.

    Science.gov (United States)

    Elhabiri, Mourad; Abada, Sabah; Sy, Mohamadou; Nonat, Aline; Choquet, Philippe; Esteban-Gómez, David; Cassino, Claudio; Platas-Iglesias, Carlos; Botta, Mauro; Charbonnière, Loïc J

    2015-04-20

    A series composed of a tetra-, a tris- and a bisphosphonated ligand based on a pyridine scaffold (L(4) , L(3) and L(2) , respectively) was studied within the frame of lanthanide (Ln) coordination. The stability constants of the complexes formed with lanthanide cations (Ln=La, Nd, Eu, Gd, Tb, Er and Lu) were determined by potentiometry in aqueous solutions (25.0 °C, 0.1 M NaClO4 ), showing that the tetraphosphonated complexes are among the most stable Ln(III) complexes reported in the literature. The complexation of L(4) was further studied by different titration experiments using mass spectrometry and various spectroscopic techniques including UV/Vis absorption, and steady state and time-resolved luminescence (Ln=Eu and Tb). Titration experiments confirmed the formation of highly stable [LnL(4) ] complexes. (31) P NMR experiments of the LuL(4) complex revealed an intramolecular interconversion process which was studied at different temperatures and was rationalized by DFT modelling. The relaxivity properties of the Gd(III) complexes were studied by recording their (1) H NMRD profiles at various temperatures, by temperature dependent (17) O NMR experiments (GdL(4) ) and by pH dependent relaxivity measurements at 0.47 T (GdL(3) and GdL(2) ). In addition to the high relaxivity values observed for all complexes, the results showed an important second-sphere contribution to relaxivity and pH dependent variations associated with the formation of aggregates for GdL(2) and GdL(3) . Finally, intravenous injection of GdL(4) to a mouse was followed by dynamic MRI imaging at 1.5 T, which showed that the complex can be immediately found in the blood stream and rapidly eliminated through the liver and in large part through the kidneys.

  19. Cyanomethylene-bis(phosphonate)-based lanthanide complexes: structural, photophysical, and magnetic investigations.

    Science.gov (United States)

    Maxim, Catalin; Branzea, Diana G; Tiseanu, Carmen; Rouzières, Mathieu; Clérac, Rodolphe; Andruh, Marius; Avarvari, Narcis

    2014-03-01

    The syntheses, structural investigations, magnetic and photophysical properties of a series of 10 lanthanide mononuclear complexes, containing the heteroditopic ligand cyanomethylene-bis(5,5-dimethyl-2-oxo-1,3,2λ(5)-dioxa-phosphorinane) (L), are described. The crystallographic analyses indicate two structural types: in the first one, [Ln(III)(L)3(H2O)2]·H2O (Ln = La, Pr, Nd), the metal ions are eight-coordinated within a square antiprism geometry, while the second one, [Ln(III)(L)3(H2O)]·8H2O (Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er), contains seven-coordinated Ln(III) ions within distorted monocapped trigonal prisms. Intermolecular hydrogen bonding between nitrogen atoms of the cyano groups, crystallization, and coordination water molecules leads to the formation of extended supramolecular networks. Solid-state photophysical investigations demonstrate that Eu(III) and Tb(III) complexes possess intense luminescence with relatively long excited-state lifetimes of 530 and 1370 μs, respectively, while Pr(III), Dy(III), and Ho(III) complexes have weak intensity luminescence characterized by short lifetimes ranging between a few nanoseconds to microseconds. The magnetic properties for Pr(III), Gd(III), Tb(III), Dy(III), and Ho(III) complexes are in agreement with isolated Ln(III) ions in the solid state, as suggested by the single-crystal X-ray analyses. Alternating current (ac) susceptibility measurements up to 10 kHz reveal that only the Ho(III) complex shows a frequency-dependent ac response, with a relaxation mode clearly observed at 1.85 K around 4500 Hz.

  20. A new family of [Cu(II)Ln(III)M(V)] heterotrimetallic complexes (Ln = La, Gd, Tb; M = Mo, W): model systems to probe exchange interactions and single-molecule magnet properties.

    Science.gov (United States)

    Visinescu, Diana; Alexandru, Maria-Gabriela; Madalan, Augustin M; Jeon, Ie-Rang; Mathonière, Corine; Clérac, Rodolphe; Andruh, Marius

    2016-05-01

    Four isostructural trinuclear 3d-4f-4(5)d heterotrimetallic complexes, with the general formula [L(2)CuLn(H2O)5(μ-NC)M(CN)7], were obtained from the association of binuclear 3d-4f complexes and {M(V)(CN)8}(3-) metalloligands (M = Mo, Ln = La ; M = W, Ln = La ; M = Mo, Ln = Gd ; M = Mo; Ln = Tb , where H2L(2) = 1,2-ethanediylbis(2-iminomethylene-6-methoxy-phenol)). The metalloligand coordinates through a single-cyanido group at the apical position of the copper(ii) ion belonging to the {Cu(II)Ln(III)} binuclear complex. The analysis of the magnetic data for the La(iii) derivatives (compounds and ), in the 1.85-300 K temperature range, shows a weak ferromagnetic exchange interaction between Cu(II) and Mo(V)/W(V) ions across the cyanido bridge (JCuM/kB = 3.6(6) K; g = 2.23(5) for and JCuM/kB = 3.8(6) K, g = 2.21(5) for , with H = -2JCuMSCu·SM). These results were used to simulate the magnetic properties of compound , using the isotropic spin Hamiltonian H = -2JCuMoSCu·SMo - 2JCuGdSCu·SGd. The resulting magnetic interaction between Cu(II) and Gd(III) ions via the phenoxo-bridge was found to be weakly ferromagnetic (JCuGd/kB = +4.5(2) K with JCuMo/kB = +3.6(2) K, gGd = gCu = 2.00 and gMo = 1.98). The dc magnetic properties for compound also show a predominant ferromagnetic interaction, while the ac magnetic measurements indicate the presence of the slow relaxation of the magnetization below 3.5 K.

  1. The role of equilibrium and kinetic properties in the dissociation of Gd[DTPA-bis(methylamide)] (Omniscan) at near to physiological conditions.

