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Sample records for luminescent metal complexes

  1. Metal plasmon enhanced europium complex luminescence

    International Nuclear Information System (INIS)

    Liu Feng; Aldea, Gabriela; Nunzi, Jean-Michel

    2010-01-01

    The plasmon enhanced luminescence of a rare-earth complex Tris(6, 6, 7, 7, 8, 8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionato) europium (Eu(fod) 3 ) was investigated. A polyvinyl alcohol (PVA) thin film was successfully adopted as a spacer to separate the Eu complex from the silver island film (SIF), and five-fold enhancement of the radiative decay rate of the Eu complex on SIF was demonstrated based on the luminescence intensity and lifetime measurement. Investigation of the distance dependent luminescence indicates that 7 nm is an optimal distance for SIF enhanced Eu luminescence. Plasmon enhanced rare-earth luminescence based on an organic film spacer would find potential applications in plasmon enhanced organic light emitting diode (OLED) devices.

  2. The first example of intensive luminescence of LMCT state based on metal complexes in solution

    International Nuclear Information System (INIS)

    Lukova, G.V.; Vasil'ev, V.P.; Smirnov, V.A.; Huhn, W.

    2007-01-01

    A bridge complex rac-C 6 H 10 (IndH 4 ) 2 ZrC 2 , featuring a unique long-living luminescence in liquid solutions at 20 deg C, has been prepared for the first time by catalytic hydrogenation of bis-indinyl complex C 6 H 10 (Ind) 2 Zr 2 Cl 2 . It has been identified that quantum yields of luminescence of the complex solutions at room temperature are the greatest ones for the known compounds possessing emission states of charge transfer from ligand to metal. Linear correlations of quantum yield of metal complex luminescence in a solution with steric features of the solvent molecules have been detected for the first time [ru

  3. The coordination chemistry of dipyridylbenzene: N-deficient terpyridine or panacea for brightly luminescent metal complexes?

    Science.gov (United States)

    Williams, J A Gareth

    2009-06-01

    1,3-Di(2-pyridyl)benzene (dpybH) structurally resembles the widely-used ligand terpyridine (tpy), with which it is isoelectronic. In this critical review, following a brief overview of synthetic strategies for dpybH and derivatives, we survey the different types of complex that are possible with these ligands. Whilst metals such as ruthenium(ii), osmium(ii) and platinum(ii) give a terdentate N--C--N binding mode in which cyclometallation occurs at C(2), the ions iridium(iii), rhodium(iii) and palladium(ii) favour C(4) metallation. The latter process can be blocked by appropriate ligand modification, to allow the N--C--N mode to be accessed with these metal ions too. The luminescence properties of the complexes are discussed. A huge range of emission efficiencies are encountered amongst Ir(iii) complexes containing dpyb derivatives, according to the other ligands present. Trends can be rationalised with the aid of simple frontier-orbital considerations. The Pt(ii) complexes of dipyridylbenzenes are also intensely luminescent. Their application to contemporary organic light-emitting device (OLED) technology is discussed, including white light emitters exploiting excimer emission. Their potential as cell imaging agents amenable to time-resolved detection procedures on the microsecond timescale has also been demonstrated (118 references).

  4. Development of luminescent sensors based on transition metal complexes for the detection of nitroexplosives.

    Science.gov (United States)

    Sathish, Veerasamy; Ramdass, Arumugam; Velayudham, Murugesan; Lu, Kuang-Lieh; Thanasekaran, Pounraj; Rajagopal, Seenivasan

    2017-12-12

    The detection of chemical explosives is a major area of research interest and is essential for the military as well as homeland security to counter the catastrophic effects of global terrorism. In recent years, tremendous effort has been devoted to the development of luminescent materials for the detection of explosives in the vapor, solution, and solid states with a high degree of selectivity and sensitivity and a rapid response time. Apart from the wide range of organic fluorescent chemosensors, transition metal complexes play a prominent role in the sensing of nitroaromatic explosives owing to their rich photophysical characteristics. This review briefly summarizes the salient features of the design and preparation of transition metal (Zn(ii), Ir(iii), Pd(ii), Pt(ii), Re(i) and Ru(ii)) complexes/metallacycles/metallosupramolecules with emphasis on their photophysical properties, sensing behavior, mechanism of action, and the driving forces for detecting explosives and future prospects and challenges. Most of the probes that have been reported to date act as "turn-off" luminescent sensors because their emission (intensity, lifetime, and quantum yield) is eventually quenched upon sensing with nitroaromatic compounds (NACs) through photo-induced electron or energy transfer. These unique properties of transition metal complexes in response to explosives open up new vistas for the development of real world applications such as on-site detection, in-field security, forensic research, etc.

  5. Luminescent hybrid materials based on (8-hydroxyquinoline)-substituted metal-organic complexes and lead-borate glasses

    Science.gov (United States)

    Petrova, Olga B.; Anurova, Maria O.; Akkuzina, Alina A.; Saifutyarov, Rasim R.; Ermolaeva, Ekaterina V.; Avetisov, Roman I.; Khomyakov, Andrew V.; Taydakov, Ilya V.; Avetissov, Igor Ch.

    2017-07-01

    Novel luminescent organic-inorganic hybrid materials based on 8-hydroxyquinoline metal complexes (Liq, Kq, Naq, Rbq, Mgq2, Srq2, Znq2, Scq3, Alq3, Gaq3, and Inq3) have been synthesized by a high temperature exchange reaction with 80PbF2-20B2O3 inorganic low-melting glass. The mechanical and optical properties, transmission spectra, emission an excitation photoluminescence, and luminescence kinetic of hybrid materials were studied. All hybrid materials showed a wide luminescence band in the range 400-700 nm.

  6. The diversity of five metal-organic complexes based on an unsymmetrical biphenyl tetracarboxylate: Synthesis, structures, magnetism and luminescence

    Science.gov (United States)

    Feng, Si-si; Xie, Ling; Lu, Li-ping; Zhu, Miao-li; Su, Feng

    2018-02-01

    Careful investigation of the effects of metal ions and pH value resulted in five multi-dimensional metal-organic complexes, [Co5(μ3-OH)2(α-bptc)2(H2O)6]n (1), {(H3O)2[Co4(μ3-O)(α-bptc)2(H2O)]·4H2O}n (2), {K2[Zn4(μ3-OH)2(α-bptc)2(H2O)3]}n (3), [Zn4(α-bptc)2(H2O)3]n (4), and {[Cd4(α-bptc)2(H2O)7]·2H2O}n (5) (α-H4bptc = 2,3,3',4'-biphenyl tetracarboxylic acid). The complexes consisted of different highly connected secondary building units (SBUs) assembled via hydrothermal in situ routes. The pH value as well as the kinds of metal ions influenced the coordination modes of α-H4bptc and also introduced the hydroxyl ligand at high pH value, resulting in the diversity of SBUs and dimensionality. Variable temperature magnetic measurements indicated the antiferromagnetic behavior in the Co5 core in 1, and the intra-chain ferrimagnetic behavior in complex 2. Moreover, the luminescent properties of the complexes 3-5 indicated the existence of intra-ligand charge transfer.

  7. Luminescence from metals and insulators

    International Nuclear Information System (INIS)

    Crawford, O.H.

    1985-01-01

    The term luminescence is normally applied to light emission that is not explainable by the mechanisms discussed by the other speakers in this meeting. Specifically, it is not transition radiation, surface plasmon radiation, or bremsstrahlung. One normally thinks of luminescence as arising from one-electron transitions within a medium. This talk consists of an overview of luminescence from condensed matter under irradiation by either energetic particles or photons. The author begins with organic molecules, where luminescence is best understood, and then discusses inorganic insulators and metals. Finally, the dependence of yield upon projectile species and velocity is discussed, and predictions are made concerning the relative effectiveness of electrons, protons, and hydrogen atoms in exciting luminescence

  8. Transition Metal Complexes as Photosensitizers for Near-Infrared Lanthanide Luminescence

    NARCIS (Netherlands)

    Klink, S.I.; Keizer, Henk; van Veggel, F.C.J.M.

    2000-01-01

    We thank Roel Fokkens and Nico Nibbering (University of Amsterdam) for recording and discussing the MALDI-TOF mass spectra. Martijn Werts (University of Amsterdam) is gratefully acknowledged for his support with the time-resolved luminescence measurements. This research has been financially

  9. Luminescent Metal Nanoclusters for Potential Chemosensor Applications

    Directory of Open Access Journals (Sweden)

    Muthaiah Shellaiah

    2017-12-01

    Full Text Available Studies of metal nanocluster (M-NCs-based sensors for specific analyte detection have achieved significant progress in recent decades. Ultra-small-size (<2 nm M-NCs consist of several to a few hundred metal atoms and exhibit extraordinary physical and chemical properties. Similar to organic molecules, M-NCs display absorption and emission properties via electronic transitions between energy levels upon interaction with light. As such, researchers tend to apply M-NCs in diverse fields, such as in chemosensors, biological imaging, catalysis, and environmental and electronic devices. Chemo- and bio-sensory uses have been extensively explored with luminescent NCs of Au, Ag, Cu, and Pt as potential sensory materials. Luminescent bi-metallic NCs, such as Au-Ag, Au-Cu, Au-Pd, and Au-Pt have also been used as probes in chemosensory investigations. Both metallic and bi-metallic NCs have been utilized to detect various analytes, such as metal ions, anions, biomolecules, proteins, acidity or alkalinity of a solution (pH, and nucleic acids, at diverse detection ranges and limits. In this review, we have summarized the chemosensory applications of luminescent M-NCs and bi-metallic NCs.

  10. Naturally Efficient Emitters: Luminescent Organometallic Complexes Derived from Natural Products

    Science.gov (United States)

    Zhang, Wen-Hua; Young, David J.

    2013-08-01

    Naturally occurring molecules offer intricate structures and functionality that are the basis of modern medicinal chemistry, but are under-represented in materials science. Herein, we review recent literature describing the use of abundant and relatively inexpensive, natural products for the synthesis of ligands for luminescent organometallic complexes used for organic light emitting diodes (OLEDs) and related technologies. These ligands are prepared from the renewable starting materials caffeine, camphor, pinene and cinchonine and, with the exception of caffeine, impart performance improvements to the emissive metal complexes and resulting OLED devices, with emission wavelengths that span the visible spectrum from blue to red. The advantages of these biologically-derived molecules include improved solution processibility and phase homogeneity, brighter luminescence, higher quantum efficiencies and lower turn-on voltages. While nature has evolved these carbon-skeletons for specific purposes, they also offer some intriguing benefits in materials science and technology.

  11. Metal luminescence in a bright disintegrated prominence

    International Nuclear Information System (INIS)

    Yakovkin, N.A.; Zel'dina, M.Yu.; Rakhubovskij, A.S.; AN Ukrainskoj SSR, Kiev. Glavnaya Astronomicheskaya Observatoriya)

    1975-01-01

    It is found that Na, Mg, Ca, Sc, Ti, Fe, Sr, and Ba contents in a protuberance relative to the hydrogen content is about the same as in photosphere and chromosphere (except for the Na abundance). The metals are in the state of single ionization with the exception of calcium [Ca ++ ] approximately [Ca + ], strontium [Sr ++ ] = 0.5 [Sr + ], and barium [Ba ++ ] = 6Ba + , whose secondary ionization occurs from metastable states by Lsub(α)-emission in the protuberance. The Lsub(α)-emission ionizes neutral iron as well. Primary ionization of remaining metals is performed by the solar near ultraviolet. Luminescence in metal lines is provided by the photosphere emission scattering, and only H and KCa + lines are excited by electron impacts

  12. Luminescent properties of terbium complex with phenylanthranilic acid

    International Nuclear Information System (INIS)

    Alakaeva, L.A.; Kalazhokova, I.A.; Naurzhanova, F.Kh.

    1990-01-01

    Existence of terbium luminescence reaction in complex with phenanthranilic acid (FAA) is ascertained. The optimal conditions of terbium complexing with FAA are found. The ratio of components in the complex is 1:1. The influence of foreign rare earth in terbium luminescence intensity in complex with FAA is studied

  13. Metal-enhanced luminescence: Current trend and future perspectives- A review

    International Nuclear Information System (INIS)

    Ranjan, Rajeev; Esimbekova, Elena N.; Kirillova, Maria A.; Kratasyuk, Valentina A.

    2017-01-01

    Optically enhanced biosensing strategies are prerequisites for developing miniature and highly sensitive multiplexed analytical platforms. Such smart biosensing systems are highly promising for use in the fields of biomedicine and environmental monitoring. Optical signal enhancement during bioassays is attributed to the complex opto-electronic interactions of incoming photonic signals at the nanomaterial interface. Research on the use of metals other than gold and silver for such purposes tends to extend the spectral window to observe luminescence enhancement effects. Such manifold increase in luminescence may be explained by the principles of plasmon coupling, directional emission led high collection efficiency, Rayleigh scattering and related opto-electronic events. The present review begins with a mechanistic description of important phenomena associated with metal-induced luminescence enhancement, particularly focusing on the origin of metal-enhanced luminescence. This review further analyses the hybrid nanostructure capabilities responsible for maintaining unique opto-electronic properties during bio-functionalisation. Current research trends in this area, future scope of this field for designing useful bioassays and concluding remarks are then discussed. - Highlights: • Nanomaterials significantly differ from their bulk counterparts. • Strong and pronounced photophysical effects at the metal surface provide opportunities for designing novel biosensors. • Metal-enhanced luminescence increases the quantum yield of luminescent reactions. • Under optimal conditions, plasmon coupling enhances the optical effects at the nanometal surface.

  14. Metal-enhanced luminescence: Current trend and future perspectives- A review

    Energy Technology Data Exchange (ETDEWEB)

    Ranjan, Rajeev [Laboratory of Bioluminescent Biotechnologies, Department of Biophysics, Institute of Fundamental Biology and Biotechnology, Siberian Federal University, 79 Svobodny Prospect, Krasnoyarsk 660041 (Russian Federation); Esimbekova, Elena N., E-mail: esimbekova@yandex.ru [Laboratory of Bioluminescent Biotechnologies, Department of Biophysics, Institute of Fundamental Biology and Biotechnology, Siberian Federal University, 79 Svobodny Prospect, Krasnoyarsk 660041 (Russian Federation); Institute of Biophysics SB RAS, Federal Research Center “Krasnoyarsk Science Center SB RAS”, Akademgorodok 50/50, Krasnoyarsk 660036 (Russian Federation); Kirillova, Maria A. [Laboratory of Bioluminescent Biotechnologies, Department of Biophysics, Institute of Fundamental Biology and Biotechnology, Siberian Federal University, 79 Svobodny Prospect, Krasnoyarsk 660041 (Russian Federation); Kratasyuk, Valentina A. [Laboratory of Bioluminescent Biotechnologies, Department of Biophysics, Institute of Fundamental Biology and Biotechnology, Siberian Federal University, 79 Svobodny Prospect, Krasnoyarsk 660041 (Russian Federation); Institute of Biophysics SB RAS, Federal Research Center “Krasnoyarsk Science Center SB RAS”, Akademgorodok 50/50, Krasnoyarsk 660036 (Russian Federation)

    2017-06-08

    Optically enhanced biosensing strategies are prerequisites for developing miniature and highly sensitive multiplexed analytical platforms. Such smart biosensing systems are highly promising for use in the fields of biomedicine and environmental monitoring. Optical signal enhancement during bioassays is attributed to the complex opto-electronic interactions of incoming photonic signals at the nanomaterial interface. Research on the use of metals other than gold and silver for such purposes tends to extend the spectral window to observe luminescence enhancement effects. Such manifold increase in luminescence may be explained by the principles of plasmon coupling, directional emission led high collection efficiency, Rayleigh scattering and related opto-electronic events. The present review begins with a mechanistic description of important phenomena associated with metal-induced luminescence enhancement, particularly focusing on the origin of metal-enhanced luminescence. This review further analyses the hybrid nanostructure capabilities responsible for maintaining unique opto-electronic properties during bio-functionalisation. Current research trends in this area, future scope of this field for designing useful bioassays and concluding remarks are then discussed. - Highlights: • Nanomaterials significantly differ from their bulk counterparts. • Strong and pronounced photophysical effects at the metal surface provide opportunities for designing novel biosensors. • Metal-enhanced luminescence increases the quantum yield of luminescent reactions. • Under optimal conditions, plasmon coupling enhances the optical effects at the nanometal surface.

  15. Calibration beads containing luminescent lanthanide ion complexes

    Science.gov (United States)

    The reliability of lanthanide luminescence measurements, by both flow cytometry and digital microscopy, will be enhanced by the availability of narrow-band emitting lanthanide calibration beads. These beads can also be used to characterize spectrographic instruments, including mi...

  16. Synthesis, characterization and luminescent properties of lanthanide complexes with an unsymmetrical tripodal ligand

    Energy Technology Data Exchange (ETDEWEB)

    Yan Zhenzhong [State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Tang Yu [State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China)], E-mail: tangyu@lzu.edu.cn; Liu Weisheng; Tan Minyu [State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China)

    2008-09-15

    Solid complexes of lanthanide nitrates with a new unsymmetrical tripodal ligand, bis[(2'-benzylaminoformyl)phenoxyl)ethyl](ethyl)amine (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 also investigated. Under the excitation of UV light, these complexes exhibited characteristic emission of central metal ions.

  17. Terbium and dysprosium complexes luminescence at low temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Meshkova, S B; Kravchenko, T B; Kononenko, L.I.; Poluehktov, N S [AN Ukrainskoj SSR, Odessa. Fiziko-Khimicheskij Inst.

    1979-01-01

    The variation is studied of the luminescence intensity of terbium and dysprosium complexes used in the analysis as solutions are cooled down to the liquid nitrogen temperature. Three groups of methods have been studied: observation of fluorescence of aqueous solutions, precipitate and extract suspensions in organic solvents. The brightest luminescence and greatest increase in luminescence intensity are observed at freezing of complex solvents with 1,2-dioxybenzene-3,5-disulfonic acid (DBSA) and iminodiacetic acid (IDA) and DBSA+EDTA, as well as in the case of benzene extracting of complexes with phenanthroline and salicylic acid. Otherwise the intensity increases 2-14-fold and for the complex of terbium with acetoacetic ester 36-fold.

  18. Synthesis and characterization of substituted Schiff-base ligands and their d(10) metal complexes: structure-induced luminescence tuning behaviors and applications in co-sensitized solar cells.

    Science.gov (United States)

    Dong, Yu-Wei; Fan, Rui-Qing; Wang, Ping; Wei, Li-Guo; Wang, Xin-Ming; Zhang, Hui-Jie; Gao, Song; Yang, Yu-Lin; Wang, Yu-Lei

    2015-03-28

    Nine IIB group complexes, [ZnL1Cl2] (Zn1), [CdL1Cl2]2 (Cd1), [HgL1Cl2] (Hg1), [ZnL2Cl2] (Zn2), [CdL2Cl2] (Cd2), [HgL2Cl2] (Hg2), [ZnL3Cl2] (Zn3), [CdL3Cl2] (Cd3) and [HgL3Cl2] (Hg3), have been synthesized from the corresponding ortho-(6-methoxy-pyridyl)(CH[double bond, length as m-dash]NAr) (where Ar = 2,6-iPr2C6H3, L1; 4-MeC6H4, L2; 2-OMeC6H4, L3) Schiff base and structurally characterized by elemental analysis, FT-IR, (1)H NMR and X-ray single-crystal analysis. Crystallographic studies reveal that the center metal of the complexes adopts a distorted tetrahedron geometry (except for Cd1 and Cd3, which display square pyramidal geometry) and C-HCl hydrogen bonds and ππ stacking interactions contribute to three-dimensional supramolecular structures. The series of complexes exhibit tunable luminescence from blue, through green, to light yellow by varying the temperature (298 K and 77 K), both in solution and in the solid state. Moreover, the quantum yields range from 0.027 to 0.422, and decrease according to the order of the periodic table (Zn > Cd > Hg). These results indicate that the center atom of the complexes leads to the geometry differences and hence to the tunable luminescence properties. Because Zn1-Zn3 exhibited higher molar extinction coefficients and a distinct absorption region, they were employed as co-sensitizers in ruthenium dye N719-sensitized photoanodes to deliver light-electricity efficiency enhancement, being assembled with counter-electrodes and electrolyte to prepare ZnX/N719 (where ZnX = Zn1, Zn2, and Zn3) co-sensitized dye sensitized solar cell (DSSC) devices. The prepared co-absorbent could overcome the deficiency of N719 absorption in the low-wavelength region of the visible spectrum, and offset competitive visible-light absorption of I3(-). Application of these prepared complexes in N719-sensitized solar cells enhanced their performance by 10-36%, which indicated a potential application of these types of complexes in DSSCs.

  19. Conducting metal dithiolate complexes

    DEFF Research Database (Denmark)

    Underhill, A. E.; Ahmad, M. M.; Turner, D. J.

    1985-01-01

    Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound......Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound...

  20. Oligocyclopentadienyl transition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    de Azevedo, Cristina G.; Vollhardt, K. Peter C.

    2002-01-18

    Synthesis, characterization, and reactivity studies of oligocyclopentadienyl transition metal complexes, namely those of fulvalene, tercyclopentadienyl, quatercyclopentadienyl, and pentacyclopentadienyl(cyclopentadienyl) are the subject of this account. Thermal-, photo-, and redox chemistries of homo- and heteropolynuclear complexes are described.

  1. Luminescent Dinuclear Ruthenium Terpyridine Complexes with a Bis-Phenylbenzimidazole Spacer.

    Science.gov (United States)

    Mondal, Debiprasad; Biswas, Sourav; Paul, Animesh; Baitalik, Sujoy

    2017-07-17

    A conjugated bis-terpyridine bridging ligand, 2-(4-(2,6-di(pyridin-2-yl)pyridin-4-yl)phenyl)-6-(2-(4-(2,6-di(pyridin-2-yl)pyridin-4-yl)phenyl)-1H-benzo[d]imidazol-6-yl)-1H-benzo[d] imidazole (tpy-BPhBzimH 2 -tpy), was designed in this work by covalent coupling of 3,3'-diaminobenzidine and two 4'-(p-formylphenyl)-2,2':6',2″-terpyridine units to synthesize a new series of bimetallic Ru(II)-terpyridine light-harvesting complexes. Photophysical and electrochemical properties were modulated by the variation of the terminal ligands in the complexes. The new compounds were thoroughly characterized by 1 H NMR spectroscopy, high-resolution mass spectrometry, and elemental analysis. Absorption spectra of the complexes consist of very strong ligand-centered π-π* and n-π* transitions in the UV, metal-to-ligand, and intraligand charge transfer bands in the visible regions. Steady-state and time-resolved emission spectral measurements indicate that the complexes exhibit moderately intense luminescence at room temperature within the spectral domain of 653-687 nm having luminescence lifetimes in the range between 6.3 and 55.2 ns, depending upon terminal tridentate ligand and solvent. Variable-temperature luminescence measurements suggest substantial increase of the energy gap between luminescent 3 metal-to-ligand charge transfer state and nonluminescent 3 metal centered in the complexes compared to the parent [Ru(tpy) 2 ] 2+ . Each of the three bimetallic complexes exhibits only one reversible couple in the positive potential window with almost no detectable splitting corresponding to simultaneous oxidation of the two remote Ru centers. All the complexes possess a number of imidazole NH protons, which became sufficiently acidic upon metal ion coordination. By utilizing these NH protons, we thoroughly studied anion recognition properties of the complexes in pure organic as well as predominantly aqueous media through multiple optical channels and spectroscopic methods. Finally

  2. Luminescent micro- and nanofibers based on novel europium phthalate complex

    Energy Technology Data Exchange (ETDEWEB)

    Enculescu, M., E-mail: mdatcu@infim.ro [National Institute of Materials Physics, Multifunctional Materials and Structures, PO Box MG-7, 77125 Magurele-Bucharest (Romania); Preda, N.; Matei, E.; Enculescu, I. [National Institute of Materials Physics, Multifunctional Materials and Structures, PO Box MG-7, 77125 Magurele-Bucharest (Romania)

    2012-09-14

    We synthesized by wet chemical route a novel europium-potassium phthalate complex Eu{sup 3+}K{sup +}[(COO){sub 2}(C{sub 6}H{sub 4})]{sub 2}. The compound is a white powder insoluble in water. X-ray diffraction evaluation shows that we obtained a new crystalline compound with no traces of the starting materials (potassium hydrogen phthalate and europium chloride). Scanning electron microscopy reveals that the powder consists of fiber-shaped structures with sizes larger than 250 nm in diameter. Energy dispersive X-ray analysis proves that the compound has a 1:1 europium-potassium ratio. Fourier transform infrared spectroscopy confirms the presence of the phthalate in the new compound. Photoluminescence and cathodoluminescence measurements show that the fiber-shaped structures are intensely luminescent with emission bands corresponding to the {sup 5}D{sub 0} {yields} {sup 7}F{sub J} (J = 1-4) Eu (III) ion's transitions in the region between 580 nm and 700 nm, the most intense maximum being observed around 615 nm. Up-converted luminescence with a maximum at 315 nm was recorded. -- Highlights: Black-Right-Pointing-Pointer A new europium-potassium phthalate complex was synthesized by wet chemical route. Black-Right-Pointing-Pointer Fiber-shaped crystalline structures with sizes larger than 250 nm. Black-Right-Pointing-Pointer The most probable structure of the molecule is [C{sub 6}H{sub 4}(COO{sup -}){sub 2}]{sub 2} K{sup +}Eu{sup 3+}. Black-Right-Pointing-Pointer Intense luminescence due to Eu{sup 3+} ions {sup 5}D{sub 0} {yields} {sup 7}F{sub J} transitions. Black-Right-Pointing-Pointer Up-converted luminescence with a maximum at 315 nm was recorded.

  3. Mitochondria Targeting with Luminescent Rhenium(I) Complexes.

    Science.gov (United States)

    Skiba, Joanna; Bernaś, Tytus; Trzybiński, Damian; Woźniak, Krzysztof; Ferraro, Giarita; Marasco, Daniela; Merlino, Antonello; Shafikov, Marsel Z; Czerwieniec, Rafał; Kowalski, Konrad

    2017-05-15

    Two new neutral fac -[Re(CO)₃(phen)L] compounds ( 1 , 2 ), with phen = 1,10-phenanthroline and L = O₂C(CH₂)₅CH₃ or O₂C(CH₂)₄C≡CH, were synthetized in one-pot procedures from fac -[Re(CO)₃(phen)Cl] and the corresponding carboxylic acids, and were fully characterized by IR and UV-Vis absorption spectroscopy, ¹H- and 13 C-NMR, mass spectrometry and X-ray crystallography. The compounds, which display orange luminescence, were used as probes for living cancer HeLa cell staining. Confocal microscopy revealed accumulation of both dyes in mitochondria. To investigate the mechanism of mitochondrial staining, a new non-emissive compound, fac -[Re(CO)₃(phen)L], with L = O₂C(CH₂)₃((C₅H₅)Fe(C₅H₄), i.e., containing a ferrocenyl moiety, was synthetized and characterized ( 3 ). 3 shows the same mitochondrial accumulation pattern as 1 and 2 . Emission of 3 can only be possible when ferrocene-containing ligand dissociates from the metal center to produce a species containing the luminescent fac -[Re(CO)₃(phen)]⁺ core. The release of ligands from the Re center was verified in vitro through the conjugation with model proteins. These findings suggest that the mitochondria accumulation of compounds 1 - 3 is due to the formation of luminescent fac -[Re(CO)₃(phen)]⁺ products, which react with cellular matrix molecules giving secondary products and are uptaken into the negatively charged mitochondrial membranes. Thus, reported compounds feature a rare dissociation-driven mechanism of action with great potential for biological applications.

  4. Mitochondria Targeting with Luminescent Rhenium(I Complexes

    Directory of Open Access Journals (Sweden)

    Joanna Skiba

    2017-05-01

    Full Text Available Two new neutral fac-[Re(CO3(phenL] compounds (1,2, with phen = 1,10-phenanthroline and L = O2C(CH25CH3 or O2C(CH24C≡CH, were synthetized in one-pot procedures from fac-[Re(CO3(phenCl] and the corresponding carboxylic acids, and were fully characterized by IR and UV-Vis absorption spectroscopy, 1H- and 13C-NMR, mass spectrometry and X-ray crystallography. The compounds, which display orange luminescence, were used as probes for living cancer HeLa cell staining. Confocal microscopy revealed accumulation of both dyes in mitochondria. To investigate the mechanism of mitochondrial staining, a new non-emissive compound, fac-[Re(CO3(phenL], with L = O2C(CH23((C5H5Fe(C5H4, i.e., containing a ferrocenyl moiety, was synthetized and characterized (3. 3 shows the same mitochondrial accumulation pattern as 1 and 2. Emission of 3 can only be possible when ferrocene-containing ligand dissociates from the metal center to produce a species containing the luminescent fac­[Re(CO3(phen]+ core. The release of ligands from the Re center was verified in vitro through the conjugation with model proteins. These findings suggest that the mitochondria accumulation of compounds 1–3 is due to the formation of luminescent fac-[Re(CO3(phen]+ products, which react with cellular matrix molecules giving secondary products and are uptaken into the negatively charged mitochondrial membranes. Thus, reported compounds feature a rare dissociation-driven mechanism of action with great potential for biological applications.

  5. Selenophene transition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    White, Carter James [Iowa State Univ., Ames, IA (United States)

    1994-07-27

    This research shows that selenophene transition metal complexes have a chemistry that is similar to their thiophene analogs. Selenophene coordination has been demonstrated and confirmed by molecular structure in both the η5- and the η1(Se)-coordination modes. The reaction chemistry of selenophene complexes closely resembles that of the analogous thiophene complexes. One major difference, however, is that selenophene is a better donor ligand than thiophene making the selenophene complexes more stable than the corresponding thiophene complexes. The 77Se NMR chemical shift values for selenophene complexes fall within distinct regions primarily depending on the coordination mode of the selenophene ligand. In the final paper, the C-H bond activation of η1(S)-bound thiophenes, η1(S)-benzothiophene and η1(Se)-bound selenophenes has been demonstrated. The deprotonation and rearrangement of the η1(E)-bound ligand to the carbon bound L-yl complex readily occurs in the presence of base. Reprotonation with a strong acid gives a carbene complex that is unreactive towards nucleophilic attack at the carbene carbon and is stable towards exposure to air. The molecular structure of [Cp(NO)(PPh3)Re(2-benzothioenylcarbene)]O3SCF3 was determined and contains a Re-C bond with substantial double bond character. Methyl substitution for the thienylcarbene or selenylcarbene gives a carbene that rearranges thermally to give back the η1(E)-bound complex. Based on these model reactions, a new mechanism for the H/D exchange of thiophene over the hydrodesulfurization catalyst has been proposed.

  6. Hormesis response of marine and freshwater luminescent bacteria to metal exposure

    Directory of Open Access Journals (Sweden)

    KAILI SHEN

    2009-01-01

    Full Text Available The stimulatory effect of low concentrations of toxic chemicals on organismal metabolism, referred to as hormesis, has been found to be common in the widely used luminescence bioassay. This paper aims to study the hormesis phenomenon in both marine and freshwater luminescent bacteria, named Photobacterium phosphorem and Vibrio qinghaiensis. The effects of Cu (II, Zn (II, Cd (II and Cr (VI on luminescence of these two bacteria were studied for 0 to 75 minutes exposure by establishing dose- and time-response curves. A clear hormesis phenomenon was observed in all four testing metals at low concentrations under the condition of luminescence assays.

  7. Metal complex derivatives of hydrogen uranyl phosphate

    International Nuclear Information System (INIS)

    Grohol, D.; Blinn, E.L.

    1994-01-01

    Derivatives of hydrogen uranyl phosphate were prepared by incorporating transition metal complexes into the uranyl phosphate matrix. The transition metal complexes employed include bis(ethylenediamine)copper(II), bis(1,3-propanediamine)copper(II) chloride, (triethylenetetramine)copper(II), (1,4,8,11-tetraazacyclotetradecane)copper(II), (1,4,8,12-tetraazacyclopentadecane)copper(II), (1,4,8,11-tetraazacyclotetradecane)nickel(II) chloride, (triethylenetetramine)nickel(II) and others. The chemical analyses of these derivatives indicated that the incorporation of the transition metal complexes into the uranyl phosphate matrix via ion exchange was not stoichiometric. The extent of ion exchange is dependent on the size and structure of the transition metal complex. All complexes were characterized by X-ray powder diffractometry, electronic and infrared spectra, thermal analyses and chemical analysis. An attempt was made to correlate the degree of quenching of the luminescence of the uranyl ion to the spacing between the uranyl phosphate layers in the derivatives

  8. Polymetallic lanthanide (III) complexes for the design of new luminescent materials

    International Nuclear Information System (INIS)

    Marchal, C.