    Science.gov (United States)

    Baranyai, Zsolt; Brücher, Ernő; Uggeri, Fulvio; Maiocchi, Alessandro; Tóth, Imre; Andrási, Melinda; Gáspár, Attila; Zékány, László; Aime, Silvio

    2015-03-16

    [Gd(DTPA-BMA)] is the principal constituent of Omniscan, a magnetic resonance imaging (MRI) contrast agent. In body fluids, endogenous ions (Zn(2+), Cu(2+), and Ca(2+)) may displace the Gd(3+). To assess the extent of displacement at equilibrium, the stability constants of DTPA-BMA(3-) complexes of Gd(3+), Ca(2+), Zn(2+), and Cu(2+) have been determined at 37 °C in 0.15 M NaCl. The order of these stability constants is as follows: GdL≈CuL>ZnL≫CaL. Applying a simplified blood plasma model, the extent of dissociation of Omniscan (0.35 mM [Gd(DTPA-BMA)]) was found to be 17% by the formation of Gd(PO4), [Zn(DTPA-BMA)](-) (2.4%), [Cu(DTPA-BMA)](-) (0.2%), and [Ca(DTPA-BMA)](-) (17.7%). By capillary electrophoresis, the formation of [Ca(DTPA-BMA)](-) has been detected in human serum spiked with [Gd(DTPA-BMA)] (2.0 mM) at pH 7.4. Transmetallation reactions between [Gd(DTPA-BMA)] and Cu(2+) at 37 °C in the presence of citrate, phosphate, and bicarbonate ions occur by dissociation of the complex assisted by the endogenous ligands. At physiological concentrations of citrate, phosphate, and bicarbonate ions, the half-life of dissociation of [Gd(DTPA-BMA)] was calculated to be 9.3 h at pH 7.4. Considering the rates of distribution and dissociation of [Gd(DTPA-BMA)] in the extracellular space of the body, an open two-compartment model has been developed, which allows prediction of the extent of dissociation of the Gd(III) complex in body fluids depending on the rate of elimination of the contrast agent. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Aryl Bridged 1-Hydroxypyridin-2-one: Effect of the Bridge on the Eu(III) Sensitization Process

    Energy Technology Data Exchange (ETDEWEB)

    D' Aleo, Anthony; Moore, Evan G.; Szigethy, Geza; Xu, Jide; Raymond, Kenneth N.

    2009-06-17

    The efficiency of Eu3+ luminescence by energy transfer from an antenna ligand can be strongly dependent on the metal ion coordination geometry. The geometric component of the Eu(III) sensitization has been probed using series of tetradentate 1,2-HOPO derivatives that are connected by bridges of varying length and geometry. The ligands are N,N'-(1,2-phenylene)bis(1-hydroxy-6-oxo-1,6-dihydropyridine-2-carboxamide) for the ligand (L{sup 1}), 1-hydroxy-N-(2-(1-hydroxy-6-oxo-1,6-dihydropyridine-2-carboxamido)benzyl)-6-oxo-1,6-dihydropyridine-2-carboxamide (L{sup 2}) and N,N'-(1,2-phenylenebis(methylene))bis(1-hydroxy-6-oxo-1,6-dihydropyridine-2-carboxamide) (L{sup 3}). Spectroscopic characterization of both the Gd(III) and Eu(III) metal complexes, TD-DFT analysis of model compounds and evaluation of the kinetic parameters for the europium emission were completed. Some striking differences were observed in the luminescence quantum yield by altering the bridging unit. The [Eu(L{sup 2}){sub 2}]{sup -} derivative shows efficient sensitization coupled with good metal centered emission. For [Eu(L{sup 3}){sub 2}]{sup -}, the large quenching of the luminescence quantum yield compared to [Eu(L{sup 2}){sub 2}]{sup -} is primarily a result of one inner sphere water molecule bound to the europium cation while for [Eu(L{sup 1}){sub 2}]{sup -}, the low luminescence quantum yield can be attributed to inefficient sensitization of the europium ion.

  3. Gold-silver alloy nanoshells: a new candidate for nanotherapeutics and diagnostics

    Directory of Open Access Journals (Sweden)

    Karmonik Christof

    2011-01-01

    Full Text Available Abstract We have developed novel gold-silver alloy nanoshells as magnetic resonance imaging (MRI dual T 1 (positive and T 2 (negative contrast agents as an alternative to typical gadolinium (Gd-based contrast agents. Specifically, we have doped iron oxide nanoparticles with Gd ions and sequestered the ions within the core by coating the nanoparticles with an alloy of gold and silver. Thus, these nanoparticles are very innovative and have the potential to overcome toxicities related to renal clearance of contrast agents such as nephrogenic systemic fibrosis. The morphology of the attained nanoparticles was characterized by XRD which demonstrated the successful incorporation of Gd(III ions into the structure of the magnetite, with no major alterations of the spinel structure, as well as the growth of the gold-silver alloy shells. This was supported by TEM, ICP-AES, and SEM/EDS data. The nanoshells showed a saturation magnetization of 38 emu/g because of the presence of Gd ions within the crystalline structure with r 1 and r 2 values of 0.0119 and 0.9229 mL mg-1 s-1, respectively (Au:Ag alloy = 1:1. T 1- and T 2-weighted images of the nanoshells showed that these agents can both increase the surrounding water proton signals in the T 1-weighted image and reduce the signal in T 2-weighted images. The as-synthesized nanoparticles exhibited strong absorption in the range of 600-800 nm, their optical properties being strongly dependent upon the thickness of the gold-silver alloy shell. Thus, these nanoshells have the potential to be utilized for tumor cell ablation because of their absorption as well as an imaging agent.

  4. Design, synthesis and characterization of a Pt-Gd metal-organic framework containing potentially catalytically active sites.

    Science.gov (United States)

    Szeto, Kai C; Kongshaug, Kjell Ove; Jakobsen, Søren; Tilset, Mats; Lillerud, Karl Petter

    2008-04-21

    The heterobimetallic metal-organic framework {[(BPDC)PtCl(2)](3)(Gd(H(2)O)(3))(2)}.5H(2)O (BPDC = 2,2'-bipyridine-5,5'-dicarboxylate) has been designed and synthesized by hydrothermal methods. The new coordination polymer contains subunits of (BPDC)PtCl(2) (1) where both N atoms of the BPDC ligand are attached to a square-planar Pt(II) center. The two remaining cis coordination sites at Pt(II) are occupied by chloride ions. The final structure (2) of the polymeric network is obtained when Gd(III) ions link together the (BPDC)PtCl(2) units, which are organized in sheets, into larger blocks. These blocks are stacked along the crystallographic [010] direction and are held together by a hydrogen bonding scheme that involves carboxylate oxygen atoms and water molecules in the coordination sphere of Gd. The coordination polymer 2 can be obtained in a single-step reaction or in a two-step synthesis where the corresponding Pt complex (1) was first synthesized followed by reacting 1 with Gd(NO(3))(3).6H(2)O. In situ high temperature powder X-ray diffraction shows that the crystalline coordination polymer transforms into an anhydrous modification at 100 degrees C. This modification is stable to 350 degrees C, at which temperature the structure starts to decompose. The coordination sphere around platinum in the polymer closely resembles organometallic Pt complexes that have been previously found to catalytically or stoichiometrically activate and functionalize hydrocarbon C-H bonds in homogeneous systems.

  5. Lanthanide(III)/pyrimidine-4,6-dicarboxylate/oxalate extended frameworks: a detailed study based on the lanthanide contraction and temperature effects.

    Science.gov (United States)

    Cepeda, Javier; Balda, Rolindes; Beobide, Garikoitz; Castillo, Oscar; Fernández, Joaquín; Luque, Antonio; Pérez-Yáñez, Sonia; Román, Pascual; Vallejo-Sánchez, Daniel

    2011-09-05

    entropic effects at high temperatures directs the crystallization process toward less hydrated crystal structures. The magnetic data of these compounds indicate that the exchange coupling between the lanthanide atoms is almost negligible, so the magnetic behavior is dominated by the spin-orbit coupling and the ligand field perturbation. The luminescence properties that exhibit the compounds containing Nd(III), Eu(III), and Tb(III) have been also characterized.