    2008-09-01

    The incorporation of f elements in highly organized polymetallic complexes is of great interest in supramolecular chemistry and allows the combination of their nano-scopic size with the magnetic or optical properties of the metal ions. However due to the difficulty in controlling the coordination environment of these ions, the assembly of lanthanide-based polynuclear architectures has lagged behind that of other systems. These factors make the rational design for the construction of supramolecular lanthanide complexes quite challenging. In order to better understand the factors determining the assembly of lanthanide-based polymetallic arrays, we designed two different types of organic ligands, which favor, in one case, formation of infinite polymetallic complexes (coordination polymers), and in the case the assembly of discrete polymetallic architectures. Thus, we show that the use of flexible and multi-dentate picolinate-derivative ligands enables the formation of infinite and luminescent infinite frameworks which display very interesting luminescent properties. Geometry of the ligand has a great influence on the final network architecture. Particularly, implementation of four picolinate units within a tetrapodal ligand results in the controlled assembly of 1-D coordination polymers. Conversely to favor the controlled assembly of discrete polymetallic arrays we use dissymmetric ligands which displays low denticity. Complexation studies of a tridentate 8- hydroxyquinoline-derivative ligand as well as a tetradentate ligand possessing an oxazoline ring are presented. (author)

  9. Mitochondrial respiratory complex I probed by delayed luminescence spectroscopy

    Science.gov (United States)

    Baran, Irina; Ionescu, Diana; Privitera, Simona; Scordino, Agata; Mocanu, Maria Magdalena; Musumeci, Francesco; Grasso, Rosaria; Gulino, Marisa; Iftime, Adrian; Tofolean, Ioana Teodora; Garaiman, Alexandru; Goicea, Alexandru; Irimia, Ruxandra; Dimancea, Alexandru; Ganea, Constanta

    2013-12-01

    The role of mitochondrial complex I in ultraweak photon-induced delayed photon emission [delayed luminescence (DL)] of human leukemia Jurkat T cells was probed by using complex I targeting agents like rotenone, menadione, and quercetin. Rotenone, a complex I-specific inhibitor, dose-dependently increased the mitochondrial level of reduced nicotinamide adenine dinucleotide (NADH), decreased clonogenic survival, and induced apoptosis. A strong correlation was found between the mitochondrial levels of NADH and oxidized flavin mononucleotide (FMNox) in rotenone-, menadione- and quercetin-treated cells. Rotenone enhanced DL dose-dependently, whereas quercetin and menadione inhibited DL as well as NADH or FMNox. Collectively, the data suggest that DL of Jurkat cells originates mainly from mitochondrial complex I, which functions predominantly as a dimer and less frequently as a tetramer. In individual monomers, both pairs of pyridine nucleotide (NADH/reduced nicotinamide adenine dinucleotide phosphate) sites and flavin (FMN-a/FMN-b) sites appear to bind cooperatively their specific ligands. Enhancement of delayed red-light emission by rotenone suggests that the mean time for one-electron reduction of ubiquinone or FMN-a by the terminal Fe/S center (N2) is 20 or 284 μs, respectively. All these findings suggest that DL spectroscopy could be used as a reliable, sensitive, and robust technique to probe electron flow within complex I in situ.

  10. Hard X-ray-induced optical luminescence via biomolecule-directed metal clusters†

    Science.gov (United States)

    Pratx, Guillem; Sun, Conroy; Sakamoto, Masanori; Ahmad, Moiz; Volotskova, Olga; Ong, Qunxiang; Teranishi, Toshiharu; Harada, Yoshie

    2014-01-01

    Here, we demonstrate that biomolecule-directed metal clusters are applicable in the study of hard X-ray excited optical luminescence, promising a new direction in the development of novel X-ray-activated imaging probes. PMID:24463467

  11. Synthesis, crystal structures and luminescence properties of two metal carboxyphosphonates

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Chaonan; Feng, Pingjing; Li, Jintang, E-mail: leejt@xmu.edu.cn; Luo, Xuetao

    2017-05-15

    Two metal carboxyphosphonates, [Co{sub 2}(OOCC{sub 5}H{sub 3}NPO{sub 3}){sub 2·}(H{sub 2}O){sub 3}] (Compound1) and Zn{sub 3}[OOCC{sub 6}H{sub 3}CH(OH)PO{sub 3}]{sub 2·}2H{sub 2}O (Compound2) were successfully synthesized under the hydrothermal reactions. In compound 1, two (Co1-NO{sub 5}) octahedra link the (CPO{sub 3}) by sharing the corner, which link the two (Co2-O{sub 6}) octahedra. From a-axis the six clusters form the layer. Each layer is linked through hydrogen bond. In compound 2, the (Zn-O{sub 4}) tetrahedron and (CPO{sub 3}) tetrahedron are corner-shared, which arrange in line. From a-axis, each line forms the columnar. The thermal and luminescence properties of these compounds were investigated. - Graphical abstract: The synthesis conditions of the two compounds and the crystal morphology. Compound 1 shows the layer and the compound 2 shows the pillared-layer. - Highlights: • Two new carboxyphosphonate ligands have been prepared. • Using the two ligands, two metal carboxyphosphonates have been synthesized. • The two MOFs may be candidates for fluorescent materials.

  12. Luminescence behavior of the dibenzoyl methane europium(III) complexes in sol-gel derived host materials

    International Nuclear Information System (INIS)

    Wang Feng; Fan Xianping; Wang Minquan; Zhang Xianghua

    2005-01-01

    The luminescence behavior of the dibenzoyl methane europium(III) complexes (Eu(DBM) 3 ) in sol-gel derived host materials have been investigated. The steady-state excitation and emission spectra and the time-resolved spectra of the 1% EuCl 3 and 3% DBM co-doped gel indicated an efficient ligand-to-metal energy transfer. The Eu(DBM) 3 complexes in the gel showed longer 5 D 0 lifetimes in comparison with Eu(DBM) 3 .3H 2 O complexes. The luminescence intensity of the 1% EuCl 3 and 3% DBM co-doped gel decreased continuously with increasing temperature and time of heat treatment, which indicated the gradual decomposition of the Eu(DBM) 3 complexes in the gel during heat treatment

  13. Synthesis, Characterization, Luminescence and Biological Activity of Two Lanthanide Complexes Involving Mixed Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Deyun; Guo, Haifu; Qin, Liang [Zhaoqing Univ., Zhaoqing (China); Xu, Jun [Jinan Univ., Guangzhou (China)

    2013-09-15

    Two new isostructural dinuclear complexes, Ln{sub 2}(4-cpa){sub 6}(bpy){sub 2} (Ln = Eu (1); Tb (2), 4-cpa = 4-chlorophenyl-acetate, bpy = 2,2'-bipyridine), have been hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. The lanthanide ions are bridged by two bidentate and two terdentate carboxylate groups to give centrosymmetric dimers with Ln···Ln separations of 3.967(2) and 3.956(3) A, respectively. Each metal atom is nine-coordinate and exhibits a distorted tricapped trigonal prismatic geometry. Three-dimensional fluorescence spectra show that both 1 and 2 emit bright red and green luminescence at room temperature, with long lifetimes of up to 0.369 ms (at 614 nm) and 0.432 ms (at 543 nm), respectively. Moreover, poor luminescence efficiency has been noted for complex 2. The 4-Hcpa ligand and complexes 1-2 have been screened for their phytogrowth-inhibitory activities against Brassica napus L. and Echinochloa crusgalli L., and the results are compared with the activity of quizalofop-P-ethyl.

  14. Luminescent properties of europium different-ligand complexes with cyclic. beta. -diketones and diantipyrylalkanes

    Energy Technology Data Exchange (ETDEWEB)

    Ul' yanova, T M; Gerasimenko, G N; Tishchenko, M A; Vitkun, R A [AN Ukrainskoj SSR, Odessa. Fiziko-Khimicheskij Inst.

    1983-03-01

    Using luminescence method different-ligand complexing of europium ions with diantipyrylalkanes and cyclic ..beta..-diketones: 2-acetyl- and 2-benzoyl-1.3-indandions, has been studied. The optimum conditions of the formation of different-ligand complexes and the ratio of components in it are determined. Effect of alien lanthanides and diantipyrylmethane derivatives on the luminescence intensity of europium complexes is clarified. A correlation between the ratio of the luminescence intensity bands of europium complexes and the values of oscillator strengths of supersensitive transitions of neodymium and erbium absorption bands is established.

  15. Luminescence of uranyl ion complexed with 2,6-pyridine dicarboxylic acid as ligand in acetonitrile medium. Observation of co-luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Maji, Siuli; Kumar, Satendra; Sankaran, Kannan [Indira Ghandi Centre for Atomic Research, Tamil Nadu (India). Materials Chemistry Div.

    2017-10-01

    Luminescence from UO{sub 2}{sup 2+} (uranyl ion) complexed with 2,6-pyridine dicarboxylic acid (PDA) has been studied using acetonitrile (MeCN) as solvent between pH 1.0 and 6.0. The enhancement in luminescence intensity because of sensitization by PDA in the non-aqueous environment provided by the MeCN is found to be one order better than in aqueous medium. The luminescence is further enhanced by about four times following the addition of Y{sup 3+}; a process known as co-luminescence. This is the first study on co-luminescence of uranyl ion in its PDA complex. Lifetime studies indicate the presence of two species having different micro-environments. Formations of both intra and inter molecular complexes are believed to be responsible for enhancement due to co-luminescence.

  16. Luminescence of uranyl ion complexed with 2,6-pyridine dicarboxylic acid as ligand in acetonitrile medium. Observation of co-luminescence

    International Nuclear Information System (INIS)

    Maji, Siuli; Kumar, Satendra; Sankaran, Kannan

    2017-01-01

    Luminescence from UO_2"2"+ (uranyl ion) complexed with 2,6-pyridine dicarboxylic acid (PDA) has been studied using acetonitrile (MeCN) as solvent between pH 1.0 and 6.0. The enhancement in luminescence intensity because of sensitization by PDA in the non-aqueous environment provided by the MeCN is found to be one order better than in aqueous medium. The luminescence is further enhanced by about four times following the addition of Y"3"+; a process known as co-luminescence. This is the first study on co-luminescence of uranyl ion in its PDA complex. Lifetime studies indicate the presence of two species having different micro-environments. Formations of both intra and inter molecular complexes are believed to be responsible for enhancement due to co-luminescence.

  17. Plasmon-enhanced luminescence of Sm complex using silver nanoparticles in Polyvinyl Alcohol

    Energy Technology Data Exchange (ETDEWEB)

    Kaur, Gagandeep; Verma, R.K.; Rai, D.K. [Laser and Spectroscopy Laboratory, Department of Physics, Banaras Hindu University, India 221005 (India); Rai, S.B., E-mail: sbrai49@yahoo.co.in [Laser and Spectroscopy Laboratory, Department of Physics, Banaras Hindu University, India 221005 (India)

    2012-07-15

    Silver (Ag) nanoparticles (NPs) were prepared by laser ablation in water with an aim to enhance the luminescence of rare earth coordinated complex in polymer host. A fixed concentration of the complex containing Samarium (Sm), Salicylic acid (Sal) and 1, 10-phenanthroline (Phen) were combined with different concentrations of silver NPs in PolyVinyl Alcohol at room temperature. Absorption spectrum and XRD patterns of the sample show that the Sm(Sal){sub 3}Phen complex is accompanied by Ag NPs. The luminescence from the complex was recorded in the presence and absence of Ag NPs using two different excitation wavelengths viz. 400 and 355 nm. Of these, 400 nm radiation falls in the surface plasmon resonance of Ag NPs. It was found that the Ag NPs led to a significant enhancement in luminescence of the complex. Surprisingly, a high concentration of Ag NPs tends to quench the luminescence. - Highlights: Black-Right-Pointing-Pointer Sm complex with Ag nanoparticles in PVA was prepared at room temperature. Black-Right-Pointing-Pointer UV-vis absorption and XRD confirms the presence of Sm complex and Ag NPs. Black-Right-Pointing-Pointer Enhancement in luminescence of complex was observed with Ag NPs. Black-Right-Pointing-Pointer Coupling between radiative transitions of Sm and SPR of NPs enhances the emission. Black-Right-Pointing-Pointer The higher concentration of Ag NPs quenches the luminescence of the complex.

  18. Synthesis and luminescence properties of hybrid organic-inorganic transparent titania thin film activated by in- situ formed lanthanide complexes

    Science.gov (United States)

    Wang, Yige; Wang, Li; Li, Huanrong; Liu, Peng; Qin, Dashan; Liu, Binyuan; Zhang, Wenjun; Deng, Ruiping; Zhang, Hongjie

    2008-03-01

    Stable transparent titania thin films were fabricated at room temperature by combining thenoyltrifluoroacetone (TTFA)-modified titanium precursors with amphiphilic triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, P123) copolymers. The obtained transparent titania thin films were systematically investigated by IR spectroscopy, PL emission and excitation spectroscopy and transmission electron microscopy. IR spectroscopy indicates that TTFA coordinates the titanium center during the process of hydrolysis and condensation. Luminescence spectroscopy confirms the in-situ formation of lanthanide complexes in the transparent titania thin film. TEM image shows that the in-situ formed lanthanide complexes were homogeneously distributed throughout the whole thin film. The quantum yield and the number of water coordinated to lanthanide metal center have been theoretically determined based on the luminescence data.

  19. Luminescent hybrid films obtained by covalent grafting of terbium complex to silica network

    International Nuclear Information System (INIS)

    Liu Fengyi; Fu Lianshe; Wang Jun; Liu Ze; Li Huanrong; Zhang Hongjie

    2002-01-01

    Luminescent hybrid thin films consisting of terbium complex covalently bonded to a silica-based network have been obtained in situ via a sol-gel approach. A new monomer, N-(4-benzoic acid-yl), N'-(propyltriethoxysilyl)urea (PABI), has been synthesized by grafting isocyanatopropyltriethoxysilane (ICPTES) to p-aminobenzoic acid and characterized by 1 H NMR, IR and MS. The monomer acts as a ligand for Tb 3+ ion and as a sol-gel precursor. Band emission from Tb 3+ ion due to an efficient ligand-to-metal energy transfer was observed by UV excitation. The decay curves of Tb 3+ in the hybrid films were measured. The energy difference between the triplet state energy of PABI and the 5 D 4 level of Tb 3+ ion falls in the exciting range to sensitize Tb 3+ ion fluorescence

  20. Structural, luminescence and biological studies of trivalent lanthanide complexes with N,N Prime -bis(2-hydroxynaphthylmethylidene)-1,3-propanediamine Schiff base ligand

    Energy Technology Data Exchange (ETDEWEB)

    Taha, Ziyad A., E-mail: tahaz33@just.edu.jo [Department of Applied Chemistry, Faculty of Arts and Sciences, Jordan University of Science and Technology, P.O. Box 3030, Irbid 22110 (Jordan); Ajlouni, Abdulaziz M. [Department of Applied Chemistry, Faculty of Arts and Sciences, Jordan University of Science and Technology, P.O. Box 3030, Irbid 22110 (Jordan); Al Momani, Waleed [Department of Allied Medical Sciences, Al Balqa Applied University (Jordan)

    2012-11-15

    New eight lanthanide metal complexes were prepared. These complexes were characterized by elemental analysis, molar conductivity measurements, spectral analysis ({sup 1}H NMR, FT-IR, UV-vis), luminescence and thermal gravimetric analysis. All Ln(III) complexes were 1:1 electrolytes as established by their molar conductivities. The microanalysis and spectroscopic analysis revealed eight-coordinated environments around lanthanide ions with two nitrate ligands behaving in a bidentate manner. The other four positions were found to be occupied with tetradentate L{sub III} ligand. Tb-L{sub III} and Sm-L{sub III} complexes exhibited characteristic luminescence emissions of the central metal ions and this was attributed to efficient energy transfer from the ligand to the metal center. The L{sub III} and Ln-L{sub III} complexes showed antibacterial activity against a number of pathogenic bacteria. - Highlights: Black-Right-Pointing-Pointer Ln(III) ion adopts an eight-coordinate geometry. Black-Right-Pointing-Pointer Luminescence spectra of Sm-L{sub III} and Tb-L{sub III} complexes display the metal centered line emission. Black-Right-Pointing-Pointer Energy transfer process from L{sub III} to Sm in Sm-L{sub III} complex is more efficient than to Tb in Tb-L{sub III} complex. Black-Right-Pointing-Pointer Ln(III) complexes may serve as models for biologically important species.

  1. Structure and luminescent investigation of new Ln(III)-TTA complexes containing N-methyl-ε-caprolactam as ligand

    Energy Technology Data Exchange (ETDEWEB)

    Borges, Alex Santos, E-mail: alexb@ifes.edu.br [Coordenadoria de Química e Biologia, IFES, Vitória, ES 29040-780 (Brazil); Caliman, Ewerton Valadares [Coordenadoria de Engenharia Metalúrgica, IFES, Vitória, ES 29040-780 (Brazil); Dutra, José Diogo L. [Departamento de Química Fundamental, UFPE, Recife, PE 50590-470 (Brazil); Da Silva, Jeferson G. [Departamento de Farmácia, UFJF, Governador Valadares, MG 35010-17 (Brazil); Araujo, Maria Helena, E-mail: maria.araujo@pq.cnpq.br [Departamento de Química, UFMG, Belo Horizonte, MG 31270-901 (Brazil)

    2016-02-15

    The synthesis and photoluminescent properties of Ln(III)-TTA complexes (Ln=Eu(III) and Sm(III) ions; TTA=3-thenoyltrifluoroacetonate) with N-methyl-ε-caprolactam (NMC) are reported. The Ln complexes were characterized by elemental analysis, complexometric titration with EDTA and infrared spectroscopy. The molecular structures of the [Eu(TTA){sub 3}(NMC)(H{sub 2}O)] and [Sm(TTA){sub 3}(NMC)(H{sub 2}O)]·H{sub 2}O compounds were determined by single crystal X-ray crystallography. In these structures, the three TTA molecules are coordinated to the metal in anionic form as bidentate ligands, while the H{sub 2}O and NMC molecules are coordinated to the metal in neutral form as monodentated ligands. The coordination polyhedron around the Ln(III) atom can be described as square antiprismatic molecular geometry. The geometry of the [Eu(TTA){sub 3}(NMC)(H{sub 2}O)] complex was optimized with the Sparkle/RM1 model for Ln(III) complexes, allowing analysis of intramolecular energy transfer processes of the Eu(III) compound. The spectroscopic properties of the 4f{sup 6} intraconfigurational transitions of the Eu(III) complex were then studied experimentally and theoretically. The low value of emission quantum efficiency of {sup 5}D{sub 0} emitting level (η) of Eu(III) ion (ca. 36%) is due to the vibrational modes of the water molecule that act as luminescence quenching. In addition, the luminescence decay curves, the experimental intensity parameters (Ω{sub λ}), lifetimes (τ), radiative (A{sub rad}) and non-radiative (A{sub nrad}) decay rates, theoretical quantum yield (q{sub cal}) were also determined and discussed. - Highlights: • New Ln-TTA complexes with lactam were obtained and their luminescence investigated. • Jablonsky diagram for the Eu(III) complex shows the main channel for the IET process. • Data confirm the potentiality of the Eu(III) complex to produce red luminescence. • LUMPAC has provided useful information on the luminescence of the Eu

  2. Study of Polymeric Luminescent Blend (PC/PMMA) Doped with Europium Complex under Gamma-Iradiation

    International Nuclear Information System (INIS)

    Parra, D. F.

    2006-01-01

    Spectroscopic properties of blends formed by bisphenol-A polycarbonate (PC) and poly(methyl methacrylate) (PMMA) doped with europium in organic complex were studied. Polymeric luminescent blends are potential materials for many applications; however, little information has been reported concerning the stability under thermal and radiation conditions. Luminescent films were synthesized from europium thenoyltrifluoroacetonate at different concentrations doped in PC/PMMA blends. Films produced of the luminescent polymer blend were irradiated in a 60 C o source. Their luminescent properties, in the solid state, as well as, the thermal oxidative resistance after gamma irradiation was investigated. These systems were characterized by elemental analysis, thermogravimetry (TGA), differential scanning calorimetry (DSC) and infrared spectroscopy (FTIR). Based on TGA data, the thermal stability of PC/PMMA:(tta)3 system is higher than the polymer blend. The DSC results indicated that those new systems are chemically stables. The emission spectra of the Eu 3 +-tta complex doped in the PC/PMMA recorded at 298 and 77 K exhibited the characteristic bands arising from the 5 D 0 →7 F J transitions (J = 0-6). The luminescence intensity decreases with increasing of precursor concentration in the doped polymer obtained by chemical reaction. This result is different from that of samples obtained by physical method in melting doping. The blend was irradiated under ionizing radiation of 60 C o source. After irradiation of the luminescent films the physical properties of luminescence, thermal and oxidative stability were evaluated.(Fapesp and Cnpq financial support)

  3. 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.

  4. Complex metal hydrides

    DEFF Research Database (Denmark)

    Ley, Morten Brix

    2014-01-01

    og batterier de to mest lovende energibærere til mobile applikationer. Komplekse metalhydrider er blevet undersøgt i vid udstrækning over de sidste tyve år, siden de gravimetrisk og volumetrisk kan indeholde store mængder brint. Derfor er metal borhydrider velegnet til faststofopbevaring af brint...

  5. Mesoporous material grafted with luminescent molecules for the design of selective metal ion chemosensor

    International Nuclear Information System (INIS)

    Zhang Huidong; Zhang Ping; Ye Kaiqi; Sun Yinghui; Jiang Shimei; Wang Yue; Pang Wenqin

    2006-01-01

    Luminescent Schiff-base groups have been successfully grafted on the surface of mesoporous material MCM-48. The grafted Schiff-base groups were employed to prepare luminescent Schiff-base-Zn complex that was covalently bound to the MCM-48 surface. These luminescent mesoporous materials were characterized with X-ray, UV-VIS and emission spectroscopic methods. Experimental results demonstrated that MCM-48 modified with functional groups exhibited novel luminescent property. The chemosensing property of modified MCM-48 sample was investigated. It was demonstrated that the fluorescence of MCM-48 solid with Schiff-base groups could be completely quenched by Cu 2+ cation and this mesoporous material was suitable for sensing Cu 2+ cation in aqueous media

  6. Luminescence and circularly polarized luminescence of macrocyclic Eu(III) and Tb(III) complexes embedded in xerogel and sol-gel SiO2 glasses

    International Nuclear Information System (INIS)

    Morita, M.; Rau, D.; Kai, T.

    2002-01-01

    Luminescence, time-resolved luminescence, circularly polarized luminescence (CPL) and decay profiles of Ln(III)(15-crownether-5) (Ln=Ce, Sm, Eu, Tb) and Tb(III)-(R),(S)-cyclen derivative complexes doped in xerogel and sol-gel silica glasses are measured at temperatures down to 10 K to characterize luminescence properties and the electronic structure in the excited states. Luminescence spectral profiles and calculation of crystal field parameters (B 0 (2) ,B 2 (2) ) in the 5 D 0 → 7 F J (J=1,2) transition give evidence of the fact that the pentagonal and planar structure of Eu(III) (15-crownether-5) does hold in xerogel and sol-gel glasses prepared at temperatures below 100 deg. C. As annealing temperatures are increased from 80 deg. C to 750 deg. C, Eu(III) complexes in sol-gel glasses are found to decompose gradually to SiO 2 :Eu 3+ . Tb(III)-(R) and (S)-cyclen derivative complexes in xerogel reveal at room temperature and 10 K sharp CPL spectra with luminescence dissymmetry factors g lum =-0.1 and 0.1, respectively. These complexes doped in sol-gel glasses represent luminescence characteristics of rare earth ions encapsulated in the nano-porous host

  7. Probes of the metal-to-ligand charge-transfer excited states in ruthenium-Am(m)ine-bipyridine complexes: the effects of NH/ND and CH/CD isotopic substitution on the 77 K luminescence.

    Science.gov (United States)

    Chen, Yuan-Jang; Xie, Puhui; Endicott, John F; Odongo, Onduru S

    2006-06-29

    The effects of ligand perdeuteration on the metal-to-ligand charge-transfer (MLCT) excited-state emission properties at 77 K are described for several [Ru(L)(4)bpy](2+) complexes in which the emission process is nominally [uIII,bpy-] --> [RuII,bpy]. The perdeuteration of the 2,2'-bipyridine (bpy) ligand is found to increase the zero-point energy differences between the ground states and MLCT excited states by amounts that vary from 0 +/- 10 to 70 +/- 10 cm(-1) depending on the ligands L. This indicates that there are some vibrational modes with smaller force constants in the excited states than in the ground states for most of these complexes. These blue shifts increase approximately as the energy difference between the excited and ground states decreases, but they are otherwise not strongly correlated with the number of bipyridine ligands in the complex. Careful comparisons of the [Ru(L)(4)(d(8)-bpy)](2+) and [Ru(L)(4)(h(8)-bpy](2+) emission spectra are used to resolve the very weak vibronic contributions of the C-H stretching modes as the composite contributions of the corresponding vibrational reorganizational energies. The largest of these, 25 +/- 10 cm(-1), is found for the complexes with L = py or bpy/2 and smaller when L = NH(3). Perdeuteration of the am(m)ine ligands (NH(3), en, or [14]aneN(4)) has no significant effect on the zero-point energy difference, and the contributions of the NH stretching vibrational modes to the emission band shape are too weak to resolve. Ligand perdeuteration does increase the excited-state lifetimes by a factor that is roughly proportional to the excited-state-ground-state energy difference, even though the CH and NH vibrational reorganizational energies are too small for nuclear tunneling involving these modes to dominate the relaxation process. It is proposed that metal-ligand skeletal vibrational modes and configurational mixing between metal-centered, bpy-ligand-centered, and MLCT excited states are important in

  8. Luminescent properties of terbium complexes with catecholamines and their application in analysis

    International Nuclear Information System (INIS)

    Kravchenko, T.B.; Bel'tyukova, S.V.; Kononenko, L.I.; Poluehktov, N.S.

    1982-01-01

    Tb complexing with a representative of catecholamines - adrenaline - is studied using the luminescence method. It is found, that the complexing takes place in alkaline medium (pH 12.0). To prevent from compound oxidation with air oxygen and to create the necessary pH in solution sodium borohydride is used. The highest luminescence intensity is achieved when the reaction occurs in aqueous-isopropanol solutions. It is established that in the complexes formed the ratio of components is the following: Tb:adrenaline=1:3. Luminescent properties of Tb complex with adrenaline are used to determine the latter. The least detectable amount of adrenaline constitutes 0.02 μg, the determination error does not exceed 5.5% [ru

  9. benzimidazole metal complexes

    Indian Academy of Sciences (India)

    aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, Université des Frères. Mentouri .... determine the quantum chemical parameters for the title ..... retical study of benzazole thioether and its zinc complex.

  10. Label free luminescence strategy for sensitive detection of ATP using aptamer-Ru(II) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Babu, Eththilu [Department of Physical Che mistry, School of Chemistry, Madurai Kamaraj University, Madurai 625021, Tamil Nadu (India); Muthu Mareeswaran, Paulpandian [Department of Physical Che mistry, School of Chemistry, Madurai Kamaraj University, Madurai 625021, Tamil Nadu (India); Department of Industrial Chemistry, Alagappa Univesity, Karaikudi 630003, Tamil Nadu (India); Ramdass, Arumugam [Department of Physical Che mistry, School of Chemistry, Madurai Kamaraj University, Madurai 625021, Tamil Nadu (India); Research Department of Chemistry, Aditanar College of Arts and Science, Tiruchendur 628216, Tamil Nadu (India); Ramesh, Pandian [UCIBIO-REQUIMTE, Departmento de Química, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica (Portugal); Rajagopal, Seenivasan, E-mail: rajagopalseenivasan@yahoo.com [Department of Physical Che mistry, School of Chemistry, Madurai Kamaraj University, Madurai 625021, Tamil Nadu (India)

    2016-07-15

    A simple and sensitive aptamer-based luminescence strategy for ATP detection is developed using Ru(II) complexes as probe molecule. It is based on the fact that Ru(II)-dppz complexes show the light switching behavior with DNA aptamers and found to show significant luminescence spectral change on the addition of ATP molecules. The binding efficiencies of aptamer with ATP, ADP and AMP are calculated and compared. The structural change of aptamer is also studied using circular dichroism (CD) spectral techniques. Moreover, the binding nature of aptamer with ATP, ADP and AMP is demonstrated by computational techniques. The proposed strategy was successfully applied to the detection of ATP.

  11. Label free luminescence strategy for sensitive detection of ATP using aptamer-Ru(II) complexes

    International Nuclear Information System (INIS)

    Babu, Eththilu; Muthu Mareeswaran, Paulpandian; Ramdass, Arumugam; Ramesh, Pandian; Rajagopal, Seenivasan

    2016-01-01

    A simple and sensitive aptamer-based luminescence strategy for ATP detection is developed using Ru(II) complexes as probe molecule. It is based on the fact that Ru(II)-dppz complexes show the light switching behavior with DNA aptamers and found to show significant luminescence spectral change on the addition of ATP molecules. The binding efficiencies of aptamer with ATP, ADP and AMP are calculated and compared. The structural change of aptamer is also studied using circular dichroism (CD) spectral techniques. Moreover, the binding nature of aptamer with ATP, ADP and AMP is demonstrated by computational techniques. The proposed strategy was successfully applied to the detection of ATP.

  12. Novel Luminescent Probe Based on a Terbium(III) Complex for Hemoglobin Determination

    Science.gov (United States)

    Yegorova, A. V.; Leonenko, I. I.; Aleksandrova, D. I.; Scrypynets, Yu. V.; Antonovich, V. P.; Ukrainets, I. V.

    2014-09-01

    We have studied the spectral luminescent properties of Tb(III) and Eu(III) complexes with a number of novel derivatives of oxoquinoline-3-carboxylic acid amides (L1-L5 ). We have observed quenching of the luminescence of 1:1 Tb(III)-L1-5 complexes by hemoglobin (Hb), which is explained by resonance energy transfer of electronic excitation from the donor (Tb(III)-L1-5 ) to the acceptor (Hb). Using the novel luminescent probe Tb(III)-L1, we have developed a method for determining Hb in human blood. The calibration Stern-Volmer plot is linear in the Hb concentration range 0.6-36.0 μg/mL, detection limit 0.2 μg/mL (3·10-9 mol/L).

  13. Synthesis and luminescence properties of europium and terbium complexes with pyridine- or bipyridine-linked oligothiophene ligand

    International Nuclear Information System (INIS)

    Liu Ping; Huang Mingsheng; Pan Wanzhang; Zhang Yamin; Hu Jianhua; Deng Wenji

    2006-01-01

    With an aim to develop novel luminescence materials, europium and terbium complexes of 2,5-(2-thiophene)-pyridine (TPY) and 5,5'-bis(5-(2,2'-bithiophene))-2,2'-bipyridine (B2TBPY) were synthesized, and their luminescence properties studied. The complexes exhibit ligand-sensitized emission, which is typical of Eu(III) and Tb(III) ions

  14. Transition Metal Complexes and Catalysis

    Indian Academy of Sciences (India)

    approaches towards the study of bonding in transition metal complexes. Despite .... industrial scale reactions for the production of organic compounds using transition ..... It has found several applications as an engineering thermoplastic. .... and processes of interest to the company, that is, applied research. It is this very ...

  15. Sensitive luminescent determination of DNA using the terbium(III)-difloxacin complex

    International Nuclear Information System (INIS)

    Yegorova, Alla V.; Scripinets, Yulia V.; Duerkop, Axel; Karasyov, Alexander A.; Antonovich, Valery P.; Wolfbeis, Otto S.

    2007-01-01

    The interaction of the terbium-difloxacin complex (Tb-DFX) with DNA has been examined by using UV-vis absorption and luminescence spectroscopy. The Tb-DFX complex shows an up to 85-fold enhancement of luminescence intensity upon titration with DNA. The long decay times allow additional detection schemes like time-resolved measurements in microplate readers to enhance sensitivity by off-gating short-lived background luminescence. Optimal conditions are found at equimolar concentrations of Tb 3+ and DFX (0.1 or 1 μM) at pH 7.4. Under these conditions, the luminescence intensity is linearly dependent on the concentration of ds-DNAs and ss-DNA between 1-1500 ng mL -1 and 4.5-270 ng mL -1 , respectively. The detection limit is 0.5 ng mL -1 for ds-DNAs and 2 ng mL -1 for ss-DNA. The mechanism for the luminescence enhancement was also studied

  16. Metal complexes with 5-aminotetrazole

    International Nuclear Information System (INIS)

    Lavrenova, L.G.; Larionov, S.V.; Grankina, Z.A.; Ikorskij, V.N.