  6. Probing the magnetic and magnetothermal properties of M(II)-Ln(III) complexes (where M(II) = Ni or Zn; Ln(III) = La or Pr or Gd).

    Science.gov (United States)

    Ahmed, Naushad; Das, Chinmoy; Vaidya, Shefali; Srivastava, Anant Kumar; Langley, Stuart K; Murray, Keith S; Shanmugam, Maheswaran

    2014-12-14

    We establish the coordination potential of the Schiff base ligand (2-methoxy-6-[(E)-2'-hydroxymethyl-phenyliminomethyl]-phenolate (H2L)) via the isolation of various M(II)-Ln(III) complexes (where M(II) = Ni or Zn and Ln(III) = La or Pr or Gd). Single crystals of these five complexes were isolated and their solid state structures were determined by single crystal X-ray diffraction. Structural determination revealed molecular formulae of [NiGd(HL)2(NO3)3] (1), [NiPr(HL)2(NO3)3] (2) and [Ni2La(HL)4(NO3)](NO3)2 (3), [Zn2Gd(HL)4(NO3)](NO3)2 (4), and [Zn2Pr(HL)4(NO3)](NO3)2 (5). Complexes and were found to be neutral heterometallic dinuclear compounds, whereas 3-5 were found to be linear heterometallic trinuclear cationic complexes. Direct current (dc) magnetic susceptibility and magnetization measurements conclusively revealed that complexes 1 and 4 possess a spin ground state of S = 9/2 and 7/2 respectively. Empirically calculated ΔχMT derived from the variable temperature susceptibility data for all complexes undoubtedly indicates that the Ni(II) ion is coupled ferromagnetically with the Gd(III) ion, and antiferromagnetically with the Pr(III) ion in 1 and 2 respectively. The extent of the exchange interaction for was estimated by fitting the magnetic susceptibility data using the parameters (g = 2.028, S = 9/2, J = 1.31 cm(-1) and zJ = +0.007), supporting the phenomenon observed in an empirical approach. Similarly using a HDVV Hamiltonian, the magnetic data of 3 and 4 were fitted, yielding parameters g = 2.177, D = 3.133 cm(-1), J = -0.978 cm(-1), (for 3) and g = 1.985, D = 0.508 cm(-1) (for 4). The maximum change in magnetic entropy (-ΔSm) estimated from the isothermal magnetization data for was found to be 5.7 J kg(-1) K(-1) (ΔB = 7 Tesla) at 7.0 K, which is larger than the -ΔSm value extracted from 4 of 3.5 J kg(-1) K(-1) (ΔB = 7 Tesla) at 15.8 K, revealing the importance of the exchange interaction in increasing the overall ground state of a molecule for

  7. Self-aggregated dinuclear lanthanide(III) complexes as potential bimodal probes for magnetic resonance and optical imaging.

    Science.gov (United States)

    Regueiro-Figueroa, Martín; Nonat, Aline; Rolla, Gabriele A; Esteban-Gómez, David; de Blas, Andrés; Rodríguez-Blas, Teresa; Charbonnière, Loïc J; Botta, Mauro; Platas-Iglesias, Carlos

    2013-08-26

    Homodinuclear lanthanide complexes (Ln = La, Eu, Gd, Tb, Yb and Lu) derived from a bis-macrocyclic ligand featuring two 2,2',2''-(1,4,7,10-tetraazacyclododecane-1,4,7-triyl)triacetic acid chelating sites linked by a 2,6-bis(pyrazol-1-yl)pyridine spacer (H2L(3)) were prepared and characterized. Luminescence lifetime measurements recorded on solutions of the Eu(III) and Tb(III) complexes indicate the presence of one inner-sphere water molecule coordinated to each metal ion in these complexes. The overall luminescence quantum yields were determined (ϕ H2O = 0.01 for [Eu2(L(3))] and 0.50 for [Tb2(L(3))] in 0.01 M TRIS/HCl, pH 7.4; TRIS = tris(hydroxymethyl)aminomethane), pointing to an effective sensitization of the metal ion by the bispyrazolylpyridyl unit of the ligand, especially with Tb. The nuclear magnetic relaxation dispersion (NMRD) profiles recorded for [Gd2(L(3))] are characteristic of slowly tumbling systems, showing a low-field plateau and a broad maximum around 30 MHz. This suggests the occurrence of aggregation of the complexes giving rise to slowly rotating species. A similar behavior is observed for the analogous Gd(III) complex containing a 4,4'-dimethyl-2,2'-bipyridyl spacer ([Gd2(L(1))]). The relaxivity of [Gd2(L(3))] recorded at 0.5 T and 298 K (pH 6.9) amounts to 13.7 mM(-1)  s(-1). The formation of aggregates has been confirmed by dynamic light scattering (DLS) experiments, which provided mean particle sizes of 114 and 38 nm for [Gd2(L(1))] and [Gd2(L(3))], respectively. TEM images of [Gd2(L(3))] indicate the formation of nearly spherical nanosized aggregates with a mean diameter of about 41 nm, together with some nonspherical particles with larger size.

  8. The effect of fluoride and silicate ions on the coprecipitation of gadolinium with calcium in phosphoric and sulpho-phosphoric media

    Energy Technology Data Exchange (ETDEWEB)

    Bouhlassa, S.; Salhamen, F. [Univ. Mohammed V - Agdal, Rabat (Morocco). Lab. de Radiochimie

    2013-05-01

    This work was carried out with the aim to establish the effect of some impurities on the coprecipitation of gadolinium with calcium phosphate and gypsum. The tests were performed using the radioactive tracer technique to monitor the fate of gadolinium in various phosphoric and sulpho-phosphoric media containing fluoride and silicate ions as impurities. In 10{sup -2} to 10{sup -1} M NH{sub 4}H{sub 2}PO{sub 4} solution, the Gd(III) at a concentration of 10{sup -4} M is almost entirely precipitated as amorphous phosphate. However, the presence of H{sub 2}SO{sub 4} at C{sub H{sub 3SO{sub 4}}} {>=} 0.1 M, reduces the coprecipitation to less than 8 at. %, on average. The fluoride ions in solution, even at C{sub HF} {<=} 0.1 M, induce a reduction of coprecipitation of 10 to 30% according to HF concentration. In the media containing 10{sup -2} to 10{sup -1} M NH{sub 4}H{sub 2}PO{sub 4} and 10{sup -1} M H{sub 2}SO{sub 4}, the effect of HF is almost negligible in the absence of Si(IV); nevertheless, the presence of fluorosilicate in solution may contribute to the enhancement of the coprecipitation of the REE. The sulphuric acid (0.1 M) in phosphoric media (0.74 {<=} C{sub H{sub 3PO{sub 4}}} {<=} 4.44 M), leads to a significant coprecipitation of the REE (1.3 {+-} 0.2 {<=}D{sub Gd}{<=} 3.1 {+-} 0.5), whilst the addition of HF (0.1 M) to these media enhances the solubility of the REE (left angle D{sub Gd} right angle = 0.06 {+-} 0.01). XRD, IR spectroscopy and elemental analyses of the solid phases in conjunction with the variation of the distribution coefficient D indicate that the coprecipitation of the REE is likely controlled by heterovalent substitution of REE in gypsum and its precipitation as phosphate or fluorosilicate. (orig.)