    1983-01-01

    Nitrate and chloride complexes of Co(2), Ni(2), Cu(2), Cd(2), Hg(2), Pb(2) with 5 aminotetrazole (ATE) and compoUnds Zn(ATE') 2 and Cd(ATEE') 2 , where ATE' is a 5 aminotetrazole ano /nion. On the base of spectroscopic data (spectrophotometry, IR- spectra, EPR and magnetic measurements assumptions on M(2) coordination in complexes are made. Most probably ATE is a bridge ligand which is joined by two nitrogen atoms to various M(2) ions. In Co(2), Ni(2) and Cu(ATE) 3 -Cl 2 compounds the metal has a distorted actahedral coordination and forms MN 6 unit, which suggests the interaction of metal ions with ATE nitrogen atoms along the Z-axis. In the Cu(ATE) 2 (NO 3 ) 2 octahedral complex the CuN 4 O 2 coordination unit is realized at the expense of participation of nitratogroups in coordination

  17. Luminescence and Magnetic Properties of Tb(III) Complexes with TETA and Synergistic Effect by 1,10-Phenanthroline

    International Nuclear Information System (INIS)

    Kang, Jung Youl; Shin, Su jeong; Kim, Jae Kwan; Park, Kyoung Chan

    2016-01-01

    Two Tb(III) complexes, [Tb(TETA)]− and [Tb(TETA)(phen)]− (TETA = 1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetraacetate and phen=1,10-phenanthroline), were synthesized and their luminescence ("5D_4 → "7F_=_0_-_6 transitions) and magnetic properties were examined. The photoluminescence (PL) quantum yield of [Tb(TETA)(phen)]− (Q = 0.47) was significantly higher than that of [Tb(TETA)]− (Q = 0.006). The dramatic increase (78 x) in green luminescence was attributed to intramolecular energy transfer from phen to Tb(III). The energy transfer rate according to Dexter theory was found to be approximately 1011s−1. The temperature dependence of the molar susceptibilities confirmed that the two complexes behave as paramagnets obeying the Curie–Weiss law. In addition, the field-dependent magnetization of the two complexes measured in the −70 to + 70 kOe range at T=1.8K fitted well with the Brillouin function with the following values: g _e_f_f=1.5, μ B =9.27×10−21 emu, and J=6. These results provide new insights into the development of lanthanide metal complexes with tetraaza

  18. Luminescence and Magnetic Properties of Tb(III) Complexes with TETA and Synergistic Effect by 1,10-Phenanthroline

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Jung Youl; Shin, Su jeong; Kim, Jae Kwan; Park, Kyoung Chan [Hanbat National University, Daejeon (Korea, Republic of)

    2016-09-15

    Two Tb(III) complexes, [Tb(TETA)]− and [Tb(TETA)(phen)]− (TETA = 1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetraacetate and phen=1,10-phenanthroline), were synthesized and their luminescence ({sup 5}D{sub 4} → {sup 7}F{sub =0-6} transitions) and magnetic properties were examined. The photoluminescence (PL) quantum yield of [Tb(TETA)(phen)]− (Q = 0.47) was significantly higher than that of [Tb(TETA)]− (Q = 0.006). The dramatic increase (78 x) in green luminescence was attributed to intramolecular energy transfer from phen to Tb(III). The energy transfer rate according to Dexter theory was found to be approximately 1011s−1. The temperature dependence of the molar susceptibilities confirmed that the two complexes behave as paramagnets obeying the Curie–Weiss law. In addition, the field-dependent magnetization of the two complexes measured in the −70 to + 70 kOe range at T=1.8K fitted well with the Brillouin function with the following values: g {sub eff}=1.5, μ B =9.27×10−21 emu, and J=6. These results provide new insights into the development of lanthanide metal complexes with tetraaza.

  19. Amino-Functionalized Luminescent Metal-Organic Framework Test Paper for Rapid and Selective Sensing of SO2 Gas and Its Derivatives by Luminescence Turn-On Effect.

    Science.gov (United States)

    Wang, Meng; Guo, Lin; Cao, Dapeng

    2018-03-06

    Rapid and selective sensing of sulfur dioxide (SO 2 ) gas has attracted more and more attention because SO 2 not only causes environmental pollution but also severely affects the health of human beings. Here we report an amino-functionalized luminescent metal-organic framework (MOF) material (i.e., MOF-5-NH 2 ) and further investigate its sensing property for SO 2 gas and its derivatives as a luminescent probe. The results indicate that the MOF-5-NH 2 probe can selectively and sensitively sense SO 2 derivatives (i.e., SO 3 2- ) in real time by a luminescence turn-on effect with a lower detection limit of 0.168 ppm and a response time of less than 15 s. Importantly, the luminescence turn-on phenomenon can be observed by the naked eye. We also assembled MOF-5-NH 2 into a test paper to achieve the aim of portable detection, and the lower-limit concentration of the test paper for sensing SO 2 in real time was found to be about 0.05 ppm. Moreover, MOF-5-NH 2 also shows good anti-interference ability, strong luminescence stability, and reusability, which means that this material is an excellent sensing candidate. The amino functionalization may also provide a modification strategy to design luminescent sensors for other atmospheric pollutants.

  20. Sensitization effects of supramolecular assemblies on the luminescence of terbium-ion prulifloxacin complexes

    Energy Technology Data Exchange (ETDEWEB)

    Wang Hong; Yi Chongyue; Li Xue; Fang Fang [School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Yang Yajiang, E-mail: yjyang@mail.hust.edu.c [School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2011-04-15

    Luminescence enhancement of terbium-ion prulifloxacin complexes (Tb(III)-PUFX) in supramolecular hydrogels formed by assembly of 1,3:2,4-di-O-benzylidene-D-sorbitol (DBS) was investigated by steady-state fluorescence, varying temperature fluorescence and time-resolved fluorescence. The luminescence images show that Tb(III)-PUFX were dispersed in the DBS gels. The luminescence intensity of Tb(III)-PUFX in the DBS gels was significantly increased in comparison with that in corresponding aqueous solutions. The varying temperature fluorescent spectra show that the luminescence intensity of Tb(III)-PUFX decreased with an increase in the temperature. This implies that the luminescence enhancement of Tb(III)-PUFX is related to the dissociation and the formation of the DBS assemblies. Time-resolved fluorescence measurements show slower rotational motion in DBS gels in comparison with that in the corresponding aqueous solutions. This may be ascribed to a unique microstructure of three-dimensional network formed by DBC aggregates, resulting in deactivation of the nonradiative relaxation. The images of field emission scanning electron microscopy and polarized optical microscopy indicate that the morphology of the DBS assemblies was not influenced upon addition of Tb(III)-PUFX to the DBS gels.

  1. The influence of carboxilate, phosphinate and seleninate groups on luminescent properties of lanthanides complexes

    International Nuclear Information System (INIS)

    Monteiro, Jorge H.S.K.; Formiga, André L.B.; Sigoli, Fernando A.

    2014-01-01

    The lanthanides(III) complexes [Ln(bza) 3 (H 2 O) n ]·mH 2 O, [Ln(ppa) 3 (H 2 O) n ]·mH 2 O and [Ln(abse) 3 (H 2 O) n ]·mH 2 O where Ln=Eu 3+ , Gd 3+ or Tb 3+ were synthesized using sodium benzoate (Nabza), sodium phenylseleninate (Naabse) and sodium phenylphosphinate (Nappa) in order to verify the influence on coordination modes and the luminescence parameters when the carbon is exchanged by phosphorus or selenium in those ligands. The complexes' stoichiometries were determined by lanthanide(III) titration, microanalysis and TGA. The coordination modes were determined as bidentate bridging and chelate by the FT-IR. The triplet state energies of the ligands were obtained by two different approaches giving a difference of about ∼2000 cm −1 between them. The [Eu(abse) 3 (H 2 O)] complex shows the higher degree of covalence which was verified by the centroid of 5 D 0 → 7 F 0 transition (17,248 cm −1 ). On the other hand the [Ln(abse) 3 (H 2 O) n ]·mH 2 O complexes have an inefficient antenna effect verified by the low values of absolute emission quantum yields. The [Ln(ppa) 3 (H 2 O) n ]·mH 2 O complexes have higher emission decay lifetime values among the complexes which is a result of the ability of this ligand to form coordination polymers avoiding water molecules in the first coordination sphere. The [Eu(ppa) 3 ] complex has the highest point symmetry around europium(III) among the synthesized complexes, followed by the [Eu(bza) 3 (H 2 O) 2 ]·3/2(H 2 O) and [Eu(abse) 3 (H 2 O)] complexes where europium(III) show similar point symmetries. As one may expect, the triplet state energy position would change the transfer and/or back energy transfer rates from ligand to metal. The calculation of these rates show that the back energy transfer rates are more affected than the transfer ones by changing the triplet state energy in the range of ∼2000 cm −1 . The changes in the energy transfer rates from triplet state to europium(III) levels are not

  2. Controlling Second Coordination Sphere Effects in Luminescent Ruthenium Complexes by Means of External Pressure.

    Science.gov (United States)

    Pannwitz, Andrea; Poirier, Stéphanie; Bélanger-Desmarais, Nicolas; Prescimone, Alessandro; Wenger, Oliver S; Reber, Christian

    2018-06-04

    Two luminescent heteroleptic Ru II complexes with a 2,2'-biimidazole (biimH 2 ) ligand form doubly hydrogen-bonded salt bridges to 4-sulfobenzoate anions in single crystals. The structure of one of these cation-anion adducts shows that the biimH 2 ligand is deprotonated. Its 3 MLCT luminescence band does not shift significantly under the influence of an external hydrostatic pressure, a behavior typical for these electronic transitions. In contrast, hydrostatic pressure on the other crystalline cation-anion adduct induces a shift of proton density from the peripheral N-H groups of biimH 2 towards benzoate, leading to a pronounced redshift of the 3 MLCT luminescence band. Such a significant and pressure-tunable influence from an interaction in the second coordination sphere is unprecedented in artificial small-molecule-based systems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Synthesis and luminescence properties of hybrid organic-inorganic transparent titania thin film activated by in-situ formed lanthanide complexes

    International Nuclear Information System (INIS)

    Wang Yige; Wang Li; Li Huanrong; Liu Peng; Qin Dashan; Liu Binyuan; Zhang Wenjun; Deng Ruiping; Zhang Hongjie

    2008-01-01

    Stable transparent titania thin films were fabricated at room temperature by combining thenoyltrifluoroacetone (TTFA)-modified titanium precursors with amphiphilic triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, P123) copolymers. The obtained transparent titania thin films were systematically investigated by IR spectroscopy, PL emission and excitation spectroscopy and transmission electron microscopy. IR spectroscopy indicates that TTFA coordinates the titanium center during the process of hydrolysis and condensation. Luminescence spectroscopy confirms the in-situ formation of lanthanide complexes in the transparent titania thin film. TEM image shows that the in-situ formed lanthanide complexes were homogeneously distributed throughout the whole thin film. The quantum yield and the number of water coordinated to lanthanide metal center have been theoretically determined based on the luminescence data. - Graphical abstract: Novel stable luminescent organic-inorganic hybrid titania thin film with high transparency activated by in-situ formed lanthanide complexes have been obtained at room temperature via a simple one-pot synthesis approach by using TTFA-modified titanium precursor with amphiphilic triblock copolymer P123. The obtained hybrid thin film displays bright red (or green), near-monochromatic luminescence due to the in-situ formed lanthanide complex

  4. Ratiometric Time-Gated Luminescence Probe for Nitric Oxide Based on an Apoferritin-Assembled Lanthanide Complex-Rhodamine Luminescence Resonance Energy Transfer System.

    Science.gov (United States)

    Tian, Lu; Dai, Zhichao; Liu, Xiangli; Song, Bo; Ye, Zhiqiang; Yuan, Jingli

    2015-11-03

    Using apoferritin (AFt) as a carrier, a novel ratiometric luminescence probe based on luminescence resonance energy transfer (LRET) between a Tb(3+) complex (PTTA-Tb(3+)) and a rhodamine derivative (Rh-NO), PTTA-Tb(3+)@AFt-Rh-NO, has been designed and prepared for the specific recognition and time-gated luminescence detection of nitric oxide (NO) in living samples. In this LRET probe, PTTA-Tb(3+) encapsulated in the core of AFt is the energy donor, and Rh-NO, a NO-responsive rhodamine derivative, bound on the surface of AFt is the energy acceptor. The probe only emits strong Tb(3+) luminescence because the emission of rhodamine is switched off in the absence of NO. Upon reaction with NO, accompanied by the turn-on of rhodamine emission, the LRET from Tb(3+) complex to rhodamine occurs, which results in the remarkable increase and decrease of the long-lived emissions of rhodamine and PTTA-Tb(3+), respectively. After the reaction, the intensity ratio of rhodamine emission to Tb(3+) emission, I565/I539, is ∼24.5-fold increased, and the dose-dependent enhancement of I565/I539 shows a good linearity in a wide concentration range of NO. This unique luminescence response allowed PTTA-Tb(3+)@AFt-Rh-NO to be conveniently used as a ratiometric probe for the time-gated luminescence detection of NO with I565/I539 as a signal. Taking advantages of high specificity and sensitivity of the probe as well as its good water-solubility, biocompatibility, and cell membrane permeability, PTTA-Tb(3+)@AFt-Rh-NO was successfully used for the luminescent imaging of NO in living cells and Daphnia magna. The results demonstrated the efficacy of the probe and highlighted it's advantages for the ratiometric time-gated luminescence bioimaging application.

  5. Design, synthesis and characterization of a highly luminescent Eu-complex monomer featuring thenoyltrifluoroacetone and 5-acryloxyethoxymethyl-8-hydroxyquinoline

    Energy Technology Data Exchange (ETDEWEB)

    Xu Cunjin [State Key Laboratory of Chemical Engineering, Department of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027 (China); College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036 (China); Li Bogeng, E-mail: bgli@zju.edu.cn [State Key Laboratory of Chemical Engineering, Department of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027 (China); Wan Jintao; Bu Zhiyang [State Key Laboratory of Chemical Engineering, Department of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027 (China)

    2011-08-15

    A multi-functional ligand, 5-acryloxyethoxymethyl-8-hydroxyquinoline (Hamq), was synthesized, which contained a polymerizable C=C double bond for the copolymerization with other vinyl monomers and acted as photon antenna able to transfer energy to Eu{sup 3+} ions effectively. The triplet state energy of Hamq was determined to be 22,370 cm{sup -1} via the phosphorescence spectra of Hamq and its gadolinium complex. The title complex monomer Eu(tta){sub 2}(amq) was prepared by coordination reaction of Hamq with europium isopropoxide and 2-thenoyltrifluoroacetone (Htta) in dry organic solvents under argon atmosphere and characterized by elemental analysis and IR spectrum. The photophysical properties of the complex were studied in detail with UV-vis, luminescence spectra, luminescence lifetime and quantum yield. The complex exhibited nearly monochromatic red emission at 612 nm, a remarkable luminescence quantum yield at room temperature (30.6%) upon ligand excitation and a long {sup 5}D{sub 0} lifetime (389 {mu}s), which indicated that the ligand Hamq could sensitize the luminescence of Eu(III) ion efficiently in Eu(tta){sub 2}(amq), resulting in a strong luminescence of its copolymer poly[MMA-co-Eu(TTA){sub 2}(amq)] under UV excitation. The excellent luminescence properties of the complex made it not only a promising light-conversion molecular device but also an excellent luminescent monomer. - Highlights: >iWe designed and synthesized a highly luminescent Eu-complex monomer. > Quantum yield and lifetime of the complex are 30.6% and 389 {mu}s, respectively. > Excellent luminescence of the complex made it an excellent luminescent monomer.

  6. Luminescent hybrid materials functionalized with lanthanide ethylenodiaminotetraacetate complexes containing β-diketonate as antenna ligands

    Energy Technology Data Exchange (ETDEWEB)

    Aguiar, Franklin P.; Costa, Israel F.; Espínola, José Geraldo P.; Faustino, Wagner M.; Moura, Jandeilson L. [Departamento de Química-Universidade Federal da Paraíba, 58051-970 João Pessoa, PB (Brazil); Brito, Hermi F.; Paolini, Tiago B. [Departamento de Química Fundamental-Instituto de Química da Universidade de São Paulo, 05508-900 São Paulo, SP (Brazil); Felinto, Maria Cláudia F.C. [Instituto de Pesquisas energéticas e Nucleares-IPEN, 05508-900 São Paulo, SP (Brazil); Teotonio, Ercules E.S., E-mail: teotonioees@quimica.ufpb.br [Departamento de Química-Universidade Federal da Paraíba, 58051-970 João Pessoa, PB (Brazil)

    2016-02-15

    Three organic–inorganic hybrid materials based on silica gel functionalized with (3-aminopropyl)trimethoxysilane (APTS), [3-(2-aminoetilamino)-propil]-trimetoxissilano (DAPTS) and 3-[2-(2-aminoetilamino)etilamino] propiltrimetoxysilane (TAPTS) and subsequently modified with EDTA derivative were prepared by nonhomogeneous route and were then characterized. The resulting materials named SilXN-EDTA (X=1 for APTS, 2 for DAPTS and 3 for TAPTS) were used to obtain new lanthanide Ln{sup 3+}-β-diketonate (Ln{sup 3+}=Eu{sup 3+}, Gd{sup 3+} and Tb{sup 3+}) complexes covalently linked to the functionalized silica gel surfaces (named SilXN-EDTALn-dik, dik=tta, dbm, bzac and acac). The photophysical properties of the new luminescent materials were investigated and compared with those with similar system presenting water molecules coordinated to the lanthanide ions, SilXN-EDTALn-H{sub 2}O. The SilXN-EDTAEu-dik and SilXN-EDTATb-dik systems displayed characteristic red and green luminescence when excited by UV radiation. Furthermore, the quantitative results showed that the emission quantum efficiency (η), experimental intensity parameters Ω{sub 2} and Ω{sub 4}, and Einstein's emission coefficient (A{sub 0J}) of the SilXN-EDTAEu-dik materials were largely dependent on the ligands. Based on the luminescence data, the most efficient intramolecular energy transfer processes were found to the SilXN-EDTAEu-dik (dik: tta and dbm) and SilXN-EDTATb-acac materials, which exhibited more pure emission colors. These materials are promising red and green phosphors, respectively. - Highlights: • New highly luminescent hybrid materials containing lanthanide-EDTA complexes. • The effect of three silylanting agent on the adsorption and luminescent properties has been studied. • The luminescence sensitizing by different β-diketonate ligands have been investigated.

  7. 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.

  8. A ruthenium(II) complex as turn-on Cu(II) luminescent sensor based on oxidative cyclization mechanism and its application in vivo

    Science.gov (United States)

    Zhang, Yunfei; Liu, Zonglun; Yang, Kui; Zhang, Yi; Xu, Yongqian; Li, Hongjuan; Wang, Chaoxia; Lu, Aiping; Sun, Shiguo

    2015-02-01

    Copper ions play a vital role in a variety of fundamental physiological processes not only in human beings and plants, but also for extensive insects and microorganisms. In this paper, a novel water-soluble ruthenium(II) complex as a turn-on copper(II) ions luminescent sensor based on o-(phenylazo)aniline was designed and synthesized. The azo group would undergo a specific oxidative cyclization reaction with copper(II) ions and turn into high luminescent benzotriazole, triggering significant luminescent increasements which were linear to the concentrations of copper(II) ions. The sensor distinguished by its high sensitivity (over 80-fold luminescent switch-on response), good selectivity (the changes of the emission intensity in the presence of other metal ions or amino acids were negligible) and low detection limit (4.42 nM) in water. Moreover, the copper(II) luminescent sensor exhibited good photostability under light irradiation. Furthermore, the applicability of the proposed sensor in biological samples assay was also studied and imaged copper(II) ions in living pea aphids successfully.

  9. Crystal structure and luminescence of complexes of Eu(III) and Tb(III) with furan-2,5-dicarboxylate

    NARCIS (Netherlands)

    Akerboom, S.; Fu, W.T.; Lutz, M.; Bouwman, E.

    2012-01-01

    Four new Ln(III) complexes (Ln = Eu, Tb) with furan-2,5-dicarboxylic acid (H2FDA) as a ligand have been synthesized and characterized in the solid state. Luminescence studies indicate that the compounds exhibit line-like luminescence characteristic of the lanthanide centre upon excitation in the

  10. Optimization of Temperature Sensing with Polymer-Embedded Luminescent Ru(II Complexes

    Directory of Open Access Journals (Sweden)

    Nelia Bustamante

    2018-02-01

    Full Text Available Temperature is a key parameter in many fields and luminescence-based temperature sensing is a solution for those applications in which traditional (mechanical, electrical, or IR-based thermometers struggle. Amongst the indicator dyes for luminescence thermometry, Ru(II polyazaheteroaromatic complexes are an appealing option to profit from the widespread commercial technologies for oxygen optosensing based on them. Six ruthenium dyes have been studied, engineering their structure for both photostability and highest temperature sensitivity of their luminescence. The most apt Ru(II complex turned out to be bis(1,10-phenanthroline(4-chloro-1,10-phenanthrolineruthenium(II, due to the combination of two strong-field chelating ligands (phen and a substituent with electron withdrawing effect on a conjugated position of the third ligand (4-Clphen. In order to produce functional sensors, the dye has been best embedded into poly(ethyl cyanoacrylate, due to its low permeability to O2, high temperature sensitivity of the indicator dye incorporated into this polymer, ease of fabrication, and excellent optical quality. Thermosensitive elements have been fabricated thereof as optical fiber tips for macroscopic applications (water courses monitoring and thin spots for microscopic uses (temperature measurements in cell culture-on-a-chip. With such dye/polymer combination, temperature sensing based on luminescence lifetime measurements allows 0.05 °C resolution with linear response in the range of interest (0–40 °C.

  11. Luminescently tagged 2,2'-bipyridine complex of FeII: synthesis and photophysical studies of 4-[N-(2-anthryl)carbamoyl]-4'-methyl-2,2'-bipyridine.

    Science.gov (United States)

    Zigler, David F; Elvington, Mark C; Heinecke, Julie; Brewer, Karen J

    2006-08-21

    The anthracene lumiphore was linked to the chelating ligand 2,2'-bipyridine, forming 4-[N-(2-anthryl)carbamoyl]-4'-methyl-2,2'-bipyridine (bpyAnth). Coupling through an amide linkage provides some electronic isolation of the anthracene lumiphore. Electrochemistry suggested little change of the anthracene oxidation whether free (1.35 V) linked to 2,2'-bipyridine as bpyAnth (1.30 V) or appended to Fe(II) (1.29 V). The bpyAnth ligand retained the structured luminescence characteristic of anthracene at 375, 400, 419, and 441 nm. This anthracene emission persists even when bpyAnth is complexed to an Fe(II) center. The complex [Fe(bpyAnth)3]2+ is emissive, in marked contrast to typical polyazine iron(II) complexes. This bpyAnth ligand serves as a luminescently tagged analogue of 2,2'-bipyridine, useful for coordination to a variety of metals.

  12. Luminescent platinum(II) complexes with functionalized N-heterocyclic carbene or diphosphine selectively probe mismatched and abasic DNA

    OpenAIRE

    Che, CM; Chen, T; To, WP; Zou, T; FUNG, SK; Lok, CN; YANG, C; Cao, B

    2016-01-01

    The selective targeting of mismatched DNA overexpressed in cancer cells is an appealing strategy in designing cancer diagnosis and therapy protocols. Few luminescent probes that specifically detect intracellular mismatched DNA have been reported. Here we used Pt(II) complexes with luminescence sensitive to subtle changes in the local environment and report several Pt(II) complexes that selectively bind to and identify DNA mismatches. We evaluated the complexes' DNA-binding characteristics by ...

  13. Luminescent Lanthanide Metal Organic Frameworks for cis-Selective Isoprene Polymerization Catalysis

    Directory of Open Access Journals (Sweden)

    Samantha Russell

    2015-11-01

    Full Text Available In this study, we are combining two areas of chemistry; solid-state coordination polymers (or Metal-Organic Framework—MOF and polymerization catalysis. MOF compounds combining two sets of different lanthanide elements (Nd3+, Eu3+/Tb3+ were used for that purpose: the use of neodymium was required due to its well-known catalytic properties in dienes polymerization. A second lanthanide, europium or terbium, was included in the MOF structure with the aim to provide luminescent properties. Several lanthanides-based MOF meeting these criteria were prepared according to different approaches, and they were further used as catalysts for the polymerization of isoprene. Stereoregular cis-polyisoprene was received, which in some cases exhibited luminescent properties in the UV-visible range.

  14. Mitochondria Targetable Time-Gated Luminescence Probe for Singlet Oxygen Based on a β-Diketonate-Europium Complex.

    Science.gov (United States)

    Sun, Jingyan; Song, Bo; Ye, Zhiqiang; Yuan, Jingli

    2015-12-21

    Singlet oxygen ((1)O2) plays a key role in the photodynamic therapy (PDT) technique of neoplastic diseases. In this work, by using a 9,10-dimethyl-2-anthryl-containing β-diketone, 1,1,1,2,2-pentafluoro-5-(9',10'-dimethyl-2'-anthryl)-3,5-pentanedione (Hpfdap), as a (1)O2-recognition ligand, a novel β-diketonate-europium(III) complex that can act as a luminescence probe for (1)O2, [Eu(pfdap)3(tpy)] (tpy = 2,2',2″-terpyridine), has been designed and synthesized for the time-gated luminescence detection of (1)O2 in living cells. The complex is weakly luminescent due to the quenching effect of 9,10-dimethyl-2-anthryl groups. After reaction with (1)O2, accompanied by the formation of endoperoxides of 9,10-dimethyl-2-anthryl groups, the luminescence quenching disappears, so that the long-lived luminescence of the europium(III) complex is switched on. The complex showed highly selective luminescence response to (1)O2 with a remarkable luminescence enhancement. Combined with the time-gated luminescence imaging technique, the complex was successfully used as a luminescent probe for the monitoring of the time-dependent generation of (1)O2 in 5-aminolevulinic acid (a PDT drug) loaded HepG2 cells during the photodynamic process. In addition, by coloading the complex and a mitochondrial indicator, Mito-Tracker Green, into HepG2 cells, the specific localization of [Eu(pfdap)3(tpy)] molecules in mitochondria of HepG2 cells was demonstrated by confocal fluorescence imaging measurements.

  15. 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.

  16. Synthesis of mixed ligand europium complexes: Verification of predicted luminescence intensification

    International Nuclear Information System (INIS)

    Lima, Nathalia B.D.; Silva, Anderson I.S.; Gonçalves, Simone M.C.; Simas, Alfredo M.

    2016-01-01

    Mixed ligand europium complexes are predicted to be more luminescent than what would be expected from their corresponding repeating ligand compounds according to a conjecture recently advanced by our research group; a conjecture that has already been validated for strongly luminescent europium complexes. In this article, we seek to further verify the validity of this conjecture for complexes which are much more symmetric, and which thus display lower levels of luminescence. Accordingly, we synthesized complexes Eu(DBM) 3 (L) 2 , and all novel mixed ligand combinations Eu(DBM) 3 (L,L') with L and L' equal to DBSO, PTSO, and TPPO. The syntheses were carried out via displacement reactions from the starting complex Eu(DBM) 3 (H 2 O) 2 , passing through the intermediates Eu(DBM) 3 (L) 2 and finally, by displacement of L by L', arriving at Eu(DBM) 3 (L,L'). The ligands L obey the following order of displacement TPPO>PTSO>DBSO>H 2 O, which had been previously described by our group. In the present article, we further show that this displacement order could have been predicted by Sparkle/RM1 thermochemical calculations. Subsequently, we determined the radiative decay rates, A rad , for all six compounds by photophysical measurements. As expected, results show that the measured A rad values for all novel mixed ligand complexes are larger than the average of the A rad values for the corresponding repeating ligand coordination compounds. In conclusion, the present article does broaden the scope of our conjecture, which enunciates that an increase in the diversity of ligands around the europium ion tends to intensify the luminescence. - Highlights: • Mixed ligand europium complexes are predicted to be more luminescent than repeating ligand ones. • Radiative decay rates increase with structural coordination asymmetry. • The non-ionic ligands displacement order in substitution reactions is TPPO>PTSO>DBSO>H 2 O. • Sparkle/RM1 correctly predicts the

  17. Luminescent chiral ionic Ir(III) complexes: Synthesis and photophysical properties

    Energy Technology Data Exchange (ETDEWEB)

    Ricciardi, Loredana, E-mail: loredana.ricciardi@unical.it [CNR NANOTEC-Istituto di Nanotecnologia U.O.S. Cosenza, 87036 Arcavacata di Rende (CS) (Italy); La Deda, Massimo; Ionescu, Andreea; Godbert, Nicolas; Aiello, Iolinda; Ghedini, Mauro [MAT-INLAB (Laboratorio di Materiali Molecolari Inorganici), LASCAMM and CR INSTM, Unità INSTM della Calabria, Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, 87036 Arcavacata di Rende (CS) (Italy); Fusè, Marco, E-mail: marco.fuse@unimi.it [Dipartimento di Scienze Farmaceutiche, Università di Milano, Via Golgi 19, 20133 Milano (Italy); Rimoldi, Isabella; Cesarotti, Edoardo [Dipartimento di Scienze Farmaceutiche, Università di Milano, Via Golgi 19, 20133 Milano (Italy)

    2016-02-15

    Three homologous series of luminescent octahedral ionic Ir(III) complexes (1–12) with a dual stereogenic center of general formula {sup Δ,Λ} {sup (R,S)}[(ppy){sub 2}Ir(R-campy)]X, where ppy=2-phenylpyridine, R-campy=2-methyl-5,6,7,8-tetrahydroquinolin-8-amine (Me-campy) or 8-amino-5,6,7,8-tetrahydroquinolines (H-campy) and as counterions X{sup −}=Cl{sup −} or CH{sub 3}COO{sup −} have been synthesized and characterized. The NMR characterization of each complex highlighted the diastereoisomeric purity and the absolute configuration has been confirmed by Electronic Circular Dichroism spectroscopy. The absorption and the luminescence properties of the compounds in solution and in solid state have been investigated by UV–vis, steady-state emission and time-correlated single-photon counting spectroscopy. The obtained results from the 12 compounds highlight the difficult to correlate photophysical properties in solution to the stereochemistry, while excited states decay studies of the solid state samples indicate a correlation between photophysics and packing mode which is affected by the different stereochemistry. - Highlights: • Luminescent chiral ionic Ir(III) complexes have been synthesized and characterized. • Presence in the same structure of two stereogenic centers. • Use of camphorsulfonate as resolving anion to obtain enantiomerically pure samples. • Stereoisomers produce aggregates with different emitting properties. • Lifetimes from solid samples show the presence of AIPE.

  18. Synthesis and spectroscopic behavior of highly luminescent trinuclear europium complexes with tris-β-diketone ligand

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Dunjia, E-mail: dunjiawang@163.com; Pi, Yan; Liu, Hua; Wei, Xianhong; Hu, Yanjun; Zheng, Jing

    2014-11-15

    Highlights: • Synthesis of the tris-β-diketone ligand and its trinuclear europium complexes. • Photoluminescence behavior of trinuclear europium complexes. • Analysis of the Judd–Ofelt intensity parameters (Ω{sub t}), lifetime (τ) and quantum yield (η). - Abstract: A new tris-β-diketone ligand, 2-[4,6-bis-(1-benzoyl-2-oxo-2-phenyl-ethyl)-[1,3,5]triazin-2-yl] -1,3-diphenyl-propane-1,3-dione (H{sub 3}L), and its trinuclear europium complexes, Eu{sub 3}(DBM){sub 6}L (C1), Eu{sub 3}(DBM){sub 6}(Bipy){sub 3}L (C2) and Eu{sub 3}(DBM){sub 6}(Phen){sub 3}L (C3) were synthesized and their spectroscopic behaviors were studied by FT-IR, {sup 1}H NMR, UV–vis and photoluminescence spectroscopic techniques. These europium complexes exhibited the characteristic emission bands that arise from the {sup 5}D{sub 0} → {sup 7}F{sub J} (J = 0–4) transitions of the europium ion in solid state. The Ω{sub 2} and Ω{sub 4} intensity parameters, lifetime (τ) and luminescence quantum yield (η) were calculated according to the emission spectra and luminescence decay curves in solid state. The results indicated that these trinuclear europium complexes displayed a longer lifetime (τ) and higher luminescence quantum efficiency (η), especially complexes C2 (τ = 0.820 ms, η = 46.5%) and C3 (τ = 0.804 ms, η = 47.4%), which due to the effect of two additional europium ion lumophors and the introduction of the third ligands, Bipy or Phen in trinuclear complexes. Their Ω{sub 2} values demonstrated that the europium ion in these complexes is in a highly polarizable chemical environment.