  9. Biodegradable gadolinium-chelated cationic poly(urethane amide) copolymers for gene transfection and magnetic resonance imaging

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Xiaolong [Department of Radiology, Tongji Hospital, Tongji University School of Medicine, Shanghai 200065 (China); Wang, Gangmin [Department of Urology, Huashan Hospital, Fudan University, Shanghai 200040 (China); Shi, Ting [The Institute for Translational Nanomedicine, Shanghai East Hospital, Institute for Biomedical Engineering and Nanoscience, Tongji University School of Medicine, Shanghai 200092 (China); Shao, Zhihong [Department of Radiology, Tongji Hospital, Tongji University School of Medicine, Shanghai 200065 (China); Zhao, Peng; Shi, Donglu [The Institute for Translational Nanomedicine, Shanghai East Hospital, Institute for Biomedical Engineering and Nanoscience, Tongji University School of Medicine, Shanghai 200092 (China); Ren, Jie [Institute of Nano and Biopolymeric Materials, School of Materials Science and Engineering, Tongji University, 4800 Caoan Road, Shanghai 201804 (China); Lin, Chao, E-mail: chaolin@tongji.edu.cn [The Institute for Translational Nanomedicine, Shanghai East Hospital, Institute for Biomedical Engineering and Nanoscience, Tongji University School of Medicine, Shanghai 200092 (China); Wang, Peijun, E-mail: tjpjwang@sina.com [Department of Radiology, Tongji Hospital, Tongji University School of Medicine, Shanghai 200065 (China)

    2016-08-01

    Theranostic nano-polyplexes containing gene and imaging agents hold a great promise for tumor diagnosis and therapy. In this work, we develop a group of new gadolinium (Gd)-chelated cationic poly(urethane amide)s for gene delivery and T{sub 1}-weighted magnetic resonance (MR) imaging. Cationic poly(urethane amide)s (denoted as CPUAs) having multiple disulfide bonds, urethane and amide linkages were synthesized by stepwise polycondensation reaction between 1,4-bis(3-aminopropyl)piperazine and a mixture of di(4-nitrophenyl)-2, 2′-dithiodiethanocarbonate (DTDE-PNC) and diethylenetriaminepentaacetic acid (DTPA) dianhydride at varied molar ratios. Then, Gd-chelated CPUAs (denoted as GdCPUAs) were produced by chelating Gd(III) ions with DTPA residues of CPUAs. These GdCPUAs could condense gene into nanosized and positively-charged polyplexes in a physiological condition and, however, liberated gene in an intracellular reductive environment. In vitro transfection experiments revealed that the GdCPUA at a DTDE-PNC/DTPA residue molar ratio of 85/15 induced the highest transfection efficiency in different cancer cells. This efficiency was higher than that yielded with 25 kDa branched polyethylenimine as a positive control. GdCPUAs and their polyplexes exhibited low cytotoxicity when an optimal transfection activity was detected. Moreover, GdCPUAs may serve as contrast agents for T{sub 1}-weighted magnetic resonance imaging. The results of this work indicate that biodegradable Gd-chelated cationic poly(urethane amide) copolymers have high potential for tumor theranostics. - Highlights: • Novel cationic gadolinium-chelated poly(urethane amide)s (GdCPUAs) are prepared. • GdCPUAs can induce a high transfection efficacy in different cancer cells. • GdCPUAs reveal good cyto-compatibility against cancer cells. • GdCPUAs may be applied as T{sub 1}-contrast agents for magnetic resonance imaging. • GdCPUAs hold high potential for cancer theranostics.

  10. Separation and characterization of the two diastereomers for [Gd(DTPA-bz-NH2)(H2O)]2-, a common synthon in macromolecular MRI contrast agents: their water exchange and isomerization kinetics.

    Science.gov (United States)

    Burai, László; Tóth, Eva; Sour, Angélique; Merbach, André E

    2005-05-16

    Chiral, bifunctional poly(amino carboxylate) ligands are commonly used for the synthesis of macromolecular, Gd(III)-based MRI contrast agents, prepared in the objective of increasing relaxivity or delivering the paramagnetic Gd(III) to a specific site (targeting). Complex formation with such ligands results in two diastereomeric forms for the complex which can be separated by HPLC. We demonstrated that the diastereomer ratio for Ln(III) DTPA derivatives (approximately 60:40) remains constant throughout the lanthanide series, in contrast to Ln(III) EPTPA derivatives, where it varies as a function of the cation size with a maximum for the middle lanthanides (DTPA(5-) = diethylenetriaminepentaacetate; EPTPA(5-) = ethylenepropylenetriaminepentaacetate). The interconversion of the two diastereomers, studied by HPLC, is a proton-catalyzed process (k(obs) = k(1)[H(+)]). It is relatively fast for [Gd(EPTPA-bz-NH(2))(H(2)O)](2-) but slow enough for [Gd(DTPA-bz-NH(2))(H(2)O)](2-) to allow investigation of pure individual isomers (isomerization rate constants are k(1) = (3.03 +/- 0.07) x 10(4) and 11.6 +/- 0.5 s(-1) M(-1) for [Gd(EPTPA-bz-NH(2))(H(2)O)](2)(-) and [Gd(DTPA-bz-NH(2))(H(2)O)](2-), respectively). Individual water exchange rates have been determined for both diastereomers of [Gd(DTPA-bz-NH(2))(H(2)O)](2-) by a variable-temperature (17)O NMR study. Similarly to Ln(III) EPTPA derivatives, k(ex) values differ by a factor of 2 (k(ex)(298) = (5.7 +/- 0.2) x 10(6) and (3.1 +/- 0.1) x 10(6) s(-1)). This variance in the exchange rate has no consequence on the proton relaxivity of the two diastereomers, since it is solely limited by fast rotation. However, such difference in k(ex) will affect proton relaxivity when these diastereomers are linked to a slowly rotating macromolecule. Once the rotation is optimized, slow water exchange will limit relaxivity; thus, a factor of 2 in the exchange rate can lead to a remarkably different relaxivity for the diastereomer complexes

  11. Lanthanide Organophosphate Spiro Polymers: Synthesis, Structure, and Magnetocaloric Effect in the Gadolinium Polymer.