  19. Rare earth(III) complexes for the development of new magnetic and luminescent probes

    International Nuclear Information System (INIS)

    Nonat, A.

    2007-10-01

    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)

  20. Binding of chlorfenvinphos and malathion with DNA and their detection using new sensitive luminescent Tb(III) complex probe

    Energy Technology Data Exchange (ETDEWEB)

    Azab, Hassan A. [Chemistry Department, Faculty of Science, Suez Canal University, 41522 Ismailia (Egypt); Kamel, Rasha M., E-mail: rashamoka@yahoo.com [Chemistry Department, Faculty of Science, Suez University, 43518 Suez (Egypt)

    2016-02-15

    In this work, the interaction of new luminescent terbium-N(acetoacetyl)-3-allyl-2hydroxybenzaldehyde hydrazone complex in a metal ligand ratio 1:2 in ethanol was studied with different pesticides, using fluorescence technique. The results indicate that the pesticides chlorfenvinphos and malathion exhibit quenching effect on the characteristics emission peak for Tb(III) at λ=545 nm. The luminescence variations values using the probe Tb(III)(HBH){sub 2} fit Stern–Volmer equation, where the detection limits are 4.53 and 9.59 µmol/L for chlorfenvinphos and malathion, respectively. The thermodynamic parameters associated with the interaction of the complex with the two pesticides were calculated, where the reaction is spontaneous through the obtained negative values of free energy change ΔG, and the process is of exothermic nature with decrease in entropy. Hence the nature of forces acting between the complex and pesticide molecules are Vander Val's and hydrogen bond. Also, it was found that the quenching mechanism is static type. Effect of some relevant interferents on the detection of pesticides has been investigated. The new sensing complex was applied to the determination of the pesticides in different real water samples (tap, river, and waste water) with precise recovery. Also, the effect of different concentrations of pesticides on the fluorescence spectrum of DNA was studied. - Highlights: • The method can be used for detection of pesticides in environmental samples. • The DL is 4.53 and 9.59 µmol L{sup −1} for chlorfenvinphos and malathion respectively. • Stern–Volmer studies at different temperatures were studied. • Effect of some interferents on the detection of pesticides has been investigated.

  1. Highly Luminescent Dinuclear Platinum(II) Complexes Incorporating Bis-Cyclometallating Pyrazine-Based Ligands: A Versatile Approach to Efficient Red Phosphors

    OpenAIRE

    Culham, Stacey; Lanoe, Pierre-Henri; Whittle, Victoria; Durrant, Marcus; Williams, Gareth; Kozhevnikov, Valery

    2013-01-01

    A series of luminescent dinuclear platinum(II) complexes incorporating diphenylpyrazine-based bridging ligands ((LH2)-H-n) has been prepared. Both 2,5-diphenylpyrazine ((LH2)-H-2) and 2,3-diphenylpyrazine ((LH2)-H-3) are able to undergo cyclometalation of the two phenyl rings, with each metal ion binding to the two nitrogen atoms of the central heterocycle, giving, after treatment with the anion of dipivaloyl methane (dpm), complexes of formula \\{Pt(dpm)\\}(2)L-n. These compounds are isomers o...

  2. Dramatic improvement in photostability of luminescent Eu(III) complexes with tetraphenylimidodiphosphinate ligand

    International Nuclear Information System (INIS)

    Zheng, Wei; Li, Shu-Jing; Li, Cheng-Hui; Zheng, You-Xuan; You, Xiao-Zeng

    2014-01-01

    In this paper, we synthesized and characterized a new Eu(III) tetraphenylimidodiphosphinate complex with dimethyl sulfoxide (DMSO) as co-ligand. Moreover, we compared the photostability of a series of Eu(III) complexes containing tetraphenylimidodiphosphinate ligands, Eu(tpip) 3 , Eu(tpip) 3 Phen, Eu(tpip) 3 DMSO, with their analogs of 1,3-dibenzoylmethanate, Eu(dbm) 3 ∙2H 2 O, Eu(dbm) 3 Phen, Eu(dbm) 3 (DMSO) 2 . We found that the photostability of the luminescent Eu(III) complexes was significantly improved upon substitution of the 1,3-diketones with tetraphenylimidodiphosphinate ligands. -- Highlights: • We synthesized and characterized a new Eu(III) tetraphenylimidodiphosphinate complexes with dimethyl sulfoxide. • We compared the photostability of Eu(III) complex with tetraphenylimidodiphosphinate and 1,3-dibenzoylmethanate ligands. • The photostability is significantly improved in Eu(III) complexes with tetraphenylimidodiphosphinate ligands

  3. Investigation of complexing of vitamine B-6 with rare earth ions by PMR and luminescent spectroscopy

    International Nuclear Information System (INIS)

    Buiklinskij, V.D.; Zelenov, V.I.; Zolin, V.F.; Koreneva, L.G.; Panyushkin, V.T.

    1981-01-01

    To investigate the complexing of pyridoxine (P), pyridoxal (PL) and pyridoxamine (PM) with lanthanide ions the changes of PMR spectra of ligands in the presence of cerium, praseodymium, neodymium, europium, gadolinium ions, as well as luminescence and absorption spectra of europium in the presence of ligands are used. Using the optical spectroscopy it has been shown that the PL and PM complexes do not have axial symmetry. The values of parameters of the crystalline field of the second order, determining the anisotropy of magnetic susceptibility of europium complexes are evaluated. With an aid of PMR and luminescence spectroscopy it is shown that lanthanide ions coordinate the hydroxy groups of ligands. In the case of P and especially PL oxygen of the substituent in position 4 takes part in the coordination. Using the PMR spectroscopy the difference of the substituent location near C4 in the PM complex from its location in the P and PL complexes as well as the difference in the position of lanthanide ion in the complexes of all the three ligands are detected. The reasons for the differences above are discussed [ru

  4. Conversion of invisible metal-organic frameworks to luminescent perovskite nanocrystals for confidential information encryption and decryption.

    Science.gov (United States)

    Zhang, Congyang; Wang, Bo; Li, Wanbin; Huang, Shouqiang; Kong, Long; Li, Zhichun; Li, Liang

    2017-10-31

    Traditional smart fluorescent materials, which have been attracting increasing interest for security protection, are usually visible under either ambient or UV light, making them adverse to the potential application of confidential information protection. Herein, we report an approach to realize confidential information protection and storage based on the conversion of lead-based metal-organic frameworks (MOFs) to luminescent perovskite nanocrystals (NCs). Owing to the invisible and controlled printable characteristics of lead-based MOFs, confidential information can be recorded and encrypted by MOF patterns, which cannot be read through common decryption methods. Through our conversion strategy, highly luminescent perovskite NCs can be formed quickly and simply by using a halide salt trigger that reacts with the MOF, thus promoting effective information decryption. Finally, through polar solvents impregnation and halide salt conversion, the luminescence of the perovskite NCs can be quenched and recovered, leading to reversible on/off switching of the luminescence signal for multiple information encryption and decryption processes.

  5. A series of copper complexes with carbazole and oxadiazole moieties: Synthesis, characterization and luminescence performance

    Energy Technology Data Exchange (ETDEWEB)

    Bai Weiyang, E-mail: baiwy02@163.com [College of Chemistry and Chemical Engineering, Chongqing University of Technology, Chongqing 400054 (China); Sun Li [Graduate University of Chinese Academy of Sciences, Beijing 100049 (China)

    2012-10-15

    In this paper, various moieties of ethyl, carbazole and oxadiazole are attached to 2-thiazol-4-yl-1H-benzoimidazole to form a series of diamine ligands. Their corresponding Cu(I) complexes are also synthesized using bis(2-(diphenylphosphanyl)phenyl) ether as the auxiliary ligand. Crystal structures, thermal property, electronic nature and luminescence property of these Cu(I) complexes are discussed in detail. These Cu(I) complexes are found to be efficient green-emitting ones in solutions and the emissive parameters are improved largely by the incorporation of substituent moieties. Detailed analysis suggests that the effective suppression of solvent-induced exciplex quenching is responsible for this phenomenon. On the other hand, the introduction of substituent moieties exerts no obvious influence on molecular structure, thermal stability and emitting-energy of the Cu(I) complexes, owing to their absence from inner coordination sphere. - Highlights: Black-Right-Pointing-Pointer Diamine ligands with various moieties and Cu(I) complexes are synthesized. Black-Right-Pointing-Pointer Crystal structures and photophysical property are discussed in detail. Black-Right-Pointing-Pointer The incorporation of substituent moieties improves luminescence performance. Black-Right-Pointing-Pointer Solvent-induced exciplex quenching is suppressed by substituent moieties.

  6. Synthesis, structure and luminescence properties of lanthanide complex with a new tetrapodal ligand featuring salicylamide arms

    International Nuclear Information System (INIS)

    Song Xueqin; Wen Xiaoguang; Liu Weisheng; Wang Daqi

    2010-01-01

    A new tetrapodal ligand 1,1,1-tetrakis{[(2'-(2-furfurylaminoformyl))phenoxyl]methyl}methane (L) has been prepared and their coordination chemistry with Ln III ions has been investigated. The structure of {[Ln 4 L 3 (NO 3 ) 12 ].H 2 O} ∞ (Ln=Nd, Eu)] shows the binodal 4,3-connected three-dimensional interpenetration coordination polymers with topology of a (8 6 ) 3 (8 3 ) 4 notation. [DyL(NO 3 ) 3 (H 2 O) 2 ].0.5CH 3 OH and [ErL(NO 3 ) 3 (H 2 O) (CH 3 OH)].CH 3 COCH 3 is a 1:1 mononuclear complex with interesting supramolecular features. The structure of [NdL(H 2 O) 6 ].3ClO 4 .3H 2 O is a 2:1 mononuclear complex which further self-assembled through hydrogen bond to form a three-dimensional supramolecular structures. The result presented here indicates that both subtle variation of the terminal group and counter anions can be applied in the modulation of the overall molecular structures of lanthanide complex of salicylamide derivatives due to the structure specialties of this type of ligand. The luminescence properties of the Eu III complex are also studied in detail. - Grapical Abstract: We present here a series of zero- to three-dimensional lanthanide coordination structures and luminescence properties of Eu(III) complex of a new tetrapodal ligand.

  7. Investigation on three new metal carboxydiphosphonates: Syntheses, structures, magnetic and luminescent properties

    Energy Technology Data Exchange (ETDEWEB)

    Tang Sifu; Pan Xiaobo; Lv Xiaoxia [Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); Zhao Xuebo, E-mail: zhaoxb@qibebt.ac.cn [Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China)

    2013-01-15

    A new multifunctionalized phosphoric acid, (2-(diphosphonomethylamino)nicotinic acid, Py(COOH)(NHCH--(PO{sub 3}H{sub 2}){sub 2}), H{sub 5}L{sup 1}), has been employed as ligand for the construction of new metal phosphonates. By reacting it with different metal chlorides under hydrothermal condition, three new transition metal phosphonates, namely, [Co{sub 2}(HL{sup 1})(H{sub 2}O){sub 5}][H{sub 2}O]{sub 3} (1), Zn(H{sub 3}L{sup 1}) (2) and [Cd(H{sub 3}L{sup 1})(H{sub 2}O){sub 2}][H{sub 2}O] (3) were successfully obtained. The single-crystal structure measurements indicated that the coordination mode of ligand H{sub 5}L{sup 1} is metal-dependant and results in different structures. For compound 1, it features 2D layered structure. Whereas compounds 2 and 3 have 1D chain structures. Under the excitation of 250 nm light, both compounds 2 and 3 show intraligand and ligand to metal charge transfer (LMCT) emission bands at about 415 and 420 nm, respectively. Magnetic study shows that compound 1 displays antiferromagnetic behavior. - Graphical abstract: Three new metal phosphonates were synthesized from a multifunctionalized phosphonate ligand and different metal chlorides. Their structures, thermal stabilities, luminescent and magnetic properties were characterized. Highlights: Black-Right-Pointing-Pointer Three new metal phosphonates were synthesized under hydrothermal conditions. Black-Right-Pointing-Pointer Compound 1 exhibits 2D layered structure. Black-Right-Pointing-Pointer Compounds 2 and 3 have 1D infinite chain structures. Black-Right-Pointing-Pointer Compound 1 displays antiferromagnetic behavior. Black-Right-Pointing-Pointer Compounds 2 and 3 show intraligand and ligand to metal charge transfer emission bands.

  8. Luminescent cyclometalated iridium(III) polypyridine indole complexes--synthesis, photophysics, electrochemistry, protein-binding properties, cytotoxicity, and cellular uptake.

    Science.gov (United States)

    Lau, Jason Shing-Yip; Lee, Pui-Kei; Tsang, Keith Hing-Kit; Ng, Cyrus Ho-Cheong; Lam, Yun-Wah; Cheng, Shuk-Han; Lo, Kenneth Kam-Wing

    2009-01-19

    A series of luminescent cyclometalated iridium(III) polypyridine indole complexes, [Ir(N--C)(2)(N--N)](PF(6)) (HN--C = 2-phenylpyridine (Hppy), N--N = 4-((2-(indol-3-yl)ethyl)aminocarbonyl)-4'-methyl-2,2'-bipyridine (bpy-ind) (1a), N--N = 4-((5-((2-(indol-3-yl)ethyl)aminocarbonyl)pentyl)aminocarbonyl)-4'-methyl-2,2'-bipyridine (bpy-C6-ind) (1b); HN--C = 7,8-benzoquinoline (Hbzq), N--N = bpy-ind (2a), N--N = bpy-C6-ind (2b); and HN--C = 2-phenylquinoline (Hpq), N--N = bpy-ind (3a), N--N = bpy-C6-ind (3b)), have been synthesized, characterized, and their photophysical and electrochemical properties and lipophilicity investigated. Photoexcitation of the complexes in fluid solutions at 298 K and in alcohol glass at 77 K resulted in intense and long-lived luminescence (lambda(em) = 540-616 nm, tau(o) = 0.13-5.15 mus). The emission of the complexes has been assigned to a triplet metal-to-ligand charge-transfer ((3)MLCT) (dpi(Ir) --> pi*(N--N)) excited state, probably with some mixing of triplet intraligand ((3)IL) (pi --> pi*) (pq) character for complexes 3a,b. Electrochemical measurements revealed that all the complexes showed an irreversible indole oxidation wave at ca. +1.1 V versus SCE, a quasi-reversible iridium(IV/III) couple at ca. +1.3 V, and a reversible diimine reduction couple at ca. -1.3 V. The interactions of these complexes with an indole-binding protein, bovine serum albumin (BSA), have been studied by emission titrations, and the K(a) values are on the order of 10(4) M(-1). Additionally, the cytotoxicity of the complexes toward human cervix epithelioid carcinoma (HeLa) cells has been examined by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide (MTT) assay. The IC(50) values of the complexes ranged from 1.1 to 6.3 microM, which are significantly smaller than that of cisplatin (30.7 microM) under the same experimental conditions. Furthermore, the cellular uptake of the complexes has been investigated by flow cytometry and laser

  9. Construction of a self- luminescent cyanobacterial bioreporter that detects a broad range of bioavailable heavy metals in aquatic environments

    Directory of Open Access Journals (Sweden)

    Keila eMartin-Betancor

    2015-03-01

    Full Text Available A self-luminescent bioreporter strain of the unicellular cyanobacterium Synechococcus sp. PCC 7942 was constructed by fusing the promoter region of the smt locus (encoding the transcriptional repressor SmtB and the metallothionein SmtA to luxCDABE from Photorhabdus luminescens; the sensor smtB gene controlling the expression of smtA was cloned in the same vector. The bioreporter performance was tested with a range of heavy metals and was shown to respond linearly to divalent Zn, Cd, Cu, Co, Hg and monovalent Ag. Chemical modelling was used to link bioreporter response with metal speciation and bioavailability. Limits of Detection (LODs, Maximum Permissive Concentrations (MPCs and dynamic ranges for each metal were calculated in terms of free ion concentrations. The ranges of detection varied from 11 to 72 pM for Hg2+ (the ion to which the bioreporter was most sensitive to 1.54-5.35 µM for Cd2+ with an order of decreasing sensitivity as follows: Hg2+ >> Cu2+ >> Ag+ > Co2+ ≥ Zn2+ > Cd2+. However, the maximum induction factor reached 75-fold in the case of Zn2+ and 56-fold in the case of Cd2+, implying that Zn2+ is the preferred metal in vivo for the SmtB sensor, followed by Cd2+, Ag+ and Cu2+ (around 45-50-fold induction, Hg2+ (30-fold and finally Co2+ (20-fold. The bioreporter performance was tested in real environmental samples with different water matrix complexity artificially contaminated with increasing concentrations of Zn, Cd, Ag and Cu, confirming its validity as a sensor of free heavy metal cations bioavailability in aquatic environments.

  10. Metallic complexes with glyphosate: a review

    OpenAIRE

    Coutinho, Cláudia F. B.; Mazo, Luiz Henrique

    2005-01-01

    We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature.

  11. Metallic complexes with glyphosate: a review

    International Nuclear Information System (INIS)

    Coutinho, Claudia F.B.; Mazo, Luiz Henrique

    2005-01-01

    We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature. (author)

  12. Photoluminescent properties of complex metal oxide nanopowders for gas sensing

    Science.gov (United States)

    Bovhyra, R. V.; Mudry, S. I.; Popovych, D. I.; Savka, S. S.; Serednytski, A. S.; Venhryn, Yu. I.

    2018-03-01

    This work carried out research on the features of photoluminescence of the mixed and complex metal oxide nanopowders (ZnO/TiO2, ZnO/SnO2, Zn2SiO4) in vacuum and gaseous ambient. The nanopowders were obtained using pulsed laser reactive technology. The synthesized nanoparticles were characterized by X-ray diffractometry, energy-dispersive X-ray analysis, and scanning and transmission electron microscopy analysis for their sizes, shapes and collocation. The influence of gas environment on the photoluminescence intensity was investigated. A change of ambient gas composition leads to a rather significant change in the intensity of the photoluminescence spectrum and its deformation. The most significant changes in the photoluminescent spectrum were observed for mixed ZnO/TiO2 nanopowders. This obviously is the result of a redistribution of existing centers of luminescence and the appearance of new adsorption centers of luminescence on the surface of nanopowders. The investigated nanopowders can be effectively used as sensing materials for the construction of the multi-component photoluminescent sensing matrix.

  13. Synthesis, characterization and luminescence studies of gold(I–NHC amide complexes

    Directory of Open Access Journals (Sweden)

    Adrián Gómez-Suárez

    2013-10-01

    Full Text Available A flexible, efficient and straightforward methodology for the synthesis of N-heterocyclic carbene gold(I–amide complexes is reported. Reaction of the versatile building block [Au(OH(IPr] (1 (IPr = 1,3-bis(2,6-diisopropylphenylimidazol-2-ylidene with a series of commercially available (heteroaromatic amines leads to the synthesis of several [Au(NRR’(IPr] complexes in good yields and with water as the sole byproduct. Interestingly, these complexes present luminescence properties. UV–vis and fluorescence measurements have allowed the identification of their excitation and emission wavelengths (λmax. These studies revealed that by selecting the appropriate amine ligand the emission can be easily tuned to achieve a variety of colors, from violet to green.

  14. Development of a ratiometric time-resolved luminescence sensor for pH based on lanthanide complexes.

    Science.gov (United States)

    Liu, Mingjing; Ye, Zhiqiang; Xin, Chenglong; Yuan, Jingli

    2013-01-25

    Time-resolved luminescence bioassay technique using lanthanide complexes as luminescent probes/sensors has shown great utilities in clinical diagnostics and biotechnology discoveries. In this work, a novel terpyridine polyacid derivative that can form highly stable complexes with lanthanide ions in aqueous media, (4'-hydroxy-2,2':6',2''-terpyridine-6,6''-diyl) bis(methylenenitrilo) tetrakis(acetic acid) (HTTA), was designed and synthesized for developing time-resolved luminescence pH sensors based on its Eu(3+) and Tb(3+) complexes. The luminescence characterization results reveal that the luminescence intensity of HTTA-Eu(3+) is strongly dependent on the pH values in weakly acidic to neutral media (pK(a) = 5.8, pH 4.8-7.5), while that of HTTA-Tb(3+) is pH-independent. This unique luminescence response allows the mixture of HTTA-Eu(3+) and HTTA-Tb(3+) (the HTTA-Eu(3+)/Tb(3+) mixture) to be used as a ratiometric luminescence sensor for the time-resolved luminescence detection of pH with the intensity ratio of its Tb(3+) emission at 540 nm to its Eu(3+) emission at 610 nm, I(540 nm)/I(610 nm), as a signal. Moreover, the UV absorption spectrum changes of the HTTA-Eu(3+)/Tb(3+) mixture at different pHs (pH 4.0-7.0) also display a ratiometric response to the pH changes with the ratio of absorbance at 290 nm to that at 325 nm, A(290 nm)/A(325 nm), as a signal. This feature enables the HTTA-Eu(3+)/Tb(3+) mixture to have an additional function for the pH detection with the absorption spectrometry technique. For loading the complexes into the living cells, the acetoxymethyl ester of HTTA was synthesized and used for loading HTTA-Eu(3+) and HTTA-Tb(3+) into the cultured HeLa cells. The luminescence imaging results demonstrated the practical utility of the new sensor for the time-resolved luminescence cell imaging application. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Incorporation of Znq2 complexes into mesoporous silica and their transparent polymer luminescent nanocomposites

    International Nuclear Information System (INIS)

    Du Yaying; Fu Yuqin; Shi Yongli; Lue Xiaodan; Lue Changli; Su Zhongmin

    2009-01-01

    Znq 2 -functionalized colloidal mesoporous silicas (Znq 2 -CMS)/polymer transparent nanocomposites were prepared by in situ bulk polymerization. CMS nanoparticles or nanorods with hydroxyl-, mercapto- and sulfonic-functionalized interiors were obtained by different synthetic routes in the nanosize dimensions between 50 and 500 nm. The luminescent Znq 2 complex was successfully introduced in the pores of different mesoporous silicas by chemical adsorption as the driving force. The different internal circumstances of mesoporous silicas had an obvious effect on the luminescence and lifetime of Znq 2 complex. The transparent fluorescent nanocomposites were fabricated from different Znq 2 -CMS and suitable monomers. The Znq 2 -CMS were uniformly dispersed in the polymer matrix without evident aggregation. The photoluminescence properties of Znq 2 -CMS in the transparent matrix exhibited a dependence on the inner surrounding of CMS due to the interaction between Znq 2 -CMS and polymers. The maximum emission peak of the nanocomposites had a red-shift of 28 nm as compared to pure Znq 2 -CMS. - Graphical abstract: Znq 2 -functionalized colloidal mesoporous silicas (Znq 2 -CMS)/polymer transparent fluorescent nanocomposites were prepared by in situ bulk polymerization. The figure shows the synthetic scheme for the Znq 2 -CMS and their transparent bulk nanocomposites.

  16. NMR and luminescence spectroscopy study of formation of mixed β-diketonate europium complexes

    International Nuclear Information System (INIS)

    Kavun, V.Ya.; Kalinovskaya, I.V.; Karasev, V.E.; Chernyshov, B.N.; Steblevskaya, N.I.

    1987-01-01

    Methods of NMR ('H, 19 F) and luminescent spectroscopy were applied to study ligand substitution in Eu(β-dik) 3 phen-CDCl 3 -(β-dik)' systems, where β-dik-acetylacetone (AA) and hexafluoroacetyl-acetone (HFAA), phen-1.10-phenathroline at different mole ratio (m) of competing ligands (m=AA/HFAA). Formation of mixed Eu(AA) 2 (HFAA)phen and Eu(AA)(HFAA) 2 phen complexes is proved; calculation of the stark structure of 5 D 0 - 7 F j (j=0,1,2) transitions in low-temperature luminescence spectra is conducted for these complexes. It is stated that at minimum HFAA concentration in the solution the latter replaces AA from europium coordination sphere. It is shown that depending on the value in substitution of acidoligands proceeds successfully by the equations Eu(AA) 3 phen+(NHFAA) n → Eu(AA) 3-n → (HFAA) n phen+(NAA) n ; (n=1,2,3)

  17. Complexes of natural carbohydrates with metal cations

    International Nuclear Information System (INIS)

    Alekseev, Yurii E; Garnovskii, Alexander D; Zhdanov, Yu A

    1998-01-01

    Data on the interaction of natural carbohydrates (mono-, oligo-, and poly-saccharides, amino sugars, and natural organic acids of carbohydrate origin) with metal cations are surveyed and described systematically. The structural diversity of carbohydrate metal complexes, caused by some specific features of carbohydrates as ligands, is demonstrated. The influence of complex formation on the chemical properties of carbohydrates is discussed. It is shown that the formation of metal complexes plays an important role in the configurational and conformational analysis of carbohydrates. The practical significance of the coordination interaction in the series of carbohydrate ligands is demonstrated. The bibliography includes 571 references.

  18. Preparation and luminescence of silica aerogel composites containing an europium (III) phenanthroline nitrate complex

    Energy Technology Data Exchange (ETDEWEB)

    Gutzov, Stoyan, E-mail: sgutzov@chem.uni-sofia.bg [University of Sofia “St. Kliment Ohridski”, Department of Physical Chemistry, J. Bourchier Blvd. 1, 1164 Sofia (Bulgaria); Danchova, Nina; Kirilova, Rada; Petrov, Vesselin [University of Sofia “St. Kliment Ohridski”, Department of Physical Chemistry, J. Bourchier Blvd. 1, 1164 Sofia (Bulgaria); Yordanova, Stanislava [University of Sofia “St. Kliment Ohridski”, Department of Organic Chemistry, J. Bourchier Blvd. 1, 1164 Sofia (Bulgaria)

    2017-03-15

    A simple two step procedure for the functionalization of hydrophobic silica aerogel microgranules with europium ions and/or 1,10 - phenanthroline is demonstrated. The activation procedure is based on soaking aerogels in a europium nitrate solution, followed by functionalization with 1,10 – phenanthroline. The functionalized materials display strong red or blue emission at UV-excitation, coming from the formation of [Eu(phen){sub 2}](NO{sub 3}){sub 3} or Si(IV)– 1,10-phenathroline complexes in the porous system of the aerogels. The most probable site symmetry of the europium cation is C{sub 2v} confirmed by luminescence spectra analysis. Room temperature diffuse reflectance spectra and excitation/luminescence spectra are used to describe the optical properties of the hybrid composites. Excitation spectra prove an efficient energy transfer between 1,10 – phenanthroline and the Eu{sup 3+} ion. - Graphical abstract: An effective activation procedure for functionalization of silica aerogel granules with [Eu(phen){sub 2}](NO{sub 3}){sub 3} and/or 1,10 – phenanthroline /phen/ has been demonstrated in order to obtain red or blue emitting materials. Luminescence spectra (excitation at 355 nm) of functionalized aerogel granules: 1 – SiO{sub 2}:0.18phen; 2 – [Eu(phen){sub 2}](NO{sub 3}){sub 3}; 3– SiO{sub 2}:0.007Eu(phen){sub 2}(NO{sub 3}){sub 3}. The Eu{sup 3+} f-f {sup 5}D{sub 0} →{sup 7}F {sub 0,1,2,3,4} emission transitions are denoted as 0-0, 0-1, 0-2, 0-3, 0-4. The most probable site symmetry of Eu3{sup +} ion is C{sub 2v}.

  19. Theoretical studies of boron(III) complexes for the new blue luminescent material

    International Nuclear Information System (INIS)

    Lee, Jung Eun; Choi, Gyu Chul; Rim, Byung O.; Kim, Sung Min; Park, No Gill; Ha, Yun Kyoung; Kim, Young Sik

    2004-01-01

    Boron(III) complexes, BPh 2 (2-py-aza) and Bph 2 (2-py-in), are known as blue emitting materials. In this paper, we have studied various ligand effects of boron complex on the absorption (UV) and electroluminescence (EL) peaks computationally. To obtain optical properties, TD-DFT(B3LYP) methods are used with 6-31+G(d) basis set. It was found that EL peaks of those materials are calculated at 454 and 510 nm, which are considerably consistent with experimental data. From the results, we newly proposed two materials, BPh 2 (PBI-Me) and BPh 2 (PBI-Ph), as blue luminescent materials, whose calculated EL peaks are at 456 and 480 nm, respectively. Through the calculation results, newly designed compounds showed possibility as efficient and promising emitters in EL device

  20. Synthesis, structure and luminescence properties of zinc (II) complexes with terpyridine derivatives as ligands

    International Nuclear Information System (INIS)

    Chen Xuegang; Zhou Quanguo; Cheng Yanxiang; Geng Yanhou; Ma Dongge; Xie Zhiyuan; Wang Lixiang

    2007-01-01

    Five zinc (II) complexes (1-5) with 4'-phenyl-2,2':6',2''-terpyridine (ptpy) derivatives as ligands have been synthesized and fully characterized. The para-position of phenyl in ptpy is substituted by the group (R), i.e. tert-butyl (t-Bu), hexyloxy (OHex), carbazole-9-yl (Cz), naphthalen-1-yl-phenyl-amine-N-yl (NPA) and diphenyl amine-N-yl (DPA), with different electron-donating ability. With increasing donor ability of the R, the emission color of the complexes in film was modulated from violet (392 nm) to reddish orange (604 nm). The photoexcited luminescence exhibits significant solvatochromism because the emission of the complexes involves the intra-ligand charge transfer (ILCT) excited state. The electrochemical investigations show that the complexes with stronger electro-donating substituent have lower oxidation potential and then higher HOMO level. The electroluminescence (EL) properties of these zinc (II) complexes were studied with the device structure of ITO/PEDOT/Zn (II) complex: PBD:PMMA/BCP/AlQ/LiF/Al. Complexes 3, 4 and 5 exhibit EL wavelength at 552, 600 and 609 nm with maximum current efficiency of 5.28, 2.83 and 2.00 cd/A, respectively

  1. Photochemical activation and reactivity of polynuclear transition-metal-complex molecules. Progress report, June 1981-May 31, 1982

    International Nuclear Information System (INIS)

    Endicott, J.F.; Lintvedt, R.L.

    1982-01-01

    Significant results obtained during the year are summarized for the following programs: (1) reversible, two electron transfer at a single potential in binuclear complexes; (2) photophysics of polyketonate complexes; (3) synthetic strategies and characterization of heavy metal heterobinuclear complexes; (4) high yield synthesis of ligands capable of binding 3 and 4 metal ions per molecule. Electrochemical studies have uncovered a number of new binuclear metal complexes that undergo reversible two-electron reduction at single potential including Cu(II) complexes with two different coordination environments, mixed Ni(II), Cu(II) complexes and binuclear Ni(II) complexes. In each case the species that exhibit these electron transfer properties have been shown to be Na + ion-paired complexes. Several new trinuclear molecular complexes have been prepared and characterized that contain two UO 2 2+ ions and one transition metal ion. The electrochemistry, absorption spectra, and luminescence have been investigated

  2. Chiroptical methods in a wide wavelength range for obtaining Ln3+ complexes with circularly polarized luminescence of practical interest.

    Science.gov (United States)

    Górecki, Marcin; Carpita, Luca; Arrico, Lorenzo; Zinna, Francesco; Di Bari, Lorenzo

    2018-05-29

    We studied enantiopure chiral trivalent lanthanide (Ln3+ = La3+, Sm3+, Eu3+, Gd3+, Tm3+, and Yb3+) complexes with two fluorinated achiral tris(β-diketonate) ligands (HFA = hexafluoroacetylacetonate and TTA = 2-thenoyltrifluoroacetonate), incorporating a chiral bis(oxazolinyl)pyridine (PyBox) unit as a neutral ancillary ligand, by the combined use of optical and chiroptical methods, ranging from UV to IR both in absorption and circular dichroism (CD), and including circularly polarized luminescence (CPL). Ultimately, all the spectroscopic information is integrated into a total and a chiroptical super-spectrum, which allows one to characterize a multidimensional chemical space, spanned by the different Ln3+ ions, the acidity and steric demand of the diketone and the chirality of the PyBox ligand. In all cases, the Ln3+ ions endow the systems with peculiar chiroptical properties, either allied to f-f transitions or induced by the metal onto the ligand. In more detail, we found that Sm3+ complexes display interesting CPL features, which partly superimpose and partly integrate the more common Eu3+ properties. Especially, in the context of security tags, the pair Sm/Eu may be a winning choice for chiroptical barcoding.

  3. Pharmacologically significant tetraaza macrocyclic metal complexes ...

    Indian Academy of Sciences (India)

    MOHAMMAD SHAKIR

    2017-11-22

    Nov 22, 2017 ... structural biological models.6 Hence, biological prop- erties of ... poor water solubility, exhibits intrinsic resistance and ..... pdb). The metal complex files were drawn using. ChemDraw (MM2) and their energies were minimized.

  4. Development of a ratiometric time-resolved luminescence sensor for pH based on lanthanide complexes

    International Nuclear Information System (INIS)

    Liu Mingjing; Ye Zhiqiang; Xin Chenglong; Yuan Jingli

    2013-01-01

    Highlights: ► A lanthanide complex-based ratiometric luminescent pH sensor was developed. ► The sensor can luminously respond to pH in weakly acidic to neutral media. ► The sensor can be used for monitoring pH with time-resolved luminescence mode. ► The sensor can be also used for monitoring pH with absorbance mode. ► The utility of the sensor for the luminescent cell imaging was demonstrated. - Abstract: Time-resolved luminescence bioassay technique using lanthanide complexes as luminescent probes/sensors has shown great utilities in clinical diagnostics and biotechnology discoveries. In this work, a novel terpyridine polyacid derivative that can form highly stable complexes with lanthanide ions in aqueous media, (4′-hydroxy-2,2′:6′,2′′-terpyridine-6,6′′-diyl) bis(methylenenitrilo) tetrakis(acetic acid) (HTTA), was designed and synthesized for developing time-resolved luminescence pH sensors based on its Eu 3+ and Tb 3+ complexes. The luminescence characterization results reveal that the luminescence intensity of HTTA–Eu 3+ is strongly dependent on the pH values in weakly acidic to neutral media (pK a = 5.8, pH 4.8–7.5), while that of HTTA–Tb 3+ is pH-independent. This unique luminescence response allows the mixture of HTTA–Eu 3+ and HTTA–Tb 3+ (the HTTA–Eu 3+ /Tb 3+ mixture) to be used as a ratiometric luminescence sensor for the time-resolved luminescence detection of pH with the intensity ratio of its Tb 3+ emission at 540 nm to its Eu 3+ emission at 610 nm, I 540nm /I 610nm , as a signal. Moreover, the UV absorption spectrum changes of the HTTA–Eu 3+ /Tb 3+ mixture at different pHs (pH 4.0–7.0) also display a ratiometric response to the pH changes with the ratio of absorbance at 290 nm to that at 325 nm, A 290nm /A 325nm , as a signal. This feature enables the HTTA–Eu 3+ /Tb 3+ mixture to have an additional function for the pH detection with the absorption spectrometry technique. For loading the complexes into the

  5. Quinonoid metal complexes: toward molecular switches.

    Science.gov (United States)

    Dei, Andrea; Gatteschi, Dante; Sangregorio, Claudio; Sorace, Lorenzo

    2004-11-01

    The peculiar redox-active character of quinonoid metal complexes makes them extremely appealing to design materials of potential technological interest. We show here how the tuning of the properties of these systems can be pursued by using appropriate molecular synthetic techniques. In particular, we focus our attention on metal polyoxolene complexes exhibiting intramolecular electron transfer processes involving either the ligand and the metal ion or the two dioxolene moieties of a properly designed ligand thus inducing electronic bistability. The transition between the two metastable electronic states can be induced by different external stimuli such as temperature, pressure, light, or pH suggesting the use of these systems for molecular switches.

  6. Metal-Organic Framework Nanosheets for Fast-Response and Highly Sensitive Luminescent Sensing of Fe3+

    DEFF Research Database (Denmark)

    Xu, Hui; Iversen, Bo Brummerstedt

    of graphene, Since the discovery of graphene, series of two-dimensional (2-D) nanosheets materials such as metal oxides, metal hydroxides, transition metal chalcogenides (TMDs), boron nitride (BN) and black phosphorus have been of great interests, and have been extensively investigated for applications...... in electronics, lithium-ion batteries, catalysis and mechanical properties, etc. 2-D MOF nanosheets materials, as a new member of the 2-D nanomaterials family, are still at the very early stage. However, to the best of our knowledge, the 2-D MOF nanosheets materials for luminescent sensing have been rarely...

  7. Thallium and manganese complexes involved in the luminescence emission of potassium-bearing aluminosilicates

    Energy Technology Data Exchange (ETDEWEB)

    Gomez-Gonzalez, Miguel A., E-mail: miguel.gomez@mncn.csic.es [Museo Nacional de Ciencias Naturales, CSIC, Jose Gutierrez Abascal 2, Madrid E-28006 (Spain); Garcia-Guinea, Javier, E-mail: guinea@mncn.csic.es [Museo Nacional de Ciencias Naturales, CSIC, Jose Gutierrez Abascal 2, Madrid E-28006 (Spain); Garrido, Fernando, E-mail: fernando.garrido@mncn.csic.es [Museo Nacional de Ciencias Naturales, CSIC, Jose Gutierrez Abascal 2, Madrid E-28006 (Spain); Townsend, Peter D., E-mail: pdtownsend@gmail.com [School of Science and Technology, University of Sussex, Brighton BN1 9QH (United Kingdom); Marco, Jose-Francisco, E-mail: jfmarco@iqfr.csic.es [Instituto de Química-Física Rocasolano, CSIC, Calle Serrano 119, Madrid E-28006 (Spain)

    2015-03-15

    The luminescence emission at 285 nm in natural K-feldspar has been studied by Russian groups and associated with thallium ions in structural positions of K{sup +} sites as artificially thallium-doped feldspars display the same emission band. Here attention is focussed on spectra of CL emission bands centered near 285 and 560 nm from paragenetic adularia, moscovite and quartz micro-inclusions. With accesorial thallium they show clear resemblances to each other. Associated sedimentary and hydrothermal aluminosilicate samples collected from Guadalix (Madrid, Spain) were analyzed with a wide range of experimental techniques including Environmental Scanning Electron Microscopy (ESEM) with an attached X-Ray Energy-Dispersive Spectrometer (EDS) and a cathodoluminescence probe (CL) and Electron Probe Microanalysis (EPMA), X-Ray Fluorescence Spectrometry (XRF), Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES), Differential and Thermogravimetric Analyses (DTA-TG), radioluminescence (RL), Mössbauer spectroscopy and X-Ray Photoelectron Spectrometry (XPS). The luminescence emission bands at 285 and 560 nm seem to be associated with hydrous thallium–manganese complexes bonded to potassium-bearing aluminosilicates since various minerals such as K-feldspar, moscovite and quartz micro-inclusions display similar CL spectra, accesorial thallium and hydroxyl groups. The presence of iron introduces a brown color which is attributed to submicroscopic iron oxides detectable in the optical and chemical microanalysis, but this does not contribute to the luminescence emission. The XPS Mn 2p spectrum of the adularia sample at room temperature is composed of a spin–orbit doublet plus clear shake-up satellite structure ∼4 eV above the main photoemision lines and is consistent with Mn{sup 2+} in good agreement with the observed luminescence emission at 560 nm for aluminosilicates produced by a {sup 4}T1({sup 4}G)→{sup 6}A1({sup 6}S) transition in tetrahedrally

  8. Self-assembly of a helical zinc-europium complex: speciation in aqueous solution and luminescence

    Directory of Open Access Journals (Sweden)

    Emmanuel eDeiters

    2013-09-01

    Full Text Available Two new tridentate(NNO-bidentate(NN compartmental ligands, HL5 and HL6, are synthesized from pyridine and benzimidazole synthons. They react in aqueous solution under physiological conditions with ZnII, LnIII, or a mixture thereof, to yield complexes of different stoichiometries, 1:3, 2:2, 2:3, 1:1:3, the speciation of which is established by UV-visible titrations and ESI mass spectrometry. Photophysical studies of the EuIII-containing solutions in Tris-HCl 0.1 M (pH = 7.4 show that lanthanide luminescence arises from a unique N6O3 coordination site with pseudo D3 symmetry. Relevant parameters such as crystal field splitting, lifetime, radiative lifetime and intrinsic quantum yield perfectly match those reported for dinuclear 4f-4f helicates in which the EuIII ion has the same coordination environment.

  9. Fabrication of Superhydrophobic and Luminescent Rare Earth/Polymer complex Films.

    Science.gov (United States)

    Wang, Zefeng; Ye, Weiwei; Luo, Xinran; Wang, Zhonggang

    2016-04-18

    The motivation of this work is to create luminescent rare earth/polymer films with outstanding water-resistance and superhydrophobicity. Specifically, the emulsion polymerization of styrene leads to core particles. Then core-shell-structured polymer nanoparticles are synthesized by copolymerization of styrene and acrylic acid on the core surface. The coordination reaction between carboxylic groups and rare earth ions (Eu(3+) and Tb(3+)) generates uniform spherical rare earth/polymer nanoparticles, which are subsequently complexed with PTFE microparticles to obtain micro-/nano-scaled PTFE/rare earth films with hierarchical rough morphology. The films exhibit large water contact angle up to 161° and sliding angle of about 6°, and can emit strong red and green fluorescence under UV excitation. More surprisingly, it is found that the films maintain high fluorescence intensity after submersed in water and even in aqueous salt solution for two days because of the excellent water repellent ability of surfaces.

  10. Synthesis and characterization of the europium (III) complex as an organic luminescent material

    International Nuclear Information System (INIS)

    Zhuo Zuliang; Zhang Fujun; Xu Zheng; Lu Lifang; Li Junming; Wang Yongsheng; Lv Yuguang

    2010-01-01

    The red emission organic material Eu(coumarin) 3 ·2H 2 O complex was synthesized and its morphology, energy level alignment and luminescence characteristics were studied by using scanning electron microscopy, Fourier transform infrared spectra, cyclic voltammetry and ultraviolet-visible absorption spectra and fluorescence spectra. Eu(coumarin) 3 ·2H 2 O shows bright red emission originating from Eu 3+ ions under 345 nm light excitation. The luminescence lifetime of Eu 3+ in this complex is about 580 μs. To improve the quality of Eu(coumarin) 3 ·2H 2 O thin films, Eu(coumarin) 3 ·2H 2 O was doped with a poly(N-vinylcarbazole) (PVK) solution. The organic materials 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and aluminum quinoline (Alq 3 ) were used as hole-blocking and electron-transporting layers in our fabricated electroluminescence (EL) devices on indium tin oxide (ITO) substrates, respectively. The EL devices ITO/poly-(3,4-ethylenedioxythiophene):poly-(styrenesulphonic acid) (PEDOT:PSS)/emitting layer (PVK:Eu)/BCP/Alq 3 /Al were fabricated, and EL spectra were measured under different driving voltages. There is one emission peaking at 490 nm in addition to the characteristic emission peaks of Eu 3+ , which should be attributed to the spectral overlap between the PVK emission and electroplex emission originating from PVK and BCP interfaces. This explanation can be positively supported by the dependence of the EL spectral variation of ITO/ PVK/BCP/Alq 3 /Al devices on the driving voltage.

  11. Synthesis and characterization of the europium (III) complex as an organic luminescent material

    Science.gov (United States)

    Zhuo, Zuliang; Zhang, Fujun; Lv, Yuguang; Xu, Zheng; Lu, Lifang; Li, Junming; Wang, Yongsheng

    2010-11-01

    The red emission organic material Eu(coumarin)3·2H2O complex was synthesized and its morphology, energy level alignment and luminescence characteristics were studied by using scanning electron microscopy, Fourier transform infrared spectra, cyclic voltammetry and ultraviolet-visible absorption spectra and fluorescence spectra. Eu(coumarin)3·2H2O shows bright red emission originating from Eu3+ ions under 345 nm light excitation. The luminescence lifetime of Eu3+ in this complex is about 580 μs. To improve the quality of Eu(coumarin)3·2H2O thin films, Eu(coumarin)3·2H2O was doped with a poly(N-vinylcarbazole) (PVK) solution. The organic materials 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and aluminum quinoline (Alq3) were used as hole-blocking and electron-transporting layers in our fabricated electroluminescence (EL) devices on indium tin oxide (ITO) substrates, respectively. The EL devices ITO/poly-(3,4-ethylenedioxythiophene):poly-(styrenesulphonic acid) (PEDOT:PSS)/emitting layer (PVK:Eu)/BCP/Alq3/Al were fabricated, and EL spectra were measured under different driving voltages. There is one emission peaking at 490 nm in addition to the characteristic emission peaks of Eu3+, which should be attributed to the spectral overlap between the PVK emission and electroplex emission originating from PVK and BCP interfaces. This explanation can be positively supported by the dependence of the EL spectral variation of ITO/ PVK/BCP/Alq3/Al devices on the driving voltage.

  12. Synthesis and characterization of the europium (III) complex as an organic luminescent material

    Energy Technology Data Exchange (ETDEWEB)

    Zhuo Zuliang; Zhang Fujun; Xu Zheng; Lu Lifang; Li Junming; Wang Yongsheng [Key Laboratory of Luminescence and Optical Information (Beijing Jiaotong University), Ministry of Education, Beijing 100044 (China); Lv Yuguang, E-mail: fjzhang@bjtu.edu.c [The Provincial Key Laboratory of Biomaterials, College of Chemistry and Pharmacy, Jiamusi University, Jiamusi 154007 (China)

    2010-11-15

    The red emission organic material Eu(coumarin){sub 3{center_dot}}2H{sub 2}O complex was synthesized and its morphology, energy level alignment and luminescence characteristics were studied by using scanning electron microscopy, Fourier transform infrared spectra, cyclic voltammetry and ultraviolet-visible absorption spectra and fluorescence spectra. Eu(coumarin){sub 3{center_dot}}2H{sub 2}O shows bright red emission originating from Eu{sup 3+} ions under 345 nm light excitation. The luminescence lifetime of Eu{sup 3+} in this complex is about 580 {mu}s. To improve the quality of Eu(coumarin){sub 3{center_dot}}2H{sub 2}O thin films, Eu(coumarin){sub 3{center_dot}}2H{sub 2}O was doped with a poly(N-vinylcarbazole) (PVK) solution. The organic materials 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and aluminum quinoline (Alq{sub 3}) were used as hole-blocking and electron-transporting layers in our fabricated electroluminescence (EL) devices on indium tin oxide (ITO) substrates, respectively. The EL devices ITO/poly-(3,4-ethylenedioxythiophene):poly-(styrenesulphonic acid) (PEDOT:PSS)/emitting layer (PVK:Eu)/BCP/Alq{sub 3}/Al were fabricated, and EL spectra were measured under different driving voltages. There is one emission peaking at 490 nm in addition to the characteristic emission peaks of Eu{sup 3+}, which should be attributed to the spectral overlap between the PVK emission and electroplex emission originating from PVK and BCP interfaces. This explanation can be positively supported by the dependence of the EL spectral variation of ITO/ PVK/BCP/Alq{sub 3}/Al devices on the driving voltage.

  13. Synthesis and spectroscopic behavior of highly luminescent Eu 3+-dibenzoylmethanate (DBM) complexes with sulfoxide ligands

    Science.gov (United States)

    Niyama, E.; Brito, H. F.; Cremona, M.; Teotonio, E. E. S.; Reyes, R.; Brito, G. E. S.; Felinto, M. C. F. C.

    2005-09-01

    In this paper the synthesis, characterization and photoluminescent behavior of the [RE(DBM) 3L 2] complexes (RE = Gd and Eu) with a variety of sulfoxide ligands; L = benzyl sulfoxide (DBSO), methyl sulfoxide (DMSO), phenyl sulfoxide (DPSO) and p-tolyl sulfoxide (PTSO) have been investigated in solid state. The emission spectra of the Eu 3+-β-diketonate complexes show characteristics narrow bands arising from the 5D 0 → 7F J ( J = 0-4) transitions, which are split according to the selection rule for C n, C nv or C s site symmetries. The experimental Judd-Ofelt intensity parameters ( Ω2 and Ω4), radiative ( Arad) and non-radiative ( Anrad) decay rates, and R02 for the europium complexes have been determined and compared. The highest value of Ω2 (61.9 × 10 -20 cm 2) was obtained to the complex with PTSO ligand, indicating that Eu 3+ ion is in the highly polarizable chemical environment. The higher values of the experimental quantum yield ( q) and emission quantum efficiency of the emitter 5D 0 level ( η) for the Eu-complexes with DMSO, DBSO and PTSO sulfoxides suggest that these complexes are promising Light Conversion Molecular Devices (LCMDs). The lower value of quantum yield ( q = 1%), for the hydrated complex [Eu(DBM) 3(H 2O)], indicates that the luminescence quenching occurs via multiphonon relaxation by coupling with the OH-oscillators from water molecule coordinated to rare earth ion. The pure red emission of the Eu-complexes has been confirmed by ( x, y) color coordinates.

  14. The Enhanced Intramolecular Energy Transfer and Strengthened ff Luminescence of a Stable Helical Eu Complex in Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Yuki Hasegawa

    2018-01-01

    Full Text Available The luminescence of a Eu complex (EuL is enhanced by stabilization of the coordination structure in highly viscous ionic liquids. The EuL was found to maintain a stable single helical structure both in organic solvents and in the ionic liquids [BMIM][PF6] and [EMIM][PF6]. A colorless solution of EuL dissolved in [BMIM][PF6] exhibits bright red luminescence with a quantum yield of 32.3%, a value that is much higher than that in acetonitrile (12%. Estimated rate constants for the energy relaxation pathway indicate that the energy transfer efficiency is enhanced in [BMIM][PF6] as a result of the suppression of molecular fluctuations in the ligands. Additionally, a highly luminescent helical structure is preserved in [EMIM][PF6] up to 120 °C.

  15. Synthesis and optical properties of enantiomeric cinchonidine/cinchonine-terpyridine derivatives and their metal complexes

    International Nuclear Information System (INIS)

    Wang, Hui-Ting; Wu, Wen-Jie; Liu, Jiang; Chen, Meng; Qian, Dong-Jin; Zhang, Li; Liu, Minghua

    2016-01-01

    We report here the synthesis and spectroscopic properties of two enantiomeric chiral tridentate ligands (TPyCCD and TPyCCN) composed of terpyridine (TPy) and cinchonidine (CCD) or cinchonine (CCN) substituent, as well as their metal complexes with Zn 2+ , Fe 2+ , Eu 3+ , and Tb 3+ ions. For the pure ligands, the fluorescent emission intensity increased as their concentrations increased in the dilute solutions, but they decreased when the concentrations were greater than 6.9×10 −6 mol/l due to concentration quenching. No significant influence on ligand luminescence was observed for the Zn 2+ /Fe 2+ –TPyCCD and –TPyCCN metal complexes. Their lanthanide (Eu 3+ and Tb 3+ ) complexes displayed both ligand and lanthanide ion emissions, suggesting that the excited energy of both ligands could be transferred to the central Eu 3+ and Tb 3+ ions. Mirror-image circular dichroism spectra were recorded, with several signals centered at about 230, 250–270, 296, and 320 nm; the first ones corresponded to the chiral CCD and CCN substituents, while the latter ones corresponded to the TPy substituent and the metal–TPy (M-TPy) coordination units. It is suggested that the chirality of TPy and the metal complexes was induced by the coexisting chiral CCD and CCN substituents. In addition, due to formation of the metal complexes, the relative intensity of the chiral signals of M–TPy coordination units was enhanced at about 320 nm. - Highlights: • Cinchona alkaloid-terpyridine derivatives and metal complexes were prepared. • Cinchona alkaloid-terpyridine derivatives gave off luminescence at 362 nm. • Ligand excited energy could efficiently transferred to lanthanide ions. • Chirality of terpyridine and metal complexes was induced.

  16. A novel stable 3D luminescent uranyl complex for highly efficient and sensitive recognition of Ru3+ and biomolecules

    Science.gov (United States)

    Tian, Hong-Hong; Chen, Liang-Ting; Zhang, Rong-Lan; Zhao, Jian-She; Liu, Chi-Yang; Weng, Ng Seik

    2018-02-01

    A novel highly stable 3D luminescent uranyl coordination polymer, namely {[UO2(L)]·DMA}n (1), was assembled with uranyl salt and a glycine-derivative ligand [6-(carboxymethyl-amino)-4-oxo-4,5-dihydro-[1,3,5]triazin-2-ylamino]-acetic acid (H2L) under solvothermal reaction. Besides, It was found that complex 1 possesses excellent luminescent properties, particularly the efficient selectivity and sensitivity in the recognition of Ru3+, biomacromolecule bovine serum albumin (BSA), biological small molecules dopamine (DA), ascorbic acid (AA) and uric acid (UA) in the water solution based on a "turn-off" mechanism. Accordingly, the luminescent explorations also demonstrated that complex 1 could be acted as an efficient luminescent probe with high quenching efficiency and low detection limit for selectively detecting Ru3+ and biomolecules (DA, AA, UA and BSA). It was noted that the framework structure of complex 1 still remains highly stable after quenching, which was verified by powder X-ray diffraction (PXRD).

  17. A new luminescent terbium 4-methylsalicylate complex as a novel sensor for detecting the purity of methanol.

    Science.gov (United States)

    Zeng, Cheng-Hui; Yang, Yang-Yi; Zhu, Yi-Min; Wang, Hong-Ming; Chu, Tian-Shu; Ng, Seik Weng

    2012-01-01

    A new dinuclear terbium complex [Tb(2)(4-msal)(6)(H(2)O)(4)]·6H(2)O (1) (4-msal = 4-methylsalcylate) was synthesized. Its structure was determined by single crystal X-ray diffraction, and the complex was characterized by PXRD, FT-IR, fluorescence, TGA and DTA. Complex 1 exists as discrete molecules that are linked by extensive O-H … O hydrogen bonds into a 3D network. The luminescence lifetimes of 3 μM methanol solution and solid sample of 1 are 1.321 and 1.009 ms, respectively. The quantum yield of solid sample is 6.0%. The luminescence quenched more than 50% when 3% (vol/vol) different impurities (acetone, acetonitrile, chloroform, dichloromethane, dioxane, DMF, DMSO, ethanol, ether, ethyl acetate, glycol, H(2)O, hexane, TEA, THF and toluene or their mixture) were added. The inverse linear relationship between the Lg value of fluorescence intensity and the volume ratio of the minor component (to a maximum of 20%) is interpreted in terms of LgI = a-bX (I: luminescence intensity; X: volume ratio of impurities in methanol; a, b are constants). So 1 is a potential luminescent sensor for analyzing the purity of methanol. © 2012 Wiley Periodicals, Inc. Photochemistry and Photobiology © 2012 The American Society of Photobiology.

  18. Alkane Soluble Transition Metal Complexes.

    Science.gov (United States)

    1983-10-01

    lCam ludoalNm’s W S. has aA F. . Hadley. uppokli *mvahs Capm amAe Hall. 1~i. 6. 08 o.. ILDuataA ulpmr. Cai. 1d. CAM 4. 111aII. lop C Themm. - hftupvtm of...phoahines.3 descrbed previously.’ In this analyuis a series of assumption . isre onadc Our reasons for doing this were twofold. in order to enable a lhoea...nalytical method to be used. It sii be w-me First, pfmospftane complexes have been widely used as be. apparent that the assumptions that must be made

  19. Self-organization in metal complexes

    International Nuclear Information System (INIS)

    Radecka-Paryzek, W.

    1999-01-01

    Inorganic self-organization involves the spontaneous generation of well-defined supramolecular architectures from metal ions and organic ligands. The basic concept of supramolecular chemistry is a molecular recognition. When the substrate are metal ions, recognition is expressed in the stability and selectivity of metal ion complexation by organic ligands and depends on the geometry of the ligand and on their binding sites that it contains. The combination of the geometric features of the ligand units and the coordination geometries of the metal ions provides very efficient tool for the synthesis of novel, intriguing and highly sophisticated species such as catenanes, box structures, double and triple helicates with a variety of interesting properties. The article will focus on the examples of inorganic self-organization involving the templating as a first step for the assembly of supramolecular structures of high complexity. (author)

  20. On monosubstituted cyanurate complexes of transition metals

    International Nuclear Information System (INIS)

    Sejfer, G.B.; Tarasova, Z.A.

    1995-01-01

    Complex monosubstituted cyanurates of transition metals K 2 [Eh(H 2 C 3 N 3 O 3 ) 4 ]x4H 2 ) where Eh = Mn, Co, Ni, Cu, Zn, Cd are synthesized and investigated by means of IR - spectroscopy and thermal analysis methods. It is shown that only thermal decomposition of a manganese complex leads to the production of this metal oxide. All other derivatives decompose with the production of a free metal, because decomposition of these substances in argon atmosphere occurs through an intermediate production of their nitrides. An assumption is made that nitroduction of yttrium or rare earth element salts (instead of transition or alkali metal derivatives) as accelerating additions will facilitate increase of polyisocyanurate resin thermal stability. 25 refs.; 2 figs.; 3 tabs

  1. Synthesis and Luminescence Properties of Iridium(III Azide- and Triazole-Bisterpyridine Complexes

    Directory of Open Access Journals (Sweden)

    Timothy W. Schmidt

    2013-07-01

    Full Text Available We describe here the synthesis of azide-functionalised iridium(III bisterpyridines using the “chemistry on the complex” strategy. The resulting azide-complexes are then used in the copper(I-catalysed azide-alkyne Huisgen 1,3-dipolar cycloaddition “click chemistry” reaction to from the corresponding triazole-functionalised iridium(III bisterpyridines. The photophysical characteristics, including lifetimes, of these compounds were also investigated. Interestingly, oxygen appears to have very little effect on the lifetime of these complexes in aqueous solutions. Unexpectedly, sodium ascorbate acid appears to quench the luminescence of triazole-functionalised iridium(III bisterpyridines, but this effect can be reversed by the addition of copper(II sulfate, which is known to oxidize ascorbate under aerobic conditions. The results demonstrate that iridium(III bisterpyridines can be functionalized for use in “click chemistry” facilitating the use of these photophysically interesting complexes in the modification of polymers or surfaces, to highlight just two possible applications.

  2. A General Model of Sensitized Luminescence in Lanthanide-Based Coordination Polymers and Metal-Organic Framework Materials.

    Science.gov (United States)

    Einkauf, Jeffrey D; Clark, Jessica M; Paulive, Alec; Tanner, Garrett P; de Lill, Daniel T

    2017-05-15

    Luminescent lanthanides containing coordination polymers and metal-organic frameworks hold great potential in many applications due to their distinctive spectroscopic properties. While the ability to design coordination polymers for specific functions is often mentioned as a major benefit bestowed on these compounds, the lack of a meaningful understanding of the luminescence in lanthanide coordination polymers remains a significant challenge toward functional design. Currently, the study of these compounds is based on the antenna effect as derived from molecular systems, where organic antennae are used to facilitate lanthanide-centered luminescence. This molecular-based approach does not take into account the unique features of extended network solids, particularly the formation of band structure. While guidelines for the antenna effect are well established, they require modification before being applied to coordination polymers. A series of nine coordination polymers with varying topologies and organic linkers were studied to investigate the accuracy of the antenna effect in coordination polymer systems. By comparing a molecular-based approach to a band-based one, it was determined that the band structure that occurs in aggregated organic solids needs to be considered when evaluating the luminescence of lanthanide coordination polymers.

  3. Reaction mechanisms of metal complexes

    CERN Document Server

    Hay, R W

    2000-01-01

    This text provides a general background as a course module in the area of inorganic reaction mechanisms, suitable for advanced undergraduate and postgraduate study and/or research. The topic has important research applications in the metallurgical industry and is of interest in the science of biochemistry, biology, organic, inorganic and bioinorganic chemistry. In addition to coverage of substitution reactions in four-, five- and six-coordinate complexes, the book contains further chapters devoted to isomerization and racemization reactions, to the general field of redox reactions, and to the reactions of coordinated ligands. It is relevant in other fields such as organic, bioinorganic and biological chemistry, providing a bridge to organic reaction mechanisms. The book also contains a chapter on the kinetic background to the subject with many illustrative examples which should prove useful to those beginning research. Provides a general background as a course module in the area of inorganic reaction mechanis...

  4. Luminescent lanthanide complexes with 4-acetamidobenzoate: Synthesis, supramolecular assembly via hydrogen bonds, crystal structures and photoluminescence

    International Nuclear Information System (INIS)

    Yin Xia; Fan Jun; Wang Zhihong; Zheng Shengrun; Tan Jingbo; Zhang Weiguang

    2011-01-01

    Four new luminescent complexes, namely, [Eu(aba) 2 (NO 3 )(C 2 H 5 OH) 2 ] (1), [Eu(aba) 3 (H 2 O) 2 ].0.5 (4, 4'-bpy).2H 2 O (2), [Eu 2 (aba) 4 (2, 2'-bpy) 2 (NO 3 ) 2 ].4H 2 O (3) and [Tb 2 (aba) 4 (phen) 2 (NO 3 ) 2 ].2C 2 H 5 OH (4) were obtained by treating Ln(NO 3 ) 3 .6H 2 O and 4-acetamidobenzoic acid (Haba) with different coligands (4, 4'-bpy=4, 4'-bipyridine, 2, 2'-bpy=2, 2'-bipyridine, and phen=1, 10-phenanthroline). They exhibit 1D chains (1-2) and dimeric structures (3-4), respectively. This structural variation is mainly attributed to the change of coligands and various coordination modes of aba molecules. Moreover, the coordination units are further connected via hydrogen bonds to form 2D even 3D supramolecular networks. These complexes show characteristic emissions in the visible region at room temperature. In addition, thermal behaviors of four complexes have been investigated under air atmosphere. The relationship between the structures and physical properties has been discussed. - Graphical abstract: Structure variation of four complexes is attributed to the change of coligands and various coordination modes of aba molecules. Moreover, they show characteristic emissions in the visible region. Highlights: → Auxiliary ligands have played the crucial roles on the structures of the resulting complexes. → Isolated structure units are further assembled via H-bonds to form supramolecular networks. → These solid-state complexes exhibit strong, characteristic emissions in the visible region.

  5. A 3D Ag(I) metal-organic framework for sensing luminescence and photocatalytic activities

    Science.gov (United States)

    Chang, Hai-Ning; Liu, Li-Wei; Hao, Zeng Chuan; Cui, Guang-Hua

    2018-03-01

    A fluorescent metal-organic framework (MOF), [Ag(btx)0.5(DCTP)0.5]n (1) (H2DCTP = 2,5-dichloroterephthalic acid and btx = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene) has been hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, powder X-ray diffractions and thermogravimetry. The framework of 1 can be classified as a binodal (4,4)-connected PtS topological network. The fluorescence explorations demonstrated that 1 shows selective and sensitive detection towards Cr2O72- with high quenching efficiency of 1.92 × 104 M-1. The rapid and efficient response of 1 to Cr2O72- ion suggests that this material could be used as a luminescent sensor for Cr2O72- ion. Meanwhile the photocatalytic properties of 1 for the degradation of RhB have also been investigated under UV radiation. The possible photocatalytic mechanisms were also speculated. Hence, 1 can become multi-functional material in sensitive detection and effective removal of some environment pollutants in industrial waste water solutions.

  6. Using metal complex-labeled peptides for charge transfer-based biosensing with semiconductor quantum dots

    Science.gov (United States)

    Medintz, Igor L.; Pons, Thomas; Trammell, Scott A.; Blanco-Canosa, Juan B.; Dawson, Philip E.; Mattoussi, Hedi

    2009-02-01

    Luminescent colloidal semiconductor quantum dots (QDs) have unique optical and photonic properties and are highly sensitive to charge transfer in their surrounding environment. In this study we used synthetic peptides as physical bridges between CdSe-ZnS core-shell QDs and some of the most common redox-active metal complexes to understand the charge transfer interactions between the metal complexes and QDs. We found that QD emission underwent quenching that was highly dependent on the choice of metal complex used. We also found that quenching traces the valence or number of metal complexes brought into close proximity of the nanocrystal surface. Monitoring of the QD absorption bleaching in the presence of the metal complex provided insight into the charge transfer mechanism. The data suggest that two distinct charge transfer mechanisms can take place. One directly to the QD core states for neutral capping ligands and a second to surface states for negatively charged capping ligands. A basic understanding of the proximity driven charge-transfer and quenching interactions allowed us to construct proteolytic enzyme sensing assemblies with the QD-peptide-metal complex conjugates.

  7. Effect of symmetric substitution on the phenyl groups of Eu{sup 3+}-dibenzoyl methane complexes on their luminescence properties

    Energy Technology Data Exchange (ETDEWEB)

    Shukla, P. [Bio-Organic Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Sudarsan, V.; Vatsa, R.K. [Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Nayak, S.K. [Bio-Organic Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Chattopadhyay, S., E-mail: schatt@barc.gov.i [Bio-Organic Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India)

    2010-10-15

    Complexes of Eu{sup 3+} ion and ligands like dibenzoylmethane (DBM) as well as flouro- and methoxy-substituted DBMs have been prepared and characterized. Peak maxima and line shapes of the {pi}-{pi}{sup *} transitions arising from the ligands in these complexes were very sensitive to the nature of the substituents attached to the phenyl groups of DBM. Symmetric substitution at both the phenyl groups led to improved luminescence in terms of higher quantum yields of emission and longer lifetime of the excited state ({sup 5}D{sub 0}) of Eu{sup 3+} ions. Effective averaging/cancellation of the dipole-dipole interactions in symmetrically substituted ligands and the associated decrease in the extent of quenching were responsible for the improved luminescence from such complexes.