    Science.gov (United States)

    Gupta, Sandeep K; Bhat, Gulzar A; Murugavel, Ramaswamy

    2017-08-07

    Spirocyclic lanthanide organophosphate polymers, {[Ln(dipp)(dippH)(CH3OH)(H2O)2](CH3OH)2}n [Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11)], have been prepared from the reaction of Ln(NO3)3·xH2O with sterically hindered 2,6-diisopropylphenyl phosphate (dippH2) using aqueous NaOH as the base. The one-dimensional chainlike lanthanide (III) organophosphate coordination polymers have been characterized with the aid of analytical and spectroscopic methods. The single crystal structure determination of polymers (2-5 and 7-11) reveals that in these compounds the hydrophobic organic groups of the phosphate provide a protective coating for the inorganic lanthanide phosphate polymeric chain. The encapsulation of inorganic lanthanide phosphate core, which has very low solubility product, within the organic groups assists in the facile crystallization of the polymers. The di- and monoanionic organophosphate ligands dipp(2-) and dippH(-) display [2.111] and [2.110] binding modes, respectively, in 2-5 and 7. However, they exhibit only [2.110] binding mode in the case of 8-11. This results in the formation of two different types of polymers. While the lighter rare-earth metal ions in 2-5 and 7 display eight coordinate biaugmented trigonal prismatic geometry, the heavier rare-earth metal ions in 9-11 exhibit a seven coordinate capped trigonal prismatic environment. The Tb(III) ion in 8 displays distorted pentagonal bipyramidal geometry. Magnetic studies reveal the presence of weak antiferromagnetic interactions between the Ln(III) ions through the organophosphate ligand. The isotropic Gd(III) polymer 7 exhibits a maximum entropy change of 17.83 J kg(-1) K(-1) for a field change of 7.0 T at 2.5 K, which is significant considering the high molecular weight of the organophosphate ligand. These polymers represent the first family of any structurally characterized rare-earth organophosphate polymers derived from monoesters of phosphoric

  12. Sensitisation of Eu(III)- and Tb(III)-based luminescence by Ir(III) units in Ir/lanthanide dyads: evidence for parallel energy-transfer and electron-transfer based mechanisms.

    Science.gov (United States)

    Sykes, Daniel; Cankut, Ahmet J; Ali, Noorshida Mohd; Stephenson, Andrew; Spall, Steven J P; Parker, Simon C; Weinstein, Julia A; Ward, Michael D

    2014-05-07

    A series of blue-luminescent Ir(III) complexes with a pendant binding site for lanthanide(III) ions has been synthesized and used to prepare Ir(III)/Ln(III) dyads (Ln = Eu, Tb, Gd). Photophysical studies were used to establish mechanisms of Ir→Ln (Ln = Tb, Eu) energy-transfer. In the Ir/Gd dyads, where direct Ir→Gd energy-transfer is not possible, significant quenching of Ir-based luminescence nonetheless occurred; this can be ascribed to photoinduced electron-transfer from the photo-excited Ir unit (*Ir, (3)MLCT/(3)LC excited state) to the pendant pyrazolyl-pyridine site which becomes a good electron-acceptor when coordinated to an electropositive Gd(III) centre. This electron transfer quenches the Ir-based luminescence, leading to formation of a charge-separated {Ir(4+)}˙-(pyrazolyl-pyridine)˙(-) state, which is short-lived possibly due to fast back electron-transfer (transfer pathway is again operative and leads to sensitisation of Eu-based and Tb-based emission using the energy liberated from the back electron-transfer process. In addition direct Dexter-type Ir→Ln (Ln = Tb, Eu) energy-transfer occurs on a similar timescale, meaning that there are two parallel mechanisms by which excitation energy can be transferred from *Ir to the Eu/Tb centre. Time-resolved luminescence measurements on the sensitised Eu-based emission showed both fast and slow rise-time components, associated with the PET-based and Dexter-based energy-transfer mechanisms respectively. In the Ir/Tb dyads, the Ir→Tb energy-transfer is only just thermodynamically favourable, leading to rapid Tb→Ir thermally-activated back energy-transfer and non-radiative deactivation to an extent that depends on the precise energy gap between the *Ir and Tb-based (5)D4 states. Thus, the sensitised Tb(iii)-based emission is weak and unusually short-lived due to back energy transfer, but nonetheless represents rare examples of Tb(III) sensitisation by a energy donor that could be excited using visible

  13. Multifunctional dendrimer-based nanoparticles for in vivo MR/CT dual-modal molecular imaging of breast cancer

    Directory of Open Access Journals (Sweden)

    Li K

    2013-07-01

    Full Text Available Kangan Li,1,4,5,* Shihui Wen,2,* Andrew C Larson,4,5 Mingwu Shen,2 Zhuoli Zhang,4,5 Qian Chen,3 Xiangyang Shi,2,3 Guixiang Zhang1 1Department of Radiology, Shanghai First People’s Hospital, Shanghai Jiaotong University School of Medicine, Shanghai, People’s Republic of China; 2College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai, People’s Republic of China; 3State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai, People’s Republic of China; 4Departments of Radiology and Biomedical Engineering, Northwestern University, Chicago, IL, USA; 5Robert H Lurie Comprehensive Cancer Center, Chicago, IL, USA *These authors contributed equally to this work Abstract: Development of dual-mode or multi-mode imaging contrast agents is important for accurate and self-confirmatory diagnosis of cancer. We report a new multifunctional, dendrimer-based gold nanoparticle (AuNP as a dual-modality contrast agent for magnetic resonance (MR/computed tomography (CT imaging of breast cancer cells in vitro and in vivo. In this study, amine-terminated generation 5 poly(amidoamine dendrimers modified with gadolinium chelate (DOTA-NHS and polyethylene glycol monomethyl ether were used as templates to synthesize AuNPs, followed by Gd(III chelation and acetylation of the remaining dendrimer terminal amine groups; multifunctional dendrimer-entrapped AuNPs (Gd-Au DENPs were formed. The formed Gd-Au DENPs were used for both in vitro and in vivo MR/CT imaging of human MCF-7 cancer cells. Both MR and CT images demonstrate that MCF-7 cells and the xenograft tumor model can be effectively imaged. The Gd-Au DENPs uptake, mainly in the cell cytoplasm, was confirmed by transmission electron microscopy. The cell cytotoxicity assay, cell morphology observation, and flow cytometry show that the developed Gd-Au DENPs have good biocompatibility in the given concentration range. Our results

  14. A Non-Electrostatic Surface Complexation Approach to Modeling Radionuclide Migration at the Nevada Test Site: I. Iron Oxides and Calcite

    Energy Technology Data Exchange (ETDEWEB)

    Zavarin, M; Bruton, C J

    2004-12-17

    , simple binary NEM reactions adequately fit most data without need for bidentate or ternary surface reactions. For example, the decrease in U(VI) sorption as a function of carbonate alkalinity was accounted for by aqueous uranyl-carbonate complex formation. In some cases, the one-site NEM could not fit sorption data at high and low radionuclide surface loads. This failure results from multiple surface sites with varying sorption affinity as well as electrostatic effects not accounted for by our model. Calcite sorption reactions were modeled as NEM surface exchange reactions. Uncertainty in these surface exchange reactions is relatively high because few radionuclide-calcite sorption data are available. Nevertheless, 1D reactive transport simulations in alluvium comparable to that in Tompson et al. (1999) and based on the NEM database developed in this report, suggest that migration of Sm(III), Eu(III), Np(V), Pu(IV,V), and Am(III) will be significantly retarded by sedimentary carbonates. Though iron oxide minerals are usually thought to be the major contributors to radionuclide retardation, calcite will also be of paramount importance in areas where it is present (e.g. calcareous regions of NTS as well as buried carbonate paleosols at the 200 Area of the Hanford Site (south-central Washington, U.S.A.), calcareous soils of the Marshall Islands, and weathered cementitious materials at waste disposal facilities). The NEM approach provides a simple yet robust mechanistic basis for modeling radionuclide migration with a minimum number of fitting parameters.