  8. Silver-induced reconstruction of an adeninate-based metal-organic framework for encapsulation of luminescent adenine-stabilized silver clusters.

    Science.gov (United States)

    Jonckheere, Dries; Coutino-Gonzalez, Eduardo; Baekelant, Wouter; Bueken, Bart; Reinsch, Helge; Stassen, Ivo; Fenwick, Oliver; Richard, Fanny; Samorì, Paolo; Ameloot, Rob; Hofkens, Johan; Roeffaers, Maarten B J; De Vos, Dirk E

    2016-05-21

    Bright luminescent silver-adenine species were successfully stabilized in the pores of the MOF-69A (zinc biphenyldicarboxylate) metal-organic framework, starting from the intrinsically blue luminescent bio-MOF-1 (zinc adeninate 4,4'-biphenyldicarboxylate). Bio-MOF-1 is transformed to the MOF-69A framework by selectively leaching structural adenine linkers from the original framework using silver nitrate solutions in aqueous ethanol. Simultaneously, bright blue-green luminescent silver-adenine clusters are formed inside the pores of the recrystallized MOF-69A matrix in high local concentrations. The structural transition and concurrent changes in optical properties were characterized using a range of structural, physicochemical and spectroscopic techniques (steady-state and time-resolved luminescence, quantum yield determination, fluorescence microscopy). The presented results open new avenues for exploring the use of MOFs containing luminescent silver clusters for solid-state lighting and sensor applications.

  9. Synthesis and luminescent properties of two Schiff-base boron complexes

    Energy Technology Data Exchange (ETDEWEB)

    Hou Qiufei [Key Lab for Supramolecular Structure and Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Zhao Liyan [Key Lab for Supramolecular Structure and Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Zhang Hongyu [Key Lab for Supramolecular Structure and Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Wang Yue [Key Lab for Supramolecular Structure and Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Jiang Shimei [Key Lab for Supramolecular Structure and Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China)]. E-mail: smjiang@jlu.edu.cn

    2007-10-15

    Schiff bases N,N'-o-phenylenebis (salicylideneimine) (H{sub 2} L{sup 1} ), N,N'-p-phenylenebis (salicylideneimine) (H{sub 2} L{sup 2} ) and their corresponding boron complexes (BF{sub 2}){sub 2} L{sup 1} (BF{sub 2}){sub 2} L{sup 2} were synthesized, respectively. The two boron complexes have been characterized by {sup 1}H NMR, mass spectrometry and elemental analysis, while the luminescent properties of them were investigated with UV-VIS spectroscopy and photoluminescence spectroscopy. Then the three-layer devices [ITO/NPB (60 nm)/(BF{sub 2}){sub 2} L{sup 1} (50 nm)/Alq3 (20 nm)/LiF (1 nm)/Al (200 nm)] (device I) and [ITO/NPB (60 nm)/(BF{sub 2}){sub 2} L{sup 2} (50 nm)/Alq3 (20 nm)/LiF (1 nm)/Al (200 nm)] (device II) were fabricated by vacuum deposition. These two devices both exhibited blue green emission at 500 nm, but showed different luminances and efficiencies.

  10. Synthesis and luminescent properties of a novel green-emitting Tb (Ⅲ) complex based on amino-modified fluorine silicone oil and isophorone diisocyanate

    Science.gov (United States)

    Hao, Haixia; Chu, Yang; Yu, Zhenjiang; Xie, Hongde; Seo, Hyo Jin

    2017-10-01

    The novel luminescent polymer-rare earth complexes, denoted as (PFSi-IPDI)-Tb(Ⅲ)-Phen, have been successfully synthesized and can be made into flexible films. Amino-modified fluorine silicone oil-isophorone diisocyanate (PFSi-IPDI) was used as the host macromolecular ligand, and 1, 10-Phenanthroline (Phen) as the secondary small-molecular co-ligand. The luminescent lanthanide complexes were characterized by fourier transform infrared (FITR), scanning electron microscope (SEM), thermogravimetric analysis (TGA). The luminescent properties were investigated through photoluminescence excitation (PLE) and emission (PL) spectroscopy. FTIR analysis verifies the successful preparation and integration of PFSi-IPDI to Tb3+. The comparatively uniform morphological structure can be observed in the images of SEM. The polymer-rare earth complexes display the typical luminescence emission peaks under the excitation wavelength of 330 nm. From the decay curve, the short lifetime (about 0.89 ms) is observed for (PFSi-IPDI)-Tb(Ⅲ)-Phen (0.6 mol/L). Moreover, these luminescent polymer-rare earth complexes possess superior thermal stability (T5 > 195 °C). All the interesting results suggest the potential application of the luminescent polymer-rare earth complexes in green-emitting luminescent materials under high temperature.

  11. Anharmonic Vibrational Spectroscopy on Metal Transition Complexes

    Science.gov (United States)

    Latouche, Camille; Bloino, Julien; Barone, Vincenzo

    2014-06-01

    Advances in hardware performance and the availability of efficient and reliable computational models have made possible the application of computational spectroscopy to ever larger molecular systems. The systematic interpretation of experimental data and the full characterization of complex molecules can then be facilitated. Focusing on vibrational spectroscopy, several approaches have been proposed to simulate spectra beyond the double harmonic approximation, so that more details become available. However, a routine use of such tools requires the preliminary definition of a valid protocol with the most appropriate combination of electronic structure and nuclear calculation models. Several benchmark of anharmonic calculations frequency have been realized on organic molecules. Nevertheless, benchmarks of organometallics or inorganic metal complexes at this level are strongly lacking despite the interest of these systems due to their strong emission and vibrational properties. Herein we report the benchmark study realized with anharmonic calculations on simple metal complexes, along with some pilot applications on systems of direct technological or biological interest.

  12. Determination of organophosphorus pesticides in water samples by using a new sensitive luminescent probe of Eu (III) complex

    Energy Technology Data Exchange (ETDEWEB)

    Azab, Hassan A., E-mail: azab2@yahoo.com; Anwar, Z.M.; Rizk, M.A.; Khairy, Gasser M.; El-Asfoury, M.H.

    2015-01-15

    This work describes the application of fluorescence for investigating the interactions of Eu(III)-TAN-1,10 phenanthroline (where TAN=4,4,4-Trifluoro-1-(2-naphthyl)-1,3-butanedione) with pesticides Chlorpyrifos, Malathion, Endosulfan, Heptachlor. The complex was synthesized and characterized by elemental analysis, FTIR, x-ray spectroscopy, solid fluorescence and thermal analysis. The results indicated that the composition of this complex is [Eu(TAN){sub 2}(Phen)(H{sub 2}O){sub 2}]Cl. The luminescence properties of the complex in different solvents and at different pH values have been investigated. The results show that the complex exhibits more efficient luminescence at pH=7.5. The interactions of Eu-complex with different pesticides (Chlorpyrifos, Malathion, Endosulfan, and Heptachlor) in aqueous medium have been investigated by fluorescence measurements. The luminescence intensity of the probe is quenched by Malathion and enhanced by (Endosulfan, Heptachlor, and Chlorpyrifos). Direct methods for the determination of the pesticides under investigation have been developed using the luminescence variations of the probe in solution. The detection limits are 0.47, 1.02, 0.66, 0.64 µmol/L for Chlorpyrifos, Endosulfan, Heptachlor, and Malathion, respectively. The binding constants and thermodynamic parameters of the pesticides with probe were evaluated. The emission quantum yield (QY=0.71) of Eu(III)-complex was determined using tris (2,2'-bipyridyl) dichlororuthenium(II) hexahydrate. A thermodynamic analysis showed that the reaction is spontaneous with negative ΔG. Effect of some relevant interferents on the detection of pesticides has been investigated. The new method was applied to the determination of the pesticides in different types of water samples (tap, river, and waste water). - Highlights: • A new luminescent probe of Eu (III) complex has been developed for sensing some organophosphorus pesticides. • Four guest pesticides Chlorpyrifos, Malathion

  13. Determination of organophosphorus pesticides in water samples by using a new sensitive luminescent probe of Eu (III) complex

    International Nuclear Information System (INIS)

    Azab, Hassan A.; Anwar, Z.M.; Rizk, M.A.; Khairy, Gasser M.; El-Asfoury, M.H.

    2015-01-01

    This work describes the application of fluorescence for investigating the interactions of Eu(III)-TAN-1,10 phenanthroline (where TAN=4,4,4-Trifluoro-1-(2-naphthyl)-1,3-butanedione) with pesticides Chlorpyrifos, Malathion, Endosulfan, Heptachlor. The complex was synthesized and characterized by elemental analysis, FTIR, x-ray spectroscopy, solid fluorescence and thermal analysis. The results indicated that the composition of this complex is [Eu(TAN) 2 (Phen)(H 2 O) 2 ]Cl. The luminescence properties of the complex in different solvents and at different pH values have been investigated. The results show that the complex exhibits more efficient luminescence at pH=7.5. The interactions of Eu-complex with different pesticides (Chlorpyrifos, Malathion, Endosulfan, and Heptachlor) in aqueous medium have been investigated by fluorescence measurements. The luminescence intensity of the probe is quenched by Malathion and enhanced by (Endosulfan, Heptachlor, and Chlorpyrifos). Direct methods for the determination of the pesticides under investigation have been developed using the luminescence variations of the probe in solution. The detection limits are 0.47, 1.02, 0.66, 0.64 µmol/L for Chlorpyrifos, Endosulfan, Heptachlor, and Malathion, respectively. The binding constants and thermodynamic parameters of the pesticides with probe were evaluated. The emission quantum yield (QY=0.71) of Eu(III)-complex was determined using tris (2,2'-bipyridyl) dichlororuthenium(II) hexahydrate. A thermodynamic analysis showed that the reaction is spontaneous with negative ΔG. Effect of some relevant interferents on the detection of pesticides has been investigated. The new method was applied to the determination of the pesticides in different types of water samples (tap, river, and waste water). - Highlights: • A new luminescent probe of Eu (III) complex has been developed for sensing some organophosphorus pesticides. • Four guest pesticides Chlorpyrifos, Malathion, Endosulfan, and

  14. A comparative study of the structure and luminescence of mono- and dinuclear crown-ether lanthanide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Keyla M.N. de [Departamento de Química, Universidade Federal Rural de Pernambuco, Rua Dom Manoel de Medeiros, S/N – Dois Irmãos, 52171-900 Recife, Pernambuco (Brazil); Batista, Hélcio J., E-mail: helciojb@gmail.com [Departamento de Química, Universidade Federal Rural de Pernambuco, Rua Dom Manoel de Medeiros, S/N – Dois Irmãos, 52171-900 Recife, Pernambuco (Brazil); Belian, Mônica F. [Departamento de Química, Universidade Federal Rural de Pernambuco, Rua Dom Manoel de Medeiros, S/N – Dois Irmãos, 52171-900 Recife, Pernambuco (Brazil); Silva, Wagner E. [Unidade Acadêmica do Cabo de Santo Agostinho, Universidade Federal Rural de Pernambuco, 54510-000 Cabo de Santo Agostinho, Pernambuco (Brazil); Silva, Juliana A.B. da [Centro Acadêmico do Agreste, Universidade Federal de Pernambuco, 55002-970 Caruaru, Pernambuco (Brazil)

    2016-02-15

    Using as precursor the mononuclear lanthanide (Ln) macrocyclic complex, based on the 15-crown-5 ether (C) ligand and coordinated water (W) molecules, [LnCW{sub 4}]{sup 3+}, four novel analogous complexes for each of the three Ln(III) ions (Ln=Eu, Tb and Gd) were synthesized through systematic substitution of water molecules by the antenna-type ligands: 2,2′-dipyridyl (D), 1,10-phenanthroline (P) and 2,2′;6',2′′-terpyridine (T). The corresponding formulae of the complexes, obtained in a trichloride salt form, were the following: [LnCW{sub 4}]{sup 3+}, [LnCP{sub 2}]{sup 3+}, [LnCDW]{sup 3+}, [LnCDP]{sup 3+}, and [LnCT]{sup 3+}. The compounds were characterized by elemental analysis, UV and infrared spectroscopy and investigated through luminescence spectroscopy. For the Eu(III) and Tb(III) complex series, the most luminescent ones were [EuCDP]{sup 3+} and [TbCT]{sup 3+}, respectively. Motivated by this fact, two dinuclear analogous Eu(III) and Tb(III) complexes, based on the two-site coordinating macrocyclic ligand lariat-silacrown ether (S), as well as analogous Gd(III) complexes, were obtained as hexachloride salts with the following formulae: [Eu{sub 2}SD{sub 2}P{sub 2}]{sup 6+}, [Gd{sub 2}SD{sub 2}P{sub 2}]{sup 6+}, [Tb{sub 2}ST{sub 2}]{sup 6+} and [Gd{sub 2}ST{sub 2}]{sup 6+}. Also, [Eu{sub 2}SW{sub 8}]{sup 6+}, [Tb{sub 2}SW{sub 8}]{sup 6+} and [Gd{sub 2}SW{sub 8}]{sup 6+} complexes were prepared and used as reference non-antenna type dinuclear compounds. Comparing the luminescence between the antenna mononuclear complexes with the analogous dinuclear ones, for Eu(III) and Tb(III) ions, almost no change was observed. On the other hand, in the particular case of Eu(III), comparing the mono- and dinuclear non-antenna reference complexes [EuCW{sub 4}]{sup 3+} and [Eu{sub 2}SW{sub 8}]{sup 6+}, a surprisingly much higher luminescence intensity was observed for the dinuclear complex (~ one order of magnitude). The proposed cause for this behavior is the

  15. Versatile lanthanide-azide complexes with azide/carboxylate/hydroxy mixed bridged chain exhibiting magnetic and luminescent properties

    International Nuclear Information System (INIS)

    Wang Haichao; Xue Min; Guo Qian; Zhao Jiongpeng; Liu Fuchen; Ribas, Joan

    2012-01-01

    Two new lanthanide-azide complexes, [Ln 2 (N 3 )(isonic) 2 (OH) 3 (Hisonic)(H 2 O)] n (Ln=Yb for 1 and Tb for 2, isonic=isonicotinate), were obtained in hydrothermal condition. X-ray diffraction analysis indicated the two complexes are isomorphic chain structure in which the Ln III ions are mixed bridged by the azide anions, hydroxyl anions and carboxylate groups of the isonicotinate ligands. Further studies indicated weak antiferromagnetic interactions between the Ln III ions in 1 and 2, and complex 2 exhibit green sensitized Luminescent character of Tb III ion. - Graphical abstract: Two new 1D lanthanide-azide complexes, [Ln 2 (N 3 )(isonic) 2 (OH) 3 (Hisonic)(H 2 O)] n (Ln=Yb III for 1 and Tb III for 2, isonic=isonicotinate), were synthesized by hydrothermal reaction and exhibit interesting magnetism and fluorescence properties. Highlights: ► The research provided a new method for synthesizing lanthanide-azide complexes. ► The complexes have an interesting azide/hydroxyl/carboxylate mixed bridged1D chain structure. ► The antiferromagnetic coupling between the complexes and 2 displays green luminescence.

  16. COMPLEXES POLYMETALLIQUES DE LANTHANIDES (III) POUR LE DEVELOPPEMENT DE NOUVEAUX MATERIAUX LUMINESCENTS

    OpenAIRE

    Marchal , Claire

    2008-01-01

    The incorporation of f elements in highly organized polymetallic complexes is of great interest in supramolecularchemistry and allows the combination of their nanoscopic size with the magnetic or optical properties of the metal ions. However due to the difficulty in controlling the coordination environment of these ions, the assembly of lanthanide-based polynuclear architectures has lagged behind that of other systems. These factors make the rational design for the construction of supramolecu...

  17. Luminescence quenching by heavy metal ions of probes based on anthracene, pyrene, and eosin in human serum albumin

    Science.gov (United States)

    Naumova, E. V.; Melnikov, A. G.; Melnikov, G. V.

    2013-05-01

    Fluorescence and phosphorescence quenching processes of polar and non-polar luminescent probes associated with human serum albumin (HSA) in phosphate buffer at pH 7.4 were studied. Stern-Volmer quenching constants of anthracene and pyrene fluorescence and eosin phosphorescence and rate constants for quenching of eosin triplet states were determined. The polarity index of pyrene bound to HSA was obtained as a function of thallium nitrate concentration. The influences of structural changes in the proteins that were stimulated by heavy-metal salts and of screening of protein charges by salt ions on quenching processes of singlet and triplet states of the probes were found.

  18. TDPAC studies on metal-complex ferrimagnets

    Energy Technology Data Exchange (ETDEWEB)

    Ohkubo, Yoshitaka [Kyoto Univ., Kumatori, Osaka (Japan). Research Reactor Inst.; Abe, Shizuko; Okada, Takuya [and others

    1997-03-01

    TDPAC spectra of {sup 117}In (left-arrow {sup 117}Cd) and {sup 111}Cd (left-arrow {sup 111m}Cd) in the mixed metal complex N(C{sub 4}H{sub 9}){sub 4}(M(II)Fe(III)(C{sub 2}O{sub 4}){sub 3})(M=Fe,Ni), the related substraces and LiNbO{sub 3} have been studied. In this paper, pure potassium iron (III) oxalate was prepared and mixed metal complexes were synthesized by changing amount of reagents and the order added, then observed by TDPAC. 2 mol%Cd was dispersed throughout potassium iron oxalate and potassium nickel oxalate, formulating M(II){sub 0.98}Cd(II){sub 0.02}C{sub 2}O{sub 4}{center_dot}2H{sub 2}O (M=Fe, Ni) with the same crystal structure. The formation reaction of mixed metal complex-Fe(II) was faster than that of iron oxalate. Its mixed metal complex-Ni(II) was slower than that of iron oxalate. The rate of quadrupole oscillation was obtained by {omega}{sub Q}({sup 117}In)=67.3 Mrad/s and {omega}{sub Q}({sup 111}Cd)=29.7 Mrad/s of which values were determined by TDPAC spectra of {sup 117}In and {sup 111}Cd in LiNbO{sub 3} at 4K. The value showed pure ion bond of oxygen coordinated with {sup 117}In and {sup 111}Cd. 0.08 {eta} was determined by TDPAC spectrum of {sup 111}Cd(left-arrow {sup 111m}Cd). The rate of {omega}{sub Q} of mixed metal oxalate complex was larger than 2.3, indicating 5s and 5p orbital electron took part in bond of oxygen of oxalic acid or approaching oxygen ion to In nucleus depend on the structual relaxation in decaying of {sup 117}In(left-arrow {sup 117}Cd). (S.Y.)

  19. Syntheses and luminescence properties of two novel lanthanide (III) perchlorate complexes with phenacyl p-tolyl sulfoxide

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Shu-Yan [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Li, Wen-Xian, E-mail: nmglwx@163.com [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Zheng, Yu-Shan [Inner Mongolia Autonomous Region Product Quality Inspection Institute, Hohhot 010070 (China); Xin, Xiao-Dong; Guo, Feng; Cao, Xiao-Fang [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China)

    2015-06-15

    Two novel solid binary complexes of rare earth perchlorate with phenacyl p-tolyl sulfoxide were synthesized and characterized by elemental analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, {sup 1}HNMR and UV spectra. The results indicated that the composition of these complexes was REL{sub 7} (ClO{sub 4}){sub 3}·6H{sub 2}O (RE=Eu (III), Tb (III), L=C{sub 6}H{sub 5}COCH{sub 2}SOC{sub 6}H{sub 4}CH{sub 3}). The study on IR spectra and {sup 1}HNMR spectra revealed that phenacyl p-tolyl sulfoxide bonded with RE{sup 3+} ions by the oxygen atom in sulfinyl group. The emission spectra illustrated that both the Eu (III) and Tb (III) complexes displayed excellent luminescence in solid state, and The most intensive characteristic emission of the Eu(III) and Tb(III) complexes were 245,400 a.u. and 298,000 a.u. respectively. The slit with was 1 nm. By analysis luminescence and phosphorescence spectrum, it was found that the ligand had the advantage to absorb energy and transfer it to the Eu (III) and Tb (III) ions. The fluorescence lifetimes of the complexes were measured as well as the quantum yield of the Eu (III) complex.

  20. Zinc(II) halide complexes with 2-methoxyaniline ligand: Synthesis, characterization, thermal analyses, crystal structure determination and luminescent properties

    Science.gov (United States)

    Amani, Vahid

    2018-03-01

    Three new mononuclear zinc(II) complexes, [Zn(2-MeO-C6H4NH2)2X2] (X is Cl in 1, Br in 2 and I in 3), were prepared from the reactions of ZnX2 with 2-methoxyaniline (2-MeO-C6H4NH2) ligand in methanol. Suitable crystals of these complexes were obtained for X-ray diffraction measurements by slow evaporation of methanol solution at room temperature. The three complexes were thoroughly characterized by thermogravimetric analysis, elemental analysis (CHNO), spectral methods (IR, UV-Vis, 13C{1H}NMR, 1H NMR and luminescence), and single crystal X-ray diffraction. The X-ray structural analysis indicated that in the structures of these complexes, the zinc(II) cation is four-coordinated in a distorted tetrahedral configuration by two N atoms from two 2-methoxyanyline ligands and two halide anions. Also, in these complexes intermolecular interactions, for example Nsbnd H⋯X hydrogen bonds (in 1-3), Csbnd H⋯X hydrogen bonds (in 3), Csbnd H⋯π interactions (in 1 and 2) and π⋯π interactions (in 3), are effective in the stabilization of the crystal structures. In addition, the luminescence spectra of all complexes in methanolic solution show that the intensity of their emission bands is stronger than that for free 2-methoxyaniline ligand.

  1. A colorimetric and luminescent dual-modal assay for Cu(II ion detection using an iridium(III complex.

    Directory of Open Access Journals (Sweden)

    Dik-Lung Ma

    Full Text Available A novel iridium(III complex-based chemosensor bearing the 5,6-bis(salicylideneimino-1,10-phenanthroline ligand receptor was developed, which exhibited a highly sensitive and selective color change from colorless to yellow and a visible turn-off luminescence response upon the addition of Cu(II ions. The interactions of this iridium(III complex with Cu2+ ions and thirteen other cations have been investigated by UV-Vis absorption titration, emission titration, and 1H NMR titration.

  2. Biological activities of some Fluoroquinolones-metal complexes

    African Journals Online (AJOL)

    McRoy

    DNA cleavage studies of some synthesized metal complexes of fluoroquinolone ... Although the FQs are generally characterized by a broad antimicrobial spectrum ..... six Coordinate 3rd metal complexes with N- (5 –Phenyl-3,4- thiadiazol-2-yl).

  3. Luminescent cyclometalated alkynylgold(III) complexes with 6-phenyl-2,2'-bipyridine derivatives: synthesis, characterization, electrochemistry, photophysics, and computational studies.

    Science.gov (United States)

    Au, Vonika Ka-Man; Lam, Wai Han; Wong, Wing-Tak; Yam, Vivian Wing-Wah

    2012-07-16

    A novel class of luminescent gold(III) complexes containing various tridentate cyclometalating ligands derived from 6-phenyl-2,2'-bipyridine and alkynyl ligands, [Au(RC^N^N)(C≡C-R')]PF(6), has been successfully synthesized and characterized. One of the complexes has also been determined by X-ray crystallography. Electrochemical studies show a ligand-centered reduction originated from the cyclometalating RC^N^N ligands as well as an alkynyl-centered oxidation. The electronic absorption and photoluminescence properties of the complexes have also been investigated. In acetonitrile at room temperature, the complexes show intense absorption at higher energy region with wavelength shorter than 320 nm, and a moderately intense broad absorption band at 374-406 nm, assigned as the metal-perturbed intraligand π-π* transition of the cyclometalating RC(∧)N(∧)N ligand, with some charge transfer character from the aryl ring to the bipyridine moiety. Most of the complexes have been observed to show vibronic-structured emission bands at 469-550 nm in butyronitile glass at 77 K, assigned to an intraligand excited state of the RC^N^N ligand, with some charge transfer character from the aryl to the bipyridyine moiety. Insights into the origin of the absorption and emission have also been provided by density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations.

  4. Photochemical activation and reactivity of polynuclear transition metal complex molecules. Final report

    International Nuclear Information System (INIS)

    Endicott, J.F.; Lintvedt, R.L.

    1982-06-01

    Several bi- and trinuclear metal complexes containing ligands from β-polyketonates have been synthesized and characterized including homo- and hetero-polynuclear complexes. New synthetic approaches to the preparation of heterobi- and trinuclear complexes have been developed that allow the preparation of a large number of molecules containing heavy-metal ions such as Pd 2+ or UO 2 2+ and a first-row transition-metal ion. The electrochemical properties of these complexes have been investigated and many exhibit the ability to transfer two electrons at very nearly the same potential. Photochemical studies on binuclear Cu(II) and Ni(II) showed that these compounds yielded reduced metal species and decomposition upon irradiation. Luminescence of hetero-complexes of uranyl polyketonates is observed at 77 0 K with the UO 2 2+ moiety functioning as an isolated chromophore in which emission is observed only on direct excitation of UO 2 2+ and energy transfer to lower states in the molecule is not observed

  5. The effect of complexation with platinum in polyfluorene derivatives: A photo- and electro-luminescence study

    International Nuclear Information System (INIS)

    Assaka, Andressa M.; Hu Bin; Mays, Jimmy; Iamazaki, Eduardo T.; Atvars, Teresa D.Z.; Akcelrud, Leni

    2011-01-01

    The synthesis and characterization of a polymeric structure containing fluorene units statistically linked to 3-cyclohexyl-thiophene and bipyridine PFOTBipy-poly[(4-hexylthiophene-2,5-diyl)(9,9-dihexyl-fluoren-2,7-diyl) -co-(bipyridine-5.5'-diyl)(9,9-dihexyl-fluoren-2,7-diyl)], is reported. The complexation with platinum was possible through the bipyridil units present in 10%, 50% and 100% content. The structure has a fluorenyl moiety between each bipyridine and thiophene groups resulting in a stable and efficient light-emitting polymeric material combining the well known emissive properties of fluorene, the charge mobility generated by thiophene and the electron-transfer properties of a metal complex as well. All the polymers were photo and electroluminescent materials, and showed phosphorescence at low temperatures. Photoluminescence properties were studied by steady state and time resolved spectroscopy and showed changes of both emission peak and relative intensity of the emission bands depending on the relative amount of the platinum complex. The electroluminescence followed the trends found for photoluminescence. The blue emission of the copolymer without platinum is due to the fluorenyl segments and for higher complex contents the emission is characteristic of the aggregates involving the bipyridinyl moieties. Therefore, emission color can be tuned by the complex content. The turn-on voltage was strongly reduced from 22 to 8 V for the 100% complexed copolymer, as compared to the device made with the non complexed one, but the luminance decreased, due to quenching or trapping effects. - Research Highlights: →Statistic copolymer containing fluorine, thiophene and bipyridine. →Complexation of platinum with platinum with bipyridine. →Electroluminescence and electrophosphorescence at low temperatures. →Emission color can be tuned by the complex content.

  6. Temperature dependence of the luminescence lifetime of a europium complex immobilized in different polymer matrices

    Energy Technology Data Exchange (ETDEWEB)

    Basu, Bharathi Bai J. [Surface Engineering Division, National Aerospace Laboratories, Bangalore 560017 (India)], E-mail: bharathi@css.nal.res.in; Vasantharajan, N. [Surface Engineering Division, National Aerospace Laboratories, Bangalore 560017 (India)

    2008-10-15

    The temperature dependence of the luminescence lifetime of temperature sensor films based on europium (III) thenoyltrifluoroacetonate (EuTTA) as sensor dye in various polymer matrices such as polystyrene (PS), polymethylmethacrylate (PMMA), polyurethane (PU) and model airplane dope was studied and compared. The luminescence lifetime of EuTTA was found to depend on the polymer matrix. The temperature sensitivity of lifetime was maximum for EuTTA-PS coating in the temperature range of 10-60 deg. C. The effect of concentration of the sensor dye in the polymer on the lifetime and temperature sensitivity was also studied.

  7. 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)

  8. Metal ammine complexes for hydrogen storage

    DEFF Research Database (Denmark)

    Christensen, Claus H.; Sørensen, Rasmus Zink; Johannessen, Tue

    2005-01-01

    The hopes of using hydrogen as an energy carrier are severely dampened by the fact that there is still no safe, high-density method available for storing hydrogen. We investigate the possibility of using metal ammine complexes as a solid form of hydrogen storage. Using Mg(NH3)(6)Cl-2 as the example......, we show that it can store 9.1% hydrogen by weight in the form of ammonia. The storage is completely reversible, and by combining it with an ammonia decomposition catalyst, hydrogen can be delivered at temperatures below 620 K....

  9. Evaluation of heavy metal complex phytotoxicity

    Directory of Open Access Journals (Sweden)

    Vita Vasilyevna Datsenko

    2016-07-01

    Full Text Available The experimental data dealing with the effect of heavy metals contained in the technogenic contaminated soils on plant objects under controlled conditions was discussed. The aim of this work is to define the quantitative indicators of copper and zinc potential phytotoxicity, namely germination energy, simultaneous germination and duration of the test plants. It was found that the activity of the test plant growth is linked with copper and zinc complex action. Joint effect of copper and zinc is manifested both in inhibition of lettuce growth and determined, above all, by the nature contamination, soil properties and biological specificity of the test plants.

  10. Time-dependent density functional theory study of the luminescence properties of gold phosphine thiolate complexes.

    Science.gov (United States)

    Guidez, Emilie B; Aikens, Christine M

    2015-04-09

    The origin of the emission of the gold phosphine thiolate complex (TPA)AuSCH(CH3)2 (TPA = 1,3,5-triaza-7-phosphaadamantanetriylphosphine) is investigated using time-dependent density functional theory (TDDFT). This system absorbs light at 3.6 eV, which corresponds mostly to a ligand-to-metal transition with some interligand character. The P-Au-S angle decreases upon relaxation in the S1 and T1 states. Our calculations show that these two states are strongly spin-orbit coupled at the ground state geometry. Ligand effects on the optical properties of this complex are also discussed by looking at the simple AuP(CH3)3SCH3 complex. The excitation energies differ by several tenths of an electronvolt. Excited state optimizations show that the excited singlet and triplet of the (TPA)AuSCH(CH3)2 complex are bent. On the other hand, the Au-S bond breaks in the excited state for the simple complex, and TDDFT is no longer an adequate method. The excited state energy landscape of gold phosphine thiolate systems is very complex, with several state crossings. This study also shows that the formation of the [(TPA)AuSCH(CH3)2]2 dimer is favorable in the ground state. The inclusion of dispersion interactions in the calculations affects the optimized geometries of both ground and excited states. Upon excitation, the formation of a Au-Au bond occurs, which results in an increase in energy of the low energy excited states in comparison to the monomer. The experimentally observed emission of the (TPA)AuSCH(CH3)2 complex at 1.86 eV cannot be unambiguously assigned and may originate from several excited states.

  11. Electrogenerated luminescence of chosen lanthanide complexes at stationary oxide-covered aluminium electrode

    Energy Technology Data Exchange (ETDEWEB)

    Staninski, Krzysztof [Department of Rare Earths, Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, Poznan 60-780 (Poland); Lis, Stefan [Department of Rare Earths, Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, Poznan 60-780 (Poland)], E-mail: blis@amu.edu.pl

    2008-02-28

    The electrochemiluminescence (ECL) of aqueous solutions of Tb{sup 3+}, Dy{sup 3+}, and Eu{sup 3+} complexes having a variety of ligand groups was studied using an oxide-covered aluminium electrode. The ligand groups, under study, were the aromatic acids (salicylic, phthalic), the chelatic ligands (ethylenediamine DL(o-hydroxy-phenylacetic acid), EDDHA and ethylenediamine tetraacetic acid, EDTA), as well as Schiff bases: 1,10-disalicylidene-4,7-diaza-1,10-decyldiamine and 2-salicylideneamine-2-hydroxymethyl-1,3-propanediol. The results show that the generated emissions were mainly the result of energy transfer from the ligands to the metals. The best ECL properties were observed in the case of the complexes Tb(III)-EDDHA, Dy(III)-EDDHA, and Dy(III)-salicylic acid. In the ternary systems: Schiff base-Tb(III)-Eu(III) energy transfer to the emitting level of the Eu(III) ion was observed.

  12. Electrogenerated luminescence of chosen lanthanide complexes at stationary oxide-covered aluminium electrode

    International Nuclear Information System (INIS)

    Staninski, Krzysztof; Lis, Stefan

    2008-01-01

    The electrochemiluminescence (ECL) of aqueous solutions of Tb 3+ , Dy 3+ , and Eu 3+ complexes having a variety of ligand groups was studied using an oxide-covered aluminium electrode. The ligand groups, under study, were the aromatic acids (salicylic, phthalic), the chelatic ligands (ethylenediamine DL(o-hydroxy-phenylacetic acid), EDDHA and ethylenediamine tetraacetic acid, EDTA), as well as Schiff bases: 1,10-disalicylidene-4,7-diaza-1,10-decyldiamine and 2-salicylideneamine-2-hydroxymethyl-1,3-propanediol. The results show that the generated emissions were mainly the result of energy transfer from the ligands to the metals. The best ECL properties were observed in the case of the complexes Tb(III)-EDDHA, Dy(III)-EDDHA, and Dy(III)-salicylic acid. In the ternary systems: Schiff base-Tb(III)-Eu(III) energy transfer to the emitting level of the Eu(III) ion was observed

  13. Complexes in polyvalent metal - Alkali halide melts

    International Nuclear Information System (INIS)

    Akdeniz, Z.; Tosi, M.P.

    1991-03-01

    Experimental evidence is available in the literature on the local coordination of divalent and trivalent metal ions by halogens in some 140 liquid mixtures of their halides with alkali halides. After brief reference to classification criteria for main types of local coordination, we focus on statistical mechanical models that we are developing for Al-alkali halide mixtures. Specifically, we discuss theoretically the equilibrium between (AlF 6 ) 3- and (AlF 4 ) - complexes in mixtures of AlF 3 and NaF as a function of composition in the NaF-rich region, the effect of the alkali counterion on this equilibrium, the possible role of (AlF 5 ) 2- as an intermediate species in molten cryolite, and the origin of the different complexing behaviours of Al-alkali fluorides and chlorides. We also present a theoretical scenario for processes of structure breaking and electron localization in molten cryolite under addition of sodium metal. (author). 26 refs, 2 tabs

  14. A luminescent metal-organic framework for sensing methanol in ethanol solution.

    Science.gov (United States)

    Jin, Zhao; He, Hongming; Zhao, Huanyu; Borjigin, Tsolmon; Sun, Fuxing; Zhang, Daming; Zhu, Guangshan

    2013-10-07

    A new luminescent Zn-MOF has been synthesized under hydrothermal condition using a semi-rigid ligand H3pcoip (4-(2-carboxyphenoxy)isophthalic acid) is reported. The luminescence properties of 1 in methanol, ethanol, and water have been investigated. Interestingly, compound 1 has a unique response to methanol compared to ethanol and water. Moreover, 1 displays a turn-on switching property triggered by methanol solvent molecules and a high sensitivity towards methanol concentration as low as 2 × 10(-7) (V(MeOH)/V(total)) in ethanol solution. The results indicate that the Zn-MOF has potential application as a sensor for detecting methanol in ethanol solution with excellent selectivity and high sensitivity.

  15. Luminescent, magnetic and ferroelectric properties of noncentrosymmetric chain-like complexes composed of nine-coordinate lanthanide ions.

    Science.gov (United States)

    Li, Xi-Li; Chen, Chun-Lai; Xiao, Hong-Ping; Wang, Ai-Ling; Liu, Cai-Ming; Zheng, Xianjun; Gao, Li-Jun; Yang, Xiao-Gang; Fang, Shao-Ming

    2013-11-21

    Reaction of the chiral ligand (-)-4,5-pinenepyridyl-2-pyrazine (L) with Ln(hfac)3·2H2O precursors [hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate, Ln = Sm(3+) (1), Eu(3+) (2), Tb(3+) (3) and Dy(3+) (4)] in methanol solution led to the formation of four noncentrosymmetric lanthanide complexes with the general formula [Ln(hfac)3L]n·H2O. The single-crystal X-ray diffraction analyses revealed that they are isostructural and take a one-dimensional (1D) chain structure based on the Ln(hfac)3L repeating units, in which the nine-coordinate Ln(3+) ions reside in a tricapped trigonal prism (TTP) environment never reported in previous 1D chain lanthanide complexes. The investigations of their photophysical properties showed that complexes 1, and 3 exhibit characteristic emissions of Sm(3+), Eu(3+) and Tb(3+) ions with respective luminescent lifetime values of 0.065, 1.066 and 0.129 ms, while complex 4 does not display any emission. The different luminescent intensities and lifetimes among them were further discussed in detail. Moreover, the magnetic properties of complexes 1-4 were assessed with a special emphasis on the Dy(3+) complex 4. Alternating-current (ac) magnetic susceptibility measurements indicated that field-induced two-step slow magnetic relaxation processes were observed in 4, indicating the single-molecule magnet (SMM) behavior of 4. In addition, the noncentrosymmetric complexes 1-4 crystallizing in the same polar point group (Cs) exhibit both ferroelectric and nonlinear optical properties at room temperature. All these features make them multifunctional crystalline molecule materials.

  16. Mononuclear mercury(II) complexes containing bipyridine derivatives and thiocyanate ligands: Synthesis, characterization, crystal structure determination, and luminescent properties

    Science.gov (United States)

    Amani, Vahid; Alizadeh, Robabeh; Alavije, Hanieh Soleimani; Heydari, Samira Fadaei; Abafat, Marzieh

    2017-08-01

    A series of mercury(II) complexes, [Hg(Nsbnd N)(SCN)2] (Nsbnd N is 4,4‧-dimethyl-2,2‧-bipyridine in 1, 5,5‧-dimethyl-2,2‧-bipyridine in 2, 6,6‧-dimethyl-2,2‧-bipyridine in 3 and 6-methyl-2,2‧-bipyridine in 4), were prepared from the reactions of Hg(SCN)2 with mentioned ligands in methanol. Suitable crystals of these complexes were obtained for X-ray diffraction measurement by methanol diffusion into a DMSO solution. The four complexes were thoroughly characterized by spectral methods (IR, UV-Vis, 13C{1H}NMR, 1H NMR and luminescence), elemental analysis (CHNS) and single crystal X-ray diffraction. The X-ray structural analysis indicated that in the structures of these complexes, the mercury(II) cation is four-coordinated in a distorted tetrahedral configuration by two S atoms from two thiocyanate anions and two N atoms from one chelating 2,2‧-bipyridine derivative ligand. Also, in these complexes intermolecular interactions, for example Csbnd H⋯N hydrogen bonds (in 1-4), Csbnd H⋯S hydrogen bonds (in 1, 2 and 4), π … π interactions (in 2-4), Hg⋯N interactions (in 2) and S⋯S interactions (in 4), are effective in the stabilization of the crystal structures and the formation of the 3D supramolecular complexes. Furthermore, the luminescence spectra of the title complexes show that the intensity of their emission bands are stronger than the emission bands for the free bipyridine derivative ligands.

  17. Luminescence and energy transfer

    Energy Technology Data Exchange (ETDEWEB)

    Blasse, G; Bleijenberg, K C; Powell, R C

    1980-01-01

    This paper deals with the luminescence of uranate centres in solids. The luminescence properties are influenced by the coordination number of the hexavalent uranium ion and by the crystallographic surroundings of the uranate centre. Transitions playing a role in the luminescence processes within the octahedral UO/sub 6//sup 6 -/ group are discussed using the results from both theoretical and experimental studies on another octahedral uranium complex: UF/sub 6/. The luminescence of the octahedral uranate group in oxidic compounds is discussed. Attention is paid to the vibrational structure, which is observed in the luminescence spectra at low temperatures and to the temperature quenching of the luminescence. The temperature quenching of the uranate luminescence in uranium-doped tungstates with ordered perovskite structure can be described in terms of a three state single configurational coordinate diagram. The complicated luminescence spectra of uranium-activated sodium fluoride (NaF-U) crystals have been unraveled using chemical variation of the crystal compositions and using site selective laser excitation techniques. Four different luminescent uranate centres have been observed in NaF-U. A model for the configurations of the luminescent centres has been deduced using the results from ionic conductivity experiments.

  18. Hot-Electron Intraband Luminescence from Single Hot Spots in Noble-Metal Nanoparticle Films

    Science.gov (United States)

    Haug, Tobias; Klemm, Philippe; Bange, Sebastian; Lupton, John M.

    2015-08-01

    Disordered noble-metal nanoparticle films exhibit highly localized and stable nonlinear light emission from subdiffraction regions upon illumination by near-infrared femtosecond pulses. Such hot spot emission spans a continuum in the visible and near-infrared spectral range. Strong plasmonic enhancement of light-matter interaction and the resulting complexity of experimental observations have prevented the development of a universal understanding of the origin of light emission. Here, we study the dependence of emission spectra on excitation irradiance and provide the most direct evidence yet that the continuum emission observed from both silver and gold nanoparticle aggregate surfaces is caused by recombination of hot electrons within the conduction band. The electron gas in the emitting particles, which is effectively decoupled from the lattice temperature for the duration of emission, reaches temperatures of several thousand Kelvin and acts as a subdiffraction incandescent light source on subpicosecond time scales.

  19. Novel Metals and Metal Complexes as Platforms for Cancer Therapy

    OpenAIRE

    Frezza, Michael; Hindo, Sarmad; Chen, Di; Davenport, Andrew; Schmitt, Sara; Tomco, Dajena; Dou, Q. Ping

    2010-01-01

    Metals are essential cellular components selected by nature to function in several indispensable biochemical processes for living organisms. Metals are endowed with unique characteristics that include redox activity, variable coordination modes, and reactivity towards organic substrates. Due to their reactivity, metals are tightly regulated under normal conditions and aberrant metal ion concentrations are associated with various pathological disorders, including cancer. For these reasons, coo...

  20. Extraction of fluoride metal complexes by octanols

    International Nuclear Information System (INIS)

    Baklanova, I.V.; Nikolaev, A.I.; Il'in, E.G.; Majorov, V.G.

    2005-01-01

    The extraction of niobium(V) and tantalum(V) by octanols, including 1-octanol, 2-octanol, and iso-octanol (2-ethylhexanol), was studied. The composition of the octanols and their solubility in various aqueous solutions were evaluated. The capacity of the octanols for tantalum(V) and niobium(V), the extraction properties of the octanols, the viscosity of extracts under conditions of metal fluoride extraction, and the temperature dependence of the viscosity of the octanols were studied. The composition of the extracted complexes was studied by IR and NMR spectroscopy and chemical analysis, and the hydration-solvation mechanism of the extraction of tantalum(V) and niobium(V) was supported [ru

  1. 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

  2. METAL COMPLEXES OF SALICYLHYDROXAMIC ACID AND 1,10 ...

    African Journals Online (AJOL)

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    Metal complexes which are formed in biological systems between a ligand and a metal ion are in dynamic ... In a continuation of our research work oriented towards studying the .... Antimicrobial activity techniques. Preparation of test samples.

  3. Luminescent zinc(ii) and copper(i) complexes for high-performance solution-processed monochromic and white organic light-emitting devices.

    Science.gov (United States)

    Cheng, Gang; So, Gary Kwok-Ming; To, Wai-Pong; Chen, Yong; Kwok, Chi-Chung; Ma, Chensheng; Guan, Xiangguo; Chang, Xiaoyong; Kwok, Wai-Ming; Che, Chi-Ming

    2015-08-01

    The synthesis and spectroscopic properties of luminescent tetranuclear zinc(ii) complexes of substituted 7-azaindoles and a series of luminescent copper(i) complexes containing 7,8-bis(diphenylphosphino)-7,8-dicarba- nido -undecaborate ligand are described. These complexes are stable towards air and moisture. Thin film samples of the luminescent copper(i) complexes in 2,6-dicarbazolo-1,5-pyridine and zinc(ii) complexes in poly(methyl methacrylate) showed emission quantum yields of up to 0.60 (for Cu-3 ) and 0.96 (for Zn-1 ), respectively. Their photophysical properties were examined by ultrafast time-resolved emission spectroscopy, temperature dependent emission lifetime measurements and density functional theory calculations. Monochromic blue and orange solution-processed OLEDs with these Zn(ii) and Cu(i) complexes as light-emitting dopants have been fabricated, respectively. Maximum external quantum efficiency (EQE) of 5.55% and Commission Internationale de l'Eclairage (CIE) coordinates of (0.16, 0.19) were accomplished with the optimized Zn-1 -OLED while these values were, respectively 15.64% and (0.48, 0.51) for the optimized Cu-3 -OLED. Solution-processed white OLEDs having maximum EQE of 6.88%, CIE coordinates of (0.42, 0.44), and colour rendering index of 81 were fabricated by using these luminescent Zn(ii) and Cu(i) complexes as blue and orange light-emitting dopant materials, respectively.

  4. Theoretical studies of transition metal complexes with nitriles and isocyanides

    International Nuclear Information System (INIS)

    Kuznetsov, Maksim L

    2002-01-01

    Theoretical studies of transition metal complexes with nitriles and isocyanides are reviewed. The electronic structures and the nature of coordination bonds in these complexes are discussed. The correlation between the electronic structures of transition metal complexes with nitriles and isocyanides and their structural properties, spectroscopic characteristics, and reactivities are considered. The bibliography includes 121 references.

  5. Metal complexation capacity of Antarctic lacustrine sediments.

    Science.gov (United States)

    Alberti, Giancarla; Mussi, Matteo; Quattrini, Federico; Pesavento, Maria; Biesuz, Raffaela

    2018-04-01

    The purpose of this study is to implement a work that is a part of a project funded by the Italian National Antarctic Research Program (PNRA, Piano Nazionale di Ricerche in Antartide) within the main thematic focus "Chemical Contamination-Global Change". This research was devoted to detect and characterize micro and nano components with strong complexing capability towards metal ions at trace level in sea water, lakes and lacustrine sediments, sampled during the XXII expedition of PNRA. In particular, in the present work, the sorption complexation capacity of an Antarctic lacustrine sediments toward Cu(II) and Pb(II) is described. The characterization of the sorption was undertaken, studying kinetics and isotherm profiles. The lake here considered is Tarn Flat in the area of Terra Nova Bay. The sorption equilibria of Cu(II) and Pb(II) on the lacustrine sediments were reached in about 10 h, and they were best modelled by the Langmuir equation. Preliminary, to establish if the data here obtained were consistent with those reported for the same area in other expeditions, a common multivariate techniques, namely the principal component analysis (PCA), was applied and finally the consistency of the data has been confirmed. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Synthesis and luminescence of Eu3+ and Tb3+ complexes with novel calix[4]arene ligands carrying 2,2'-bipyridine subunits

    International Nuclear Information System (INIS)

    Sabbatini, N.; Guardigli, M.; Manet, I.; Ungaro, R.; Casnati, A.; Fischer, C.; Ziessel, R.; Ulrich, G.

    1995-01-01

    Eu 3+ and Tb 3+ complexes with novel branched calix[4]arene ligands incorporating 2,2' -bipyridine subunits functionalized in the 6- or 5,5'-positions have been synthesized and their photophysical properties investigated. High luminescence intensity was obtained for the Eu 3+ complex of the calix[4]arene ligand carrying four 5,5' -substituted- 2,2' -bipyridines, which has high molar extinction coefficients (ε max 39 600 M -1 cm -1 ) and a high luminescence quantum yield (15%). (authors). 12 refs., 2 figs., 1 tab

  7. Effect of solvents on relation of intensities of bands of luminescence spectra of terbium and dysprosium ions in solutions of their complexes with acetoacetic ester

    International Nuclear Information System (INIS)

    Kononenko, L.I.; Bel'tyukova, S.V.; Meshkova, S.B.; Kravchenko, T.B.; Poluehktov, N.S.

    1978-01-01

    An investigation is made of the effect of different solvents on the ratio of the intensity of luminescence spectrum bands of terbium and dysprosium ions, corresponding and not corresponding to ''supersensitive'' transitions in complex compounds with acetoacetic ether. A dependence is established between these values and the dielectric constant of the solvent, and also parallels in their changes, which indicate the similar manifestation of the effect of solvents in both elements. A correlation is observed between ratios of the intensity of luminescence spectrum bands and values of forces of neodymium complex absorption band oscillators in different solvents

  8. Complex metal hydrides for hydrogen, thermal and electrochemical energy storage

    DEFF Research Database (Denmark)

    Møller, Kasper T.; Sheppard, Drew; Ravnsbæk, Dorthe B.

    2017-01-01

    field. This review illustrates that complex metal hydrides may store hydrogen in the solid state, act as novel battery materials, both as electrolytes and electrode materials, or store solar heat in a more efficient manner as compared to traditional heat storage materials. Furthermore, it is highlighted...... how complex metal hydrides may act in an integrated setup with a fuel cell. This review focuses on the unique properties of light element complex metal hydrides mainly based on boron, nitrogen and aluminum, e.g., metal borohydrides and metal alanates. Our hope is that this review can provide new...

  9. Cationic rare-earth metal SALEN complexes.

    Science.gov (United States)

    Liu, Qiancai; Meermann, Christian; Görlitzer, Hans W; Runte, Oliver; Herdtweck, Eberhardt; Sirsch, Peter; Törnroos, Karl W; Anwander, Reiner

    2008-11-28

    Complexes (Salpren(tBu,tBu))Y[N(SiHMe2)2](thf) and (SALEN(tBu,tBu))La[N(SiHMe2)2](thf) (SALEN(tBu,tBu) = Salcyc(tBu,tBu) and Salpren(tBu,tBu)) were prepared from Ln[N(SiHMe2)2]3(thf)2 and H2SALEN(tBu,tBu). The yttrium complex was characterized by X-ray crystallography revealing intrinsic solid-state structural features: the metal centre is displaced by 1.05 angstroms from the [N2O2] least squares plane of a highly bent Salpren(tBu,tBu) ligand (angle(Ph,Ph) dihedral angle of 80.4(1) degrees ) and is coordinated asymmetrically by the silylamide ligand exhibiting one significant Y---(HSi) beta-agostic interaction (Y-N1-Si1, 106.90(9) degrees; Y---Si1, 3.2317(6) angstroms). Complexes (SALEN(tBu,tBu))Ln[N(SiHMe2)2](thf)n (n = 1, Sc; n = 2, Y, La) react with ammonium tetraphenylborate to form the ion pairs [(SALEN(tBu,tBu))Ln(thf)n][BPh4]. The cationisation was proven by X-ray crystal structure analyses of [(Salpren(tBu,tBu))Sc(thf)2][B(C6H5)4].2(thf) and [(Salpren(tBu,tBu))Ln(thf)3][B(C6H5)4].4(thf) (Ln = Y, La), showing an octahedral and pentagonal-bipyramidal coordination geometry, respectively.

  10. Synthesis and characterisation of luminescent rhenium tricarbonyl complexes with axially coordinated 1,2,3-triazole ligands.

    Science.gov (United States)

    Uppal, Baljinder S; Booth, Rebecca K; Ali, Noreen; Lockwood, Cindy; Rice, Craig R; Elliott, Paul I P

    2011-08-07

    A series of 1-alkyl-4-aryl-1,2,3-triazoles (1-methyl-4-phenyl-1,2,3-triazole (1a); 1-propyl-4-phenyl-1,2,3-triazole (1b); 1-benzyl-4-phenyl-1,2,3-triazole (1c); 1-propyl-4-p-tolyl-1,2,3-triazole (1d)) have been prepared through a one-pot procedure involving in situ generation of the alkyl azide from a halide precursor followed by copper catalysed alkyne/azide cycloaddition (CuAAC) with the appropriate aryl alkyne. Cationic Re(I) complexes [Re(bpy)(CO)(3)(1a-d)]PF(6) (2a-d) were then prepared by stirring [Re(bpy)(CO)(3)Cl] with AgPF(6) in dichloromethane in the presence of ligands 1a-d. X-ray crystal structures were obtained for 2a and 2b. In the solid state, 2a adopts a highly distorted geometry, which is not seen for 2b, in which the plane of the triazole ligand tilts by 13° with respect to the Re-N bond as a result of a π-stacking interaction between the Ph substituent and one of the rings of the bpy ligand. This π-stacking interaction also results in severe twisting of the bpy ligand. Infrared spectra of 2a-d exhibit ν(CO) bands at ∼2035 and ∼1926 cm(-1) suggesting that these ligands are marginally better donors than pyridine (ν(CO) = 2037, 1932 cm(-1)). The complexes are luminescent in aerated dichloromethane at room temperature with emission maxima at 542 to 552 nm comparable to that of the pyridine analogue (549 nm) and blue shifted relative to the parent chloride complex. Long luminescent lifetimes are observed for the triazole complexes (475 to 513 ns) in aerated dichloromethane solutions at room temperature.

  11. Luminescent turn-on detection of Hg(II) via the quenching of an iridium(III) complex by Hg(II)-mediated silver nanoparticles.

    Science.gov (United States)

    Liu, Jinshui; Vellaisamy, Kasipandi; Yang, Guanjun; Leung, Chung-Hang; Ma, Dik-Lung

    2017-06-15

    A novel luminescent turn-on detection method for Hg(II) was developed. The method was based on the silver nanoparticle (AgNP)-mediated quenching of Ir(III) complex 1. The addition of Hg(II) ions causes the luminescence of complex 1 to be recovered due to the oxidation of AgNPs by Hg(II) ions to form Ag(I) and Ag/Hg amalgam. The luminescence intensity of 1 increased in accord with an increased Hg(II) concentration ranging from 0 nM to 180 nM, with the detection limit of 5 nM. This approach offers an innovative method for the quantification of Hg(II).

  12. Sensing of nucleosides, nucleotides and DNA using luminescent Eu complex by normal and time resolved fluorescence techniques

    Energy Technology Data Exchange (ETDEWEB)

    Azab, Hassan A.; Anwar, Zeinab M. [Chemistry Department, Faculty of Science, Suez Canal University, 41522 Ismailia (Egypt); Kamel, Rasha M., E-mail: rashamoka@yahoo.com [Chemistry Department, Faculty of Science, Suez University, 43518 Suez (Egypt); Rashwan, Mai S. [Chemistry Department, Faculty of Science, Suez Canal University, 41522 Ismailia (Egypt)

    2016-01-15

    The interaction of Eu-1,4,7,10-tetraazacyclododecane (Cyclen) complex by using 4,4,4 trifluoro-1-(2-naphthyl)1,3-butanedione (TNB) as antenna with some nucleosides (guanosine, adenosine, cytidine and inosine), nucleotides (AMP, GMP, CMP, ATP and IMP) and DNA is studied using fluorescence technique. Two detection modes are employed one is the time-resolved mode, and the other is the normal luminescence mode. The time-resolved mode is more sensing than the normal luminescence mode in the present study. By using Benesi–Hildebrand equation binding constants were determined at various temperatures. Thermodynamic parameters showed that the reaction is spontaneous through the obtained negative values of free energy change ΔG. The enthalpy ΔH and the entropy ΔS of reactions were all determined. - Highlights: • This is an application for the detection of biologically important ligands. • The detection limits, binding constants and thermodynamic parameters were evaluated. • Effect of some interferents on the detection of DNA has been investigated.

  13. Sensing of nucleosides, nucleotides and DNA using luminescent Eu complex by normal and time resolved fluorescence techniques

    International Nuclear Information System (INIS)

    Azab, Hassan A.; Anwar, Zeinab M.; Kamel, Rasha M.; Rashwan, Mai S.

    2016-01-01

    The interaction of Eu-1,4,7,10-tetraazacyclododecane (Cyclen) complex by using 4,4,4 trifluoro-1-(2-naphthyl)1,3-butanedione (TNB) as antenna with some nucleosides (guanosine, adenosine, cytidine and inosine), nucleotides (AMP, GMP, CMP, ATP and IMP) and DNA is studied using fluorescence technique. Two detection modes are employed one is the time-resolved mode, and the other is the normal luminescence mode. The time-resolved mode is more sensing than the normal luminescence mode in the present study. By using Benesi–Hildebrand equation binding constants were determined at various temperatures. Thermodynamic parameters showed that the reaction is spontaneous through the obtained negative values of free energy change ΔG. The enthalpy ΔH and the entropy ΔS of reactions were all determined. - Highlights: • This is an application for the detection of biologically important ligands. • The detection limits, binding constants and thermodynamic parameters were evaluated. • Effect of some interferents on the detection of DNA has been investigated.

  14. Synthesis, characterization, photoluminescence and cytotoxic properties of novel luminescent Eu(III)complexes based on chromone Schiff base

    Science.gov (United States)

    Saif, M.; El-Shafiy, Hoda F.; Mashaly, Mahmoud M.; Eid, Mohamed F.; Nabeel, A. I.; Fouad, R.

    2018-06-01

    Three novel Eu(III) phosphor complexes, [Eu(HL)(OH2)2(C2H5OH)](NO3)2 (1), [Eu(HL)(Bpy)(NO3)2(EtOH)] (2) and [Eu(HL)(Phen)(NO3)2(H2O)] (3) (HL = (11E)-2-hydroxy-N/-((4-oxo-4H-chromen-3-yl)methylene)benzohydrazide; Bpy = 2,2/-bibyridyl and Phen = 1,10-phenanthroline) were prepared. Elemental, thermal, FT-IR and XRD methods were used to characterize their structural configuration. The HL behaves as a monoanionic tridentate ligand. The XRD analysis shows that the ligand and its Eu3+complexes are in nano domain. From fluorescence spectroscopy, all the prepared complexes are highly luminescent, having an impressive visual emission under UV excitation. The H2L and its Eu3+nano-complexes (1-3) were tested for their in vitro cytotoxicity against Ehrlich Ascites Carcinoma cell line (EAC). The Eu(III) nano-complexes (1-3) effectively inhibited EAC growth with IC50 value of 25 μM. The high antitumor activity of the Eu(III) nano-complexes (1-3) were attributed to its chemical structure, and nano size properties.

  15. Preparation of three terbium complexes with p-aminobenzoic acid and investigation of crystal structure influence on luminescence property

    International Nuclear Information System (INIS)

    Ye Chaohong; Sun Haoling; Wang Xinyi; Li Junran; Nie Daobo; Fu Wenfu; Gao Song

    2004-01-01

    Three new rare earth p-aminobenzoic acid complexes, [Tb 2 L 6 (H 2 O) 2 ] n (1), [Tb 2 L 6 (H 2 O) 4 ].2H 2 O (2) and [Tb(phen) 2 L 2 (H 2 O) 2 ](phen)L·4H 2 O (3) (HL: p-aminobenzoic acid; phen: 1, 10-phenanthroline), with different structural forms are reported in this paper. Complex 1 is a polymolecule with a two-dimensional plane structure. Compound 2 is a binuclear molecule, and 3 appears to be a mononuclear complex. The fluorescence intensity, the fluorescence life-time and emission quantum yield of 2, which has two coordination water molecules, is better than those of 1, which has only one coordination water molecule. This is an unusual phenomenon for general fluorescent rare earth complexes. The fluorescence performance of 3 is the most unsatisfactory among the three complexes. Their crystal structures show that the coordination mode of the ligand is an important factor influencing the luminescence properties of a fluorescent rare earth complex

  16. Preparation, characterization, and luminescence properties of dysprosium perchlorate with MABA-Si and phen or dipy complexes as well as SiO{sub 2}@Dy(MABA-Si)L core-shell structure nanometermeter luminescent composites

    Energy Technology Data Exchange (ETDEWEB)

    Li, Wen-Xian, E-mail: nmglwx@163.com [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Zheng, Yu-Shan [Inner Mongolia Autonomous Region Product Quality Inspection Institute, Hohhot 010010 (China); Cao, Xiao-fang; Bai, Juan; Fu, Zhi-Fang; Bao, Jin-Rong; Li, Yi-Lian [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China)

    2016-10-15

    Two novel ternary rare earth complexes Dy(MABA-Si)·L{sub 2}(ClO{sub 4}){sub 3}·2H{sub 2}O (L= Phen or Dipy) were prepared using HOOCC{sub 6}H{sub 4}N(CONH(CH{sub 2}){sub 3}Si-(OCH{sub 2}CH{sub 3}){sub 3}){sub 2} which was abbreviated or denoted as MABA-Si. MABA-Si was the first ligand, L was the second ligand. The corresponding two SiO{sub 2}@Dy(MABA-Si)L nanometermeter luminescent composites were synthesized as well, and the silica spheres is the core, and the ternary rare earth complex Dy(MABA-Si)·L{sub 2}(ClO{sub 4}){sub 3}·2H{sub 2}O was the shell layer, who was abbreviated or denoted as Dy((MABA-Si)L). The ternary complexes have been characterized by element analysis, molar conductivity, IR spectra and {sup 1}HNMR spectra. The results showed that the chemical formula of the complex was Dy(MABA-Si)·L{sub 2}(ClO{sub 4}){sub 3}·2H{sub 2}O. The fluorescent spectra illustrated that the complexes displayed its characteristic luminescence in solid state, and the luminescence was superior than Dy{sup 3+}. The core-shell structure of SiO{sub 2}@Dy(MABA-Si)L nanometermeter luminescent composite was characterized by SEM, TEM and IR spectra. Based on the SEM photographs, the core-shell structure particles showed its regular microstructure including smooth surface, and good dispersity. The ternary complex coated on the mono-dispersed SiO{sub 2} spheres by self-assembly. The fluorescent spectra illustrated that the core-shell structure of SiO{sub 2}@Dy(MABA-Si)L nanometermeter luminescent composites exhibited stronger fluorescent than the ternary complexes. The fluorescence lifetime of the complexes and core-shell structure composites was measured as well.

  17. Highly Fluorescent Group 13 Metal Complexes with Cyclic, Aromatic Hydroxamic Acid Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, Michael; Moore, Evan G.; Raymond, Kenneth N.

    2008-02-11

    The neutral complexes of two ligands based on the 1-oxo-2-hydroxy-isoquinoline (1,2-HOIQO) motif with group 13 metals (Al, Ga, In) show bright blue-violet luminescence in organic solvents. The corresponding transition can be attributed to ligand-centered singlet emission, characterized by a small Stokes shifts of only a few nm combined with lifetimes in the range between 1-3 ns. The fluorescence efficiency is high, with quantum yields of up to 37% in benzene solution. The crystal structure of one of the indium(III) complexes (trigonal space group R-3, a = b = 13.0384(15) {angstrom}, c = 32.870(8) {angstrom}, ? = {beta} = 90{sup o}, {gamma} = 120{sup o}, V = 4839.3(14) {angstrom}{sup 3}, Z = 6) shows a six-coordinate geometry around the indium center which is close to trigonal-prismatic, with a twist angle between the two trigonal faces of 20.7{sup o}. Time-dependent density functional theory (TD-DFT) calculations (Al and Ga: B3LYP/6-31G(d)); In: B3LYP/LANL2DZ of the fac and mer isomers with one of the two ligands indicate that there is no clear preference for either one of the isomeric forms of the metal complexes. In addition, the metal centers do not have a significant influence on the electronic structure, and as a consequence, on the predominant intraligand optical transitions.

  18. Metal oxalate complexes as novel inorganic dopants: Studies on ...

    Indian Academy of Sciences (India)

    Unknown

    UV-visible and IR spectral features not only confirmed the polyaniline doping by complex anions but also substantiated ... MoS3 dopant. Although inorganic metal complexes bear- ... distilled water and then with methanol and acetone until.

  19. Lability of Nanoparticulate Metal Complexes at a Macroscopic Metal Responsive (Bio)interface

    NARCIS (Netherlands)

    Duval, Jérôme F.L.; Town, Raewyn M.; Leeuwen, Van Herman P.

    2018-01-01

    The lability of metal complexes expresses the extent of the dissociative contribution of the complex species to the flux of metal ions toward a macroscopic metal-responsive (bio)interface, for example, an electrodic sensor or an organism. While the case of molecular ligands is well-established, it

  20. A pillar-layered metal-organic framework as luminescent sensor for selective and reversible response of chloroform

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Kun; Li, Shuni; Jiang, Yucheng; Hu, Mancheng; Zhai, Quan-Guo, E-mail: zhaiqg@snnu.edu.cn

    2017-03-15

    A new 3D metal-organic framework, namely, (Zn{sub 4}(H{sub 2}BPTC){sub 2}(HCOO){sub 4}){sub n} (SNNU-1, H{sub 4}BPTC=biphenyl-3,3',5,5'-tetracarboxylic acid, SNNU=Shaanxi Normal University) has been solvothermal synthesized. Four independent tetrahedral Zn atoms are connected by organic ligands to form a 2D Zn-H{sub 2}BPTC layer, which is further bridged by in-situ generated HCOO{sup -} to give the 3D pillar-layered framework of SNNU-1. Unique Zn and H{sub 2}BPTC all act as 4-connected nodes leading to a new 4,4,4-connected topological net with point symbol of (4·5·6{sup 2}·8{sup 2})(4·5{sup 2}·6{sup 2}·8)(5{sup 2}·6{sup 3}·7). Notably, intense blue emission band is observed for SNNU-1, which exhibits solvent-dependent effect. Compared to other common organic solvents, chloroform can specially improve the photoluminescent intensity of SNNU-1. Further repeated response and release experiments clearly showed that SNNU-1 can act as luminescent sensor for selective and reversible detection of chloroform. - Graphical abstract: Zn{sup 2+} ions are bridged by aromatic tetracarboxylate ligands and inorganic formate anions to give a microporous pillar layered open-framework, which exhibits not only strong photoluminescence but also selective and reversible luminescent sensing for chloroform. - Highlights: • Novel Zn-tetracarboxylate-formate microporous pillar layered open-framework. • New 4,4,4-connected topology and rod-packing net. • Solvent-dependent photoluminescent intensity. • Selective and reversible response for chloroform.