  15. Behavior of gadolinium-based diagnostics in water treatment

    Energy Technology Data Exchange (ETDEWEB)

    Cyris, Maike

    2013-04-25

    Wastewater treatment plants throughout Europe are retrofitted for a sufficient removal of micropollutants. Most target compounds are eliminated efficiently at reasonable costs by oxidation. Sorption processes, on the other hand, are favored as no transformation products are formed. For oxidation, ozone is preferred presently. Its action is divided in two main reaction pathways: Via ozone and via hydroxyl radicals formed by ozone-matrix reactions. Oxidation efficiency strongly depends on reaction rate constants. Sorption processes are usually characterized, including sorption strength, by determination of isotherms. Also, for description of filtration processes isotherm data are necessary. So far, gadolinium chelates, used as contrast agents in magnetic resonance imaging, have not been investigated in both advanced wastewater treatment processes. The stable chelates are excreted without metabolization. Conventional wastewater treatment does not remove them substantially. They remain intact and no free Gd(III) is released. This may be changed due to oxidative treatment which potentially destroys the chelates, and Gd(III) ions which are toxic, contrary to the chelated form, may be liberated. Monitoring campaigns in wastewater and drinking water have been performed to demonstrate the relevance of gadolinium in such treatment steps. In a European monitoring campaign an average concentration of 118 ng L{sup -1} gadolinium has been determined for 75 wastewater treatment plants effluents, corresponding to a non-geogenic gadolinium concentration of 116 ng L{sup -1}. In drinking water in the Ruhr area, a densely populated region in Germany, gadolinium and the anomaly were measurable by a factor of five lower than the average in the investigated wastewater samples. The determined concentrations in drinking water are lower than acute toxic effect concentration. The speciation of gadolinium in the investigated samples is unknown, as only total element concentration has been

  16. Bifunctional Zn(II)Ln(III) dinuclear complexes combining field induced SMM behavior and luminescence: enhanced NIR lanthanide emission by 9-anthracene carboxylate bridging ligands.

    Science.gov (United States)

    Palacios, María A; Titos-Padilla, Silvia; Ruiz, José; Herrera, Juan Manuel; Pope, Simon J A; Brechin, Euan K; Colacio, Enrique

    2014-02-03

    There were new dinuclear Zn(II)-Ln(III) complexes of general formulas [Zn(μ-L)(μ-OAc)Ln(NO3)2] (Ln(III) = Tb (1), Dy (2), Er (3), and Yb (4)), [Zn(μ-L)(μ-NO3)Er(NO3)2] (5), [Zn(H2O)(μ-L)Nd(NO3)3]·2CH3OH (6), [Zn(μ-L)(μ-9-An)Ln(NO3)2]·2CH3CN (Ln(III) = Tb (7), Dy (8), Er (9), Yb(10)), [Zn(μ-L)(μ-9-An)Yb(9-An)(NO3)3]·3CH3CN (11), [Zn(μ-L)(μ-9-An)Nd(9-An)(NO3)3]·2CH3CN·3H2O (12), and [Zn(μ-L)(μ-9-An)Nd(CH3OH)2(NO3)]ClO4·2CH3OH (13) prepared from the reaction of the compartmental ligand N,N',N″-trimethyl-N,N″-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine (H2L), with ZnX2·nH2O (X = NO3(-) or OAc(-)) salts, Ln(NO3)3·nH2O, and, in some instances, 9-anthracenecarboxylate anion (9-An). In all these complexes, the Zn(II) ions invariably occupy the internal N3O2 site whereas the Ln(III) ions show preference for the O4 external site, giving rise to a Zn(μ-diphenoxo)Ln bridging fragment. Depending on the Zn(II) salt and solvent used in the reaction, a third bridge can connect the Zn(II) and Ln(III) metal ions, giving rise to triple-bridged diphenoxoacetate in complexes 1-4, diphenoxonitrate in complex 5, and diphenoxo(9-anthracenecarboxylate) in complexes 8-13. Dy(III) and Er(III) complexes 2, 8 and 3, 5, respectively, exhibit field induced single molecule magnet (SMM) behavior, with Ueff values ranging from 11.7 (3) to 41(2) K. Additionally, the solid-state photophysical properties of these complexes are presented showing that ligand L(2-) is able to sensitize Tb(III)- and Dy(III)-based luminescence in the visible region through an energy transfer process (antenna effect). The efficiency of this process is much lower when NIR emitters such as Er(III), Nd(III), and Yb(III) are considered. When the luminophore 9-anthracene carboxylate is incorporated into these complexes, the NIR luminescence is enhanced which proves the efficiency of this bridging ligand to act as antenna group. Complexes 2, 3, 5, and 8 can be considered as dual materials

  17. Synthesis, Crystal Structures, Magnetic Properties, and Theoretical Investigation of a New Series of Ni(II)-Ln(III)-W(V) Heterotrimetallics: Understanding the SMM Behavior of Mixed Polynuclear Complexes.

    Science.gov (United States)

    Vieru, Veacheslav; Pasatoiu, Traian D; Ungur, Liviu; Suturina, Elizaveta; Madalan, Augustin M; Duhayon, Carine; Sutter, Jean-Pascal; Andruh, Marius; Chibotaru, Liviu F

    2016-12-05

    The polynuclear compounds containing anisotropic metal ions often exhibit efficient barriers for blocking of magnetization at fairly arbitrary geometries. However, at variance with mononuclear complexes, which usually become single-molecule magnets (SMM) under the sole requirement of a highly axial crystal field at the metal ion, the factors influencing the SMM behavior in polynuclear complexes, especially, with weakly axial magnetic ions, still remain largely unrevealed. As an attempt to clarify these conditions, we present here the synthesis, crystal structures, magnetic behavior, and ab initio calculations for a new series of Ni(II)-Ln(III)-W(V) trimetallics, [(CN)7W(CN)Ni(H2O)(valpn)Ln(H2O)4]·H2O (Ln = Y 1, Eu 2, Gd 3, Tb 4, Dy 5, Lu 6). The surprising finding is the absence of the magnetic blockage even for compounds involving strongly anisotropic Dy(III) and Tb(III) metal ions. This is well explained by ab initio calculations showing relatively large transversal components of the g-tensor in the ground exchange Kramers doublets of 1 and 4 and large intrinsic tunneling gaps in the ground exchange doublets of 3 and 5. In order to get more insight into this behavior, another series of earlier reported compounds with the same trinuclear [W(V)Ni(II)Ln(III)] core structure, [(CN)7W(CN)Ni(dmf)(valdmpn)Ln(dmf)4]·H2O (Ln = Gd(III) 7, Tb(III) 8a, Dy(III) 9, Ho(III) 10), [(CN)7W(CN)Ni(H2O)(valdmpn)Tb(dmf)2.5(H2O)1.5]·H2O·0.5dmf 8b, and [(CN)7W(CN)Ni(H2O)(valdmpn)Er(dmf)3(H2O)1]·H2O·0.5dmf 11, has been also investigated theoretically. In this series, only 8b exhibits SMM behavior which is confirmed by the present ab initio calculations. An important feature for the entire series is the strong ferromagnetic coupling between Ni(II) and W(V), which is due to an almost perfect trigonal dodecahedron geometry of the octacyano wolframate fragment. The reason why only 8b is an SMM is explained by positive zero-field splitting on the nickel site, precluding magnetization