  1. Synthesis, structure, theoretical studies and luminescent properties of a ternary erbium(III) complex with acetylacetone and bathophenanthroline ligands

    Energy Technology Data Exchange (ETDEWEB)

    Martín-Ramos, Pablo [CEMDRX, Department of Physics, Universidade de Coimbra, Rua Larga, P-3004-516 Coimbra (Portugal); Advanced Materials Laboratory, ETSIIAA, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain); Silva, Pedro S. Pereira, E-mail: psidonio@pollux.fis.uc.pt [CEMDRX, Department of Physics, Universidade de Coimbra, Rua Larga, P-3004-516 Coimbra (Portugal); Chamorro-Posada, Pedro [Higher Technical School of Telecommunications Engineering, Universidad de Valladolid, Campus Miguel Delibes, Paseo Belén 15, 47011 Valladolid (Spain); Silva, Manuela Ramos [CEMDRX, Department of Physics, Universidade de Coimbra, Rua Larga, P-3004-516 Coimbra (Portugal); Milne, Bruce F. [Centre for Computational Physics, Department of Physics, Universidade de Coimbra, P-3004-516 Coimbra (Portugal); Donostia International Physics Centre, Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Nogueira, Fernando [Centre for Computational Physics, Department of Physics, Universidade de Coimbra, P-3004-516 Coimbra (Portugal); Martín-Gil, Jesús [Advanced Materials Laboratory, ETSIIAA, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain)

    2015-06-15

    A novel erbium(III) complex with acetylacetone (Hacac) and bathophenanthroline (4,7-diphenyl-1,10-phenanthroline, bath) ligands, formulated as [Er(acac){sub 3}(bath)], has been characterized by elemental analysis, X-ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, Raman spectroscopy, absorption and emission spectroscopies. In the theoretical part of this study, semi-empirical quantum chemistry methods using AM1, PM3, PM6 and PM7 models have been employed to predict the structure of the complex, calculate the geometric and crystallographic parameters, and make comparisons with spectroscopic data using INDO/S-CI calculations. Real-time time-dependent density-functional theory (TDDFT) has also been used to calculate the optical absorption spectrum of the complex in the gas phase. - Highlights: • Synthesis and structure of a new erbium(III) β-diketonate complex. • TDDFT used for the first time to calculate the optical absorption spectrum. • Complex show strong near-infrared luminescence at 1.53 µm due to antenna effect.

  2. Synthesis, structure, theoretical studies and luminescent properties of a ternary erbium(III) complex with acetylacetone and bathophenanthroline ligands

    International Nuclear Information System (INIS)

    Martín-Ramos, Pablo; Silva, Pedro S. Pereira; Chamorro-Posada, Pedro; Silva, Manuela Ramos; Milne, Bruce F.; Nogueira, Fernando; Martín-Gil, Jesús

    2015-01-01

    A novel erbium(III) complex with acetylacetone (Hacac) and bathophenanthroline (4,7-diphenyl-1,10-phenanthroline, bath) ligands, formulated as [Er(acac) 3 (bath)], has been characterized by elemental analysis, X-ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, Raman spectroscopy, absorption and emission spectroscopies. In the theoretical part of this study, semi-empirical quantum chemistry methods using AM1, PM3, PM6 and PM7 models have been employed to predict the structure of the complex, calculate the geometric and crystallographic parameters, and make comparisons with spectroscopic data using INDO/S-CI calculations. Real-time time-dependent density-functional theory (TDDFT) has also been used to calculate the optical absorption spectrum of the complex in the gas phase. - Highlights: • Synthesis and structure of a new erbium(III) β-diketonate complex. • TDDFT used for the first time to calculate the optical absorption spectrum. • Complex show strong near-infrared luminescence at 1.53 µm due to antenna effect

  3. Synthesis, characteristics and luminescent properties of a new Tb(III) ternary complex applied in near UV-based LED

    Science.gov (United States)

    Sun, Naiqun; Li, Liping; Yang, Yamin; Zhang, Aiqin; Jia, Husheng; Liu, Xuguang; Xu, Bingshe

    2015-11-01

    A novel Tb(III) ternary complex, Tb(p-BBA)3UA, was synthesized with 4-benzoylbenzoic acid (p-BBA) as primary ligand and undecylenic acid (UA) as reactive ligand. Tb(III) complex exhibits high thermal stability and wide and strong excitation bands from 310 nm to 400 nm when monitored at 543 nm, which matches well with the 365 nm UV chip. The complex displays Tb(III) characteristic peaks at 488, 543, 584 and 619 nm under the excitation of 365 nm UV-light. The intramolecular energy transfer process was also discussed. Meanwhile, the complex has longer fluorescence lifetime (1.317 ms) and higher quantum yield (44.8%). When used in LED with 365 nm UV chip (power efficiency is 17.3 lm/W), the complex still maintained its qualified luminescent performance. All the results indicate that Tb(p-BBA)3UA can be applied as a green component for fabrication of near UV-based white LED.

  4. Three luminescent d{sup 10} metal coordination polymers assembled from a semirigid V-shaped ligand with high selective detecting of Cu{sup 2+} ion and nitrobenzene

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Wei-Ping [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorg. Chem., College of Chemistry & Materials Science, Northwest University, Xi’an 710069 (China); Institute of Functional Materials, College of Chemistry and Pharmaceutical Engineering, Sichuan University of Science & Engineering, Zigong 643000 (China); Liu, Ping; Liang, Yu-Tong; Cui, Lin; Xi, Zheng-Ping [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorg. Chem., College of Chemistry & Materials Science, Northwest University, Xi’an 710069 (China); Wang, Yao-Yu, E-mail: wyaoyu@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorg. Chem., College of Chemistry & Materials Science, Northwest University, Xi’an 710069 (China)

    2015-08-15

    Three 2D luminescent coordination polymers with helical frameworks, [ZnL{sub 2}]{sub n} (1) and ([ML{sub 2}]·(H{sub 2}O)){sub n} (M=Zn (2), Cd (3)) (HL=4-((2-methyl-1 H-imidazol-1-yl)methyl)benzoic acid), have been assembled under hydro(solvo)thermal conditions. Complex 1 is in chiral space group and displays a rare 2D→2D 2-fold parallel interpenetrated layer network with two types of chiral double helixes. Interestingly, the single crystal structure analyses indicate the coexistence of enantiomers la and 1b in one pot, while the bulk crystallization of 1 are racemic mixtures based on the CD measurement. 2 and 3 are isostructural, in the structure, there are two kinds of 2D chiral helical-layers which stack in an -ABAB- sequence leading to the overall structure are mesomer and achiral. All compounds display intense luminescence in solid state at room temperature with high chemical and thermal stability. More importantly, 1 has been successfully applied in the detection of Cu{sup 2+} ions in aqueous media and nitrobenzene and the probable detecting mechanism was also discussed. - Graphical abstract: Three luminescent d{sup 10} metal coordination polymers with helical-layer based on 4-((2-methyl-1H-imidazol-1-yl)methyl)benzoic acid have been obtained. Compound 1 shows high selective detecting for Cu{sup 2+} ion in aqueous and nitrobenzene. - Highlights: • Three coordination polymers with chiral helical-layer have been obtained. • 1 Can luminescent detect Cu{sup 2+} ion in aqueous media and nitrobenzene. • Racemic mixture or mesomer compounds can be obtained by controlling the reaction conditions.

  5. Plasmon hybridization in complex metallic nanostructures

    Science.gov (United States)

    Hao, Feng

    With Plasmon Hybridization (PH) and Finite-Difference Time-Domain (FDTD) method, we theoretically investigated the optical properties of some complex metallic nanostructures (coupled nanoparticle/wire, nanostars, nanorings and combined ring/disk nanocavity systems). We applied the analytical formulism of PH studying the plasmonic coupling of a spherical metallic nanoparticle and an infinite long cylindrical nanowire. The plasmon resonance of the coupled system is shown shifted in frequency, which highly depends on the polarization of incident light relative to the geometry of the structure. We also showed the nanoparticle serves as an efficient antenna coupling the electromagnetic radiation into the low-energy propagating wire plasmons. We performed an experimental and theoretical analysis of the optical properties of gold nanorings with different sizes and cross sections. For light polarized parallel to the ring, the optical spectrum sensitively depends on the incident angle. When light incidence is normal to the ring, two dipolar resonance is observed. As the incident light is titled, some previously dark mulipolar plasmon resonances will be excited as a consequence of the retardation. The concept of plasmon hybridization is combined with the power of brute-force numerical methods to understand the plasmonic properties of some very complicated nanostructures. We showed the plasmons of a gold nanostar are a result of hybridization of the plasmons of the core and the tips of the particle. The core serves as a nanoantenna, dramatically enhanced the optical spectrum and the field enhancement of the nanostar. We also applied this method analyzing the plasmonic modes of a nanocavity structure composed of a nanodisk with a surrounding minoring. For the concentric combination, we showed the nature of the plasmon modes can be understood as the plasmon hybrization of an individual ring and disk. The interation results in a blueshifted and broadened superradiant antibonding

  6. Cell complexes of transition metals in biochemistry and medicine

    International Nuclear Information System (INIS)

    Voloshin, Ya.Z.; Varzatskij, O.A.; Bubnov, Yu.N.

    2007-01-01

    Basic directions and prospects of use of cell complexes of transition metals in medicine and biochemistry are considered: incapsulation of radioactive metal ions for radiotherapy and diagnostics; preparation of contrast compounds for magnetic resonance tomography, antidotes and pharmaceutical preparation of prolonged effect, preparations for boron-neutron-capture therapy of neoplasms, antioxidants; membrane transport of metal ions; study of interaction of cell metal complexes with nucleic acids; possibility of use of self-assembly of cell complexes for imitation of ligases and use of clathrochelates as linkers; design of inhibitors of viruses for AIDS therapy [ru

  7. Surface polyPEGylation of Eu3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    Science.gov (United States)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-03-01

    The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

  8. Heavy metals detection using biosensor cells of a novel marine luminescent bacterium Vibrio sp. MM1 isolated from the Caspian Sea.

    Science.gov (United States)

    Mohseni, Mojtaba; Abbaszadeh, Jaber; Maghool, Shima-Sadat; Chaichi, Mohammad-Javad

    2018-02-01

    Monitoring and assessing toxic materials which are being released into the environment along with wastewater is a growing concern in many industries. The current research describes a highly sensitive and rapid method for the detection of toxic concentrations of heavy metals in aquatic environments. Water samples were collected from southern coasts of the Caspian Sea followed by screening of luminescent bacteria. Phylogenetic analysis, including gene sequence of 16S rRNA, and biochemical tests were performed for identification of the isolate. Luminescence activity was tested and measured after treatment of the isolate with different concentrations of heavy metals and reported as EC 50 value for each metal. A luminous, gram negative bacterium with the shape of a curved rod was isolated from the Caspian Sea. Biochemical tests and 16S rRNA gene sequence analysis indicated that the isolate MM1 had more than 99% similarity to Vibrio campbellii. The novel isolate is able to emit high levels of light. Bioluminescence inhibitory assay showed that the Vibrio sp. MM1 had the highest sensitivity to zinc and the lowest sensitivity to cadmium; EC 50 values were 0.97mgl -1 and 14.54mgl -1 , respectively. The current research shows that even low concentrations of heavy metals can cause a detectable decline in luminescence activity of the novel bacterium Vibrio sp. MM1; hence, it makes a good choice for commercial kits for the purpose of monitoring toxic materials. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Europium enabled luminescent nanoparticles for biomedical applications

    Energy Technology Data Exchange (ETDEWEB)

    Syamchand, S.S., E-mail: syamchand.ss@gmail.com; Sony, G., E-mail: emailtosony@gmail.com

    2015-09-15

    Lanthanide based nanoparticles are receiving great attention ought to their excellent luminescent and magnetic properties and find challenging biomedical applications. Among the luminescent lanthanide NPs, europium based NPs (Eu-NPs) are better candidates for immunoassay and imaging applications. The Eu-NPs have an edge over quantum dots (QDs) by means of their stable luminescence, long fluorescence lifetime, sharp emission peaks with narrow band width, lack of blinking and biocompatibility. This review surveys the synthesis and properties of a variety of Eu-NPs consolidated from different research articles, for their applications in medicine and biology. The exquisite luminescent properties of Eu-NPs are explored for developing biomedical applications such as immunoassay and bioimaging including multimodal imaging. The biomedical applications of Eu-NPs are mostly diagnostic in nature and mainly focus on various key analytes present in biological systems. The luminescent properties of europium enabled NPs are influenced by a number of factors such as the site symmetry, the metal nanoparticles, metal ions, quantum dots, surfactants, morphology of Eu-NPs, crystal defect, phenomena like antenna effect and physical parameters like temperature. Through this review we explore and assimilate all the factors which affect the luminescence in Eu-NPs and coil a new thread of parameters that control the luminescence in Eu-NPs, which would provide further insight in developing Eu-based nanoprobes for future biomedical prospects. - Highlights: • The review describes 14 major factors that influence the luminescence properties of europium enabled luminescent nanoparticles (Eu-NPs). • Surveys different types of europium containing nanoparticles that have been reported for their biomedical applications. • Eu-NPs are conveniently divided into four different categories, based on the type of the substrates involved. The four categories are (1) virgin Eu-substrate based NPs; (2

  10. Europium enabled luminescent nanoparticles for biomedical applications

    International Nuclear Information System (INIS)

    Syamchand, S.S.; Sony, G.

    2015-01-01

    Lanthanide based nanoparticles are receiving great attention ought to their excellent luminescent and magnetic properties and find challenging biomedical applications. Among the luminescent lanthanide NPs, europium based NPs (Eu-NPs) are better candidates for immunoassay and imaging applications. The Eu-NPs have an edge over quantum dots (QDs) by means of their stable luminescence, long fluorescence lifetime, sharp emission peaks with narrow band width, lack of blinking and biocompatibility. This review surveys the synthesis and properties of a variety of Eu-NPs consolidated from different research articles, for their applications in medicine and biology. The exquisite luminescent properties of Eu-NPs are explored for developing biomedical applications such as immunoassay and bioimaging including multimodal imaging. The biomedical applications of Eu-NPs are mostly diagnostic in nature and mainly focus on various key analytes present in biological systems. The luminescent properties of europium enabled NPs are influenced by a number of factors such as the site symmetry, the metal nanoparticles, metal ions, quantum dots, surfactants, morphology of Eu-NPs, crystal defect, phenomena like antenna effect and physical parameters like temperature. Through this review we explore and assimilate all the factors which affect the luminescence in Eu-NPs and coil a new thread of parameters that control the luminescence in Eu-NPs, which would provide further insight in developing Eu-based nanoprobes for future biomedical prospects. - Highlights: • The review describes 14 major factors that influence the luminescence properties of europium enabled luminescent nanoparticles (Eu-NPs). • Surveys different types of europium containing nanoparticles that have been reported for their biomedical applications. • Eu-NPs are conveniently divided into four different categories, based on the type of the substrates involved. The four categories are (1) virgin Eu-substrate based NPs; (2

  11. Synthesis and Characterization of Fluoro- and Chlorobimetallic Alkoxides as Precursors for Luminescent Metal Oxide Materials via Sol-Gel Technique

    Institute of Scientific and Technical Information of China (English)

    ATHAR, Taimur; SEOK, Sang II; KWON, Jeong Oh

    2007-01-01

    Heterobimetallic alkoxides are broadly recognized as versatile precursors for luminescence materials, and efforts are being made to develop novel routes by applying the concept of geometrical molecular design, for their synthesis and to design a single source precursor suited to photoluminescent materials. Novel and new series of bimetallic alkoxides has been prepared by metathesis route. They exhibit a lower sensitivity towards hydrolysis and so they are easier to handle as compared to other alkoxides. All the compounds were characterized by elemental analysis, FT-IR and multinuclear NMR spectroscopies. FT-IR revealed that the molecular structure of these metal spectroscopy provided useful information about chemical shifts for better understanding the likely structure based on interactions with their coordinate metals. The mass spectra show similar types of fragmentation pattern.SEM-EDS analyses showed consistency with the formulation. XRD patterns show an enhanced homogeneity at high temperature. TGA measurements show that thermal decomposition occured in steps that depended entirely on the chemical compositions and the synthesis routes. SEM observation reveals that the morphology and particle size strongly depend on synthesis routes for their precursors.

  12. Investigations of gamma irradiation on the properties of luminescent films of polycarbonate(PC) matrix doped with europium complex [Eu(tta)3(H2O)2

    International Nuclear Information System (INIS)

    Forster, Pedro L.; Lugao, Ademar B.; Martins, Natalia A.; Egute, Nayara S.; Parra, Duclerc F.; Brito, Hermi F.

    2009-01-01

    Luminescent lanthanide complexes have attracted much recent interest for their application as luminescent materials. The combination of unique spectroscopic properties from rare earth complexes associated to physical and chemical intrinsic properties of polymers became more attractive in the last years. A number of advantages of these substances have been reported or realized over the much studied conjugated polymers and nonlanthanide. Luminescent films composed by diaquatris(thenoyltrifluoroacetonate)europium(III) complex [Eu(tta) 3 (H 2 O) 2 ] doped into a polycarbonate (PC) matrix were prepared and irradiated at gamma radiation with 5, 10, and 20 kGy. The PC polymer was doped with 1% (w/w) of the Eu 3+ complex. The thermal properties was investigated by utilization of differential scanning calorimeter (DSC) changes in thermal stability was observed due to the addition of doping agent into the polycarbonate matrix. Changes in photophysical properties due of gamma radiation was observed by emission, excitation spectra and fourier transformed infrared spectra (FTIR). Based on the emission spectra of PC:1% Eu(tta)3 film were observed the characteristic bands arising from the 5 D 0 7 F J transitions of Eu 3+ ion (J=0-4), indicating the ability to obtain the luminescence films. (author)

  13. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Diazo substituted carbomonocyclic... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting under...

  14. Tris-diamine-derived transition metal complexes of flurbiprofen as ...

    African Journals Online (AJOL)

    admin

    butyrylcholinesterase (BChE) inhibitory activities. Method: Tris-diamine-derived transition metal complexes of Co(II), Ni(II), and Mn(II) were synthesized and characterized ... Conductance measurements indicated that diamine-derived metal complexes of ..... contributes to enhanced biological activity, and provides novel ...

  15. Mixed Metal Complexes of Isoniazid and Ascorbic Acid: Chelation ...

    African Journals Online (AJOL)

    HP

    these ligands and their metal complexes have revealed the bi-dentate coordination of isoniazid ligand to ... of the drugs on coordination with a metal is enhanced ..... James, O.O., Nwinyi, C.O. and. Allensela, M.A. (2008). Cobalt(II) complexes of mixed antibiotics: Synthesis,. Characterization, antimicrobial potential and their.

  16. Novel luminescent Langmuir-Blodgett films of europium complex embedded in titania matrix

    International Nuclear Information System (INIS)

    Zhang Li; Liu, H.-G.; Kang, S.-Z.; Mu, Y.-D.; Qian, D.-J.; Lee, Yong-Ill; Feng Xusheng

    2005-01-01

    A stable Eu(DBM) 3 (DB-bpy)/AA/TiO 2 monolayer was formed on the surface of a composite subphase by spreading an Eu(DBM) 3 (DB-bpy)/AA/TBT chloroform solution. DBM, DB-bpy, AA and TBT refer to dibenzoylmethanate, 4,4'-Di-tert-butyl-2,2'-bipyridine, arachidic acid and tetrabutyloxyltitanium, respectively. Eu(DBM) 3 (DB-bpy)/AA/TiO 2 Langmuir-Blodgett films were deposited on solid substrates and were characterized by low-angle X-ray diffractometry, UV-visible (UV refers to ultra-violet) spectroscopy, photoluminescent spectroscopy and electron probe microanalysis. The results show that a luminescent composite film with layered structure was fabricated, which shows characteristic emission of Eu(III)

  17. Metallacyclopentadienes: structural features and coordination in transition metal complexes

    International Nuclear Information System (INIS)

    Dolgushin, Fedor M; Yanovsky, Aleksandr I; Antipin, Mikhail Yu

    2004-01-01

    Results of structural studies of polynuclear transition metal complexes containing the metallacyclopentadiene fragment are overviewed. The structural features of the complexes in relation to the nature of the substituents in the organic moiety of the metallacycles, the nature of the transition metals and their ligand environment are analysed. The main structural characteristics corresponding to different modes of coordination of metallacyclopentadienes to one or two additional metal centres are revealed.

  18. Modeling the influence of silver nanoparticles on the f–f luminescence of the EuEDTA complex in the polyvinylpirrolidone polymer

    Energy Technology Data Exchange (ETDEWEB)

    Couto dos Santos, M.A., E-mail: marcoscouto@ufs.br [Departamento de Física, Universidade Federal de Sergipe/CCET, São Cristóvão, SE 49100-000 (Brazil); Malta, O.L. [Departamento de Química Fundamental, Universidade Federalde Pernambuco/CCEN, Cidade Universitária, Recife, PE 50670-901 (Brazil); Reisfeld, R. [The Hebrew University of Jerusalem, Chemistry Institute, E. Safra Campus, 91904 Jerusalem (Israel)

    2016-02-15

    A theoretical analysis on experimental results previously obtained on the influence of silver nanoparticles in a polyvinylpirrolidone (PVP) polymer film containing a trivalent europium complex with EDTA ligand is made. Depending on the excitation source (at 393 nm with a xenon lamp or at 532 nm with a focused diode laser) the characteristic Eu{sup 3+} luminescence is observed to be enhanced by factors between 5 and 50. The theoretical analysis presumes a migration process of the EuEDTA complex units towards the silver nanoparticles, during the synthesis of the composite samples, and subsequently the treatment of the competition between local high field gradient effects and Eu{sup 3+} ion to the silver nanoparticles energy transfer successfully accounts for the observed luminescence enhancement factors. - Highlights: • Unusual luminescence enhancement of EuEDTA–silver nanoparticles–polyvinylpyrrolidone is treated theoretically. • A migration process of the EuEDTA complex units towards the silver nanoparticles is assumed. • The local high field gradient effects successfully accounts for the observed unusual luminescence enhancement factor of 50.

  19. Photophysical studies of highly luminescent europium(III) and terbium(III) complexes functionalized with amino and mercapto groups

    Energy Technology Data Exchange (ETDEWEB)

    Souza, E.R.; Monteiro, J.H.S.K.; Mazali, I.O.; Sigoli, F.A., E-mail: fsigoli@iqm.unicam.br

    2016-02-15

    This work proposes the replacement of coordinated-water molecules from the precursor complexes [Ln(aba){sub 3}(H{sub 2}O)] and [Ln(tta){sub 3}(H{sub 2}O){sub 2}], (Ln=Eu{sup 3+}, Gd{sup 3+} or Tb{sup 3+}, aba{sup −}=aminobenzoate, tta{sup −}=thenoyltrifluoroacetonate) by the ligands mercaptobenzoate (mba{sup −}), mercaptopropionate (mpa{sup −}), phenanthroline (phen), dimethylformamide (dmf) and acetoacetanilide (aaa{sup −}), leading to anionic or neutral amino (–NH{sub 2}) or mercapto (–SH) functionalized-lantanides (III) complexes with reasonable emission quantum yields for potential application on fluorescence microscopy of biological moieties. The complexes photophysical properties were studied using luminescence spectroscopy and theoretical models to determine the transfer and back energy transfer rates and quantum yields, that were compared with experimental ones. The anionic complexes [Eu(tta){sub 3}(L)]{sup −} showed high quantum yield values and their sensitization efficiency are in the range of 39–81%. The overlay of the ground state geometries, obtained from the Sparkle/PM3 model, of the complexes [Eu(tta){sub 3}(aba)]{sup −}, [Eu(tta){sub 3}(mba)]{sup −} and [Eu(tta){sub 3}(mpa)]{sup −}, suggest similar coordination polyhedrons occupied by the europium(III). The highest transfer rates T→{sup 5}D{sub 1,0} were obtained for the anionic complexes [Eu(tta){sub 3}(L)]{sup −} which might be a result of the low triplet level energies and R{sub L} values. - Highlights: • Lanthanides functionalized-complexes. • Free mercapto and amino groups. • Covalence degree of Eu-ligands. • Energy transfer rates. • Intrinsic and absolute quantum yields and sensitization.

  20. Studies in crystal structure and luminescence properties of Eu3+-doped metal tungstate phosphors for white LEDs

    International Nuclear Information System (INIS)

    Lee, Gwan-Hyoung; Kang, Shinhoo

    2011-01-01

    The correlation between the crystal structure and luminescent properties of Eu 3+ -doped metal tungstate phosphors for white LEDs was investigated. Red-emitting A 4-3x (WO 4 ) 2 :Eu x 3+ (A=Li, Na, K) and B (4-3x)/2 (WO 4 ) 2 :Eu x 3+ (B=Mg, Ca, Sr) phosphors were synthesized by solid-state reactions. The findings confirmed that these phosphors exhibited a strong absorption in the near UV to green range, due to the intra-configurational 4f-4f electron transition of Eu 3+ ions. The high doping concentration of Eu 3+ enhanced the absorption of near UV light and red emission without any detectable concentration quenching. Based on the results of a Rietveld refinement, it was attributed to the unique crystal structure. In the crystal structure of the Eu 3+ -doped metal tungstate phosphor, the critical energy transfer distance is larger than 5 A so that exchange interactions between Eu 3+ ions would occur with difficulty, even at a high doping concentration. The energy transfer between Eu 3+ ions, which causes a decrease in red emission with increasing concentration of Eu 3+ , appears to be due to electric multi-polar interactions. In addition, the Eu-O distance in the host lattice affected the shape of emission spectrum by splitting of emission peak at the 5 D 0 → 7 F 2 transition of Eu 3+ . - Highlights: → Eu 3+ -doped metal tungstate was synthesized as a red phosphor for white LEDs. → Crystal structure is tetragonal with a space group of I4 1 /c. → A strong absorption in the near UV to green range was observed. → High doping of Eu 3+ enhanced the absorption of near UV light and red emission.

  1. Luminescence properties of rare earth doped metal oxide nanostructures: A case of Eu-ZnO

    Energy Technology Data Exchange (ETDEWEB)

    Sahu, D. [School of Basic Sciences, Centurion University of Technology and Management, Odisha-752050 India (India); Acharya, B. S. [Department of Physics, C.V. Raman College of Engineering, Bhubaneswar, Odisha, India-752054 (India); Panda, N. R., E-mail: nihar@iitbbs.ac.in [School of Basic Sciences, Indian Institute of Technology Bhubaneswar, Odisha-751013 India (India)

    2016-05-06

    The present study reports the growth and luminescence properties of Eu doped ZnO nanostructures. The experiment has been carried out by synthesizing the materials by simple wet-chemical method. X-ray diffraction (XRD) studies show expansion of ZnO lattice with the incorporation of Eu ions which has been confirmed from the appearance of Eu{sub 2}O{sub 3} as a minor phase in the XRD pattern. The estimation of crystallite size from XRD results matches closely with the results obtained from transmission electron microscopy. Further, these results show the formation of nanosized Eu-ZnO particles of average size around 60 nm stacked on each other. FTIR studies show the presence of both Zn-O and Eu-O modes in the spectra supporting the results obtained from XRD. The interesting results obtained from photoluminescence (PL) measurements show the presence of both band edge emission in UV region and the defect emissions in violet, blue and green region. The appearance of {sup 5}D{sub 0}→{sup 7}F{sub J} transitions of Eu{sup 3+} ions in red region clearly suggests the possible occurrence of energy transfer between the energy states of ZnO host and Eu{sup 3+} ions.

  2. Metal-enhanced fluorescence of mixed coumarin dyes by silver and gold nanoparticles: Towards plasmonic thin-film luminescent solar concentrator

    Energy Technology Data Exchange (ETDEWEB)

    El-Bashir, S.M., E-mail: elbashireg@yahoo.com [Department of Physics and Astronomy, Science College, King Saud University, Riyadh, KSA (Saudi Arabia); Department of Physics Faculty of Science, Benha University (Egypt); Barakat, F.M.; AlSalhi, M.S. [Department of Physics and Astronomy, Science College, King Saud University, Riyadh, KSA (Saudi Arabia)

    2013-11-15

    Poly(methyl methacrylate) (PMMA) nanocomposite films doped with mixed coumarin dyestuffs and noble metal nanoparticles (60 nm silver and 100 nm gold) were prepared by spin coating technique. The effect of silver and gold nanoparticles on the film properties was studied by Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV–vis absorption and fluorescence spectroscopy measurements. DSC measurements indicated the increase of the glass transition temperature of the films by increasing nanogold concentration, recommending their promising thermal stability towards hot climates. It was found that the fluorescence signals of the mixed coumarin dyes were amplified by 5.4 and 7.15 folds as a result of metal enhanced fluorescence (MEF). The research outcomes offered a potential application of these films in solar energy conversion by plasmonic thin film luminescent solar concentrator (PTLSC). -- Graphical abstract: Plasmonic thin film luminescent solar concentrators. Highlights: • Metal enhanced fluorescence was achieved for mixed coumarin dyes doped in PMMA nanocomposite films. • The amplification of the fluorescence signals is dependent on the concentration of silver and gold nanoparticles. • These films is considered as potential candidates for plasmonic thin film luminescent solar concentrators (PTLSCs)

  3. A series of 2D metal-quinolone complexes: Syntheses, structures, and physical properties

    Energy Technology Data Exchange (ETDEWEB)

    He, Jiang-Hong [College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China); Xiao, Dong-Rong, E-mail: xiaodr98@yahoo.com.cn [College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China); Chen, Hai-Yan; Sun, Dian-Zhen; Yan, Shi-Wei; Wang, Xin; Ye, Zhong-Li [College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China); Luo, Qun-Li, E-mail: qlluo@swu.edu.cn [College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China); Wang, En-Bo, E-mail: wangeb889@nenu.edu.cn [Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun 130024 (China)

    2013-02-15

    Six novel 2D metal-quinolone complexes, namely [Cd(cfH)(bpdc)]{center_dot}H{sub 2}O (1), [M(norfH)(bpdc)]{center_dot}H{sub 2}O (M=Cd (2) and Mn (3)), [Mn{sub 2}(cfH)(odpa)(H{sub 2}O){sub 3}]{center_dot}0.5H{sub 2}O (4), [Co{sub 2}(norfH)(bpta)({mu}{sub 2}-H{sub 2}O)(H{sub 2}O){sub 2}]{center_dot}H{sub 2}O (5) and [Co{sub 3}(saraH){sub 2}(Hbpta){sub 2}(H{sub 2}O){sub 4}]{center_dot}9H{sub 2}O (6) (cfH=ciprofloxacin, norfH=norfloxacin, saraH=sarafloxacin, bpdc=4,4 Prime -biphenyldicarboxylate, odpa=4,4 Prime -oxydiphthalate, bpta=3,3 Prime ,4,4 Prime -biphenyltetracarboxylate) have been synthesized and characterized. Compounds 1-3 consist of 2D arm-shaped layers based on the 1D {l_brace}M(COO){r_brace}{sub n}{sup n+} chains. Compounds 4 and 5 display 2D structures based on tetranuclear manganese or cobalt clusters with (3,6)-connected kgd topology. Compound 6 exhibits a 2D bilayer structure, which represents the first example of metal-quinolone complexes with 2D bilayer structure. By inspection of the structures of 1-6, it is believed that the long aromatic polycarboxylate ligands are important for the formation of 2D metal-quinolone complexes. The magnetic properties of compounds 3-6 was studied, indicating the existence of antiferromagnetic interactions. Furthermore, the luminescent properties of compounds 1-2 are discussed. - Graphical abstract: Six novel 2D metal-quinolone complexes have been prepared by self-assemblies of the quinolones and metal salts in the presence of long aromatic polycarboxylates. Highlights: Black-Right-Pointing-Pointer Compounds