  18. Influence of metal loading and humic acid functional groups on the complexation behavior of trivalent lanthanides analyzed by CE-ICP-MS

    Energy Technology Data Exchange (ETDEWEB)

    Kautenburger, Ralf, E-mail: r.kautenburger@mx.uni-saarland.de [Institute of Inorganic Solid State Chemistry, Saarland University, Campus Dudweiler, Am Markt Zeile 3-5, D-66125 Saarbrücken (Germany); Hein, Christina; Sander, Jonas M. [Institute of Inorganic Solid State Chemistry, Saarland University, Campus Dudweiler, Am Markt Zeile 3-5, D-66125 Saarbrücken (Germany); Beck, Horst P. [Institute of Inorganic and Analytical Chemistry and Radiochemistry, Saarland University, Campus Dudweiler, Am Markt Zeile 5, D-66125 Saarbrücken (Germany)

    2014-03-01

    Highlights: • Free and complexed HA-Ln species are separated by CE-ICP-MS. • Weaker and stronger HA-binding sites for Ln-complexation can be detected. • Complexation by original and modified humic acid (HA) with blocked phenolic hydroxyl- and carboxyl-groups is compared. • Stronger HA-binding sites for Ln³⁺ can be assumed as chelating complexes. • Chelates consist of trivalent Ln and a combination of both OH- and COOH-groups. Abstract: The complexation behavior of Aldrich humic acid (AHA) and a modified humic acid (AHA-PB) with blocked phenolic hydroxyl groups for trivalent lanthanides (Ln) is compared, and their influence on the mobility of Ln(III) in an aquifer is analyzed. As speciation technique, capillary electrophoresis (CE) was hyphenated with inductively coupled plasma mass spectrometry (ICP-MS). For metal loading experiments 25 mg L⁻¹ of AHA and different concentrations (c Ln(Eu+Gd)} = 100–6000 μg L⁻¹) of Eu(III) and Gd(III) in 10 mM NaClO₄ at pH 5 were applied. By CE-ICP-MS, three Ln-fractions, assumed to be uncomplexed, weakly and strongly AHA-complexed metal can be detected. For the used Ln/AHA-ratios conservative complex stability constants log βLnAHA decrease from 6.33 (100 μg L⁻¹ Ln³⁺) to 4.31 (6000 μg L⁻¹ Ln³⁺) with growing Ln-content. In order to verify the postulated weaker and stronger humic acid binding sites for trivalent Eu and Gd, a modified AHA with blocked functional groups was used. For these experiments 500 μg L⁻¹ Eu and 25 mg L⁻¹ AHA and AHA-PB in 10 mM NaClO₄ at pH-values ranging from 3 to 10 have been applied. With AHA-PB, where 84% of the phenolic OH-groups and 40% of the COOH-groups were blocked, Eu complexation was significantly lower, especially at the strong binding sites. The log β-values decrease from 6.11 (pH 10) to 5.61 at pH 3 (AHA) and for AHA-PB from 6.01 (pH 7) to 3.94 at pH 3. As a potential consequence, particularly humic acids with a high amount of

  19. Lanthanide ion and tetrathiafulvalene-based ligand as a "magic" couple toward luminescence, single molecule magnets, and magnetostructural correlations.

    Science.gov (United States)

    Pointillart, Fabrice; le Guennic, Boris; Cador, Olivier; Maury, Olivier; Ouahab, Lahcène

    2015-11-17

    The synthesis of molecules featuring different properties is a perpetual challenge for the chemists' community. The coexistence and even more the synergy of those properties open new perspectives in the field of molecular devices and molecular electronics. In that sense, coordination chemistry contributed to the development of new functional molecules through, for instance, single-molecule magnets (SMMs) and light emitting molecules with potential applications in high capacity data storage and OLEDs, respectively. The appealing combination of both electronic properties into one single object may offer the possibility to have magnetized luminescent entities at nanometric scale. To that end, lanthanides seem to be one of the key ingredients since their peculiar electronic structures endow them with specific magnetic and luminescence properties. Indeed, lanthanides cover a wide range of emission wavelengths, from infrared to UV, which add up to a large variety of magnetic behaviors, from the fully isotropic spin (e.g., Gd(III)) to highly anisotropic magnetic moments (e.g., Dy(III)). In lanthanide complexes, ligands play a fundamental role because on one hand they govern the orientation of the magnetic moment of anisotropic lanthanides and on the other hand they can sensitize efficiently the luminescence. The design of appropriate organic ligands to elaborate such chemical objects with the desired property appears to be essential but remains a perpetual challenge. In this Account, we describe the design of lanthanide-based complexes that emit light, behave as SMMs, or combine both properties. We have paid peculiar attention to the design of ligands based on the tetrathiafulvalene (TTF) moiety. TTF and its derivatives are well-known chemical entities, stable at different oxidation states, and employed mainly in the synthesis of molecular conductors and superconductors. In addition to their redox properties, TTF-based derivatives act as organic chromophores for the

  20. Multimetallic complexes and functionalized gold nanoparticles based on a combination of d- and f-elements.

    Science.gov (United States)

    Sung, Simon; Holmes, Holly; Wainwright, Luke; Toscani, Anita; Stasiuk, Graeme J; White, Andrew J P; Bell, Jimmy D; Wilton-Ely, James D E T

    2014-02-17

    The new DO3A-derived dithiocarbamate ligand, DO3A-(t)Bu-CS2K, is formed by treatment of the ammonium salt [DO3A-(t)Bu]HBr with K2CO3 and carbon disulfide. DO3A-(t)Bu-CS2K reacts with the ruthenium complexes cis-[RuCl2(dppm)2] and [Ru(CH═CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole) to yield [Ru(S2C-DO3A-(t)Bu)(dppm)2](+) and [Ru(CH═CHC6H4Me-4)(S2C-DO3A-(t)Bu)(CO)(PPh3)2], respectively. Similarly, the group 10 metal complexes [Pd(C,N-C6H4CH2NMe2)Cl]2 and [PtCl2(PPh3)2] form the dithiocarbamate compounds, [Pd(C,N-C6H4CH2NMe2)(S2C-DO3A-(t)Bu)] and [Pt(S2C-DO3A-(t)Bu)(PPh3)2](+), under the same conditions. The linear gold complexes [Au(S2C-DO3A-(t)Bu)(PR3)] are formed by reaction of [AuCl(PR3)] (R = Ph, Cy) with DO3A-(t)Bu-CS2K. However, on reaction with [AuCl(tht)] (tht = tetrahydrothiophene), the homoleptic digold complex [Au(S2C-DO3A-(t)Bu)]2 is formed. Further homoleptic examples, [M(S2C-DO3A-(t)Bu)2] (M = Ni, Cu) and [Co(S2C-DO3A-(t)Bu)3], are formed from treatment of NiCl2·6H2O, Cu(OAc)2, or Co(OAc)2, respectively, with DO3A-(t)Bu-CS2K. The molecular structure of [Ni(S2C-DO3A-(t)Bu)2] was determined crystallographically. The tert-butyl ester protecting groups of [M(S2C-DO3A-(t)Bu)2] (M = Ni, Cu) and [Co(S2C-DO3A-(t)Bu)3] are cleaved by trifluoroacetic acid to afford the carboxylic acid products, [M(S2C-DO3A)2] (M = Ni, Cu) and [Co(S2C-DO3A)3]. Complexation with Gd(III) salts yields trimetallic [M(S2C-DO3A-Gd)2] (M = Ni, Cu) and tetrametallic [Co(S2C-DO3A-Gd)3], with r(1) values of 11.5 (Co) and 11.0 (Cu) mM(-1) s(-1) per Gd center. DO3A-(t)Bu-CS2K can also be used to prepare gold nanoparticles, Au@S2C-DO3A-(t)Bu, by displacement of the surface units from citrate-stabilized nanoparticles. This material can be transformed into the carboxylic acid derivative Au@S2C-DO3A by treatment with trifluoroacetic acid. Complexation with Gd(OTf)3 or GdCl3 affords Au@S2C-DO3A-Gd with an r(1) value of 4.7 mM(-1) s(-1) per chelate and 1500 mM(-1) s(-1) per

  1. Neutron Capture Experiments on Unstable Nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Jon M. Schwantes; Ralf Sudowe; Heino Nitsche; Darleane C. Hoffman

    2003-12-16

    containing about twenty times as much Sm. An exhaustive review of the literature indicated that a multiprocess approach in which Eu(III) is reduced to Eu(II) prior to separation should provide an effective and efficient means of separation from the Sm(III). To date, three multiprocess methods have been developed and tested for their ability to meet the design requirements set forth by this project. These methods combine an initial reduction step using Zn(Hg) with either cation exchange resin in (1) column form or in (2) a batch reactor and hydroxyisobutyrate (?-HIB) as the eluant for trivalent lanthanides. Another multiprocess method uses solvent extraction with 0.1 M thenoyl trifluoroacetone (TTA) in benzene. Preliminary experiments indicate that: (a) A multiprocess approach using ?-HIB as a complexing agent for trivalent lanthanides is ineffective for separating Eu from Sm because ?-HIB stabilizes Eu(III) even in the presence of excess amounts of the reductant; (b) A multiprocess approach using solvent extraction shows promise, indicating that 0.1 M TTA in benzene favors extraction of trivalent over divalent metal ions by a factor of greater than 750. However, the reduction step using Zn(Hg), when combined with the TTA extraction, becomes less effective at reducing Eu during subsequent extractions and may also affect the stability of the TTA. Use of the amalgam also introduces Zn(II) contamination that must be separated from the Eu with additional solvent extraction steps. A PhD student from the group has visited the LANSCE facility, participated in several parameter checks of the DANCE, and acquainted himself with the data acquisition system. During these initial experiments, data were collected and brought back to UC Berkeley for analysis. A high purity P-type germanium detector was purchased, set up, and calibrated to assist with the determination of separation yields and efficiencies using ?-ray spectroscopy measurements of suitable radioactive tracers.

  2. Characterization of partitioning relevant lanthanide and actinide complexes by NMR spectroscopy; Charakterisierung von partitioningrelevanten Lanthaniden- und Actinidenkomplexen mittels NMR-Spektroskopie

    Energy Technology Data Exchange (ETDEWEB)

    Adam, Christian

    2016-01-15

    In the present work the interaction of N-donor ligands, such as 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (nPrBTP) and 2,6-Bis(5-(2,2-dimethylpropyl)1H-pyrazol)-3-yl-pyridine (C5-BPP), with trivalent lanthanide and actinide ions was studied. Ligands of this type show a high selectivity for the separation of trivalent actinide ions over lanthanides from nitric acid solutions. However, the reason for this selectivity, which is crucial for future partitioning and transmutation strategies for radioactive wastes, is still unknown. So far, the selectivity of some N-donor ligands is supposed to be an effect of an increased covalency in the actinide-ligand bond, compared to the lanthanide compounds. NMR spectroscopy on paramagnetic metal complexes is an excellent tool for the elucidation of bonding modes. The overall paramagnetic chemical shift consists of two contributions, the Fermi Contact Shift (FCS), due to electron spin delocalisation through covalent bonds, and the Pseudo Contact Shift (PCS), which describes the dipolar coupling of the electron magnetic moment and the nuclear spin. By assessing the FCS share in the paramagnetic shift, the degree of covalency in the metal-ligand bond can be gauged. Several methods to discriminate FCS and PCS have been used on the data of the nPrBTP- and C5-BPP-complexes and were evaluated regarding their applicability on lanthanide and actinide complexes with N-donor ligands. The study comprised the synthesis of all Ln(III) complexes with the exceptions of Pm(III) and Gd(III) as well as the Am(III) complex as a representative of the actinide series with both ligands. All complexes were fully characterised ({sup 1}H, {sup 13}C and {sup 15}N spectra) using NMR spectroscopy. By isotope enrichment with the NMR-active {sup 15}N in positions 8 and 9 in both ligands, resonance signals of these nitrogen atoms were detected for all complexes. The Bleaneymethod relies on different temperature dependencies for FCS (T{sup -1}) and PCS (T

  3. Characterization of partitioning relevant lanthanide and actinide complexes by NMR spectroscopy; Charakterisierung von partitioningrelevanten Lanthaniden- und Actinidenkomplexen mittels NMR-Spektroskopie

    Energy Technology Data Exchange (ETDEWEB)

    Adam, Christian

    2016-01-15

    In the present work the interaction of N-donor ligands, such as 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (nPrBTP) and 2,6-Bis(5-(2,2-dimethylpropyl)1H-pyrazol)-3-yl-pyridine (C5-BPP), with trivalent lanthanide and actinide ions was studied. Ligands of this type show a high selectivity for the separation of trivalent actinide ions over lanthanides from nitric acid solutions. However, the reason for this selectivity, which is crucial for future partitioning and transmutation strategies for radioactive wastes, is still unknown. So far, the selectivity of some N-donor ligands is supposed to be an effect of an increased covalency in the actinide-ligand bond, compared to the lanthanide compounds. NMR spectroscopy on paramagnetic metal complexes is an excellent tool for the elucidation of bonding modes. The overall paramagnetic chemical shift consists of two contributions, the Fermi Contact Shift (FCS), due to electron spin delocalisation through covalent bonds, and the Pseudo Contact Shift (PCS), which describes the dipolar coupling of the electron magnetic moment and the nuclear spin. By assessing the FCS share in the paramagnetic shift, the degree of covalency in the metal-ligand bond can be gauged. Several methods to discriminate FCS and PCS have been used on the data of the nPrBTP- and C5-BPP-complexes and were evaluated regarding their applicability on lanthanide and actinide complexes with N-donor ligands. The study comprised the synthesis of all Ln(III) complexes with the exceptions of Pm(III) and Gd(III) as well as the Am(III) complex as a representative of the actinide series with both ligands. All complexes were fully characterised ({sup 1}H, {sup 13}C and {sup 15}N spectra) using NMR spectroscopy. By isotope enrichment with the NMR-active {sup 15}N in positions 8 and 9 in both ligands, resonance signals of these nitrogen atoms were detected for all complexes. The Bleaneymethod relies on different temperature dependencies for FCS (T{sup -1}) and PCS (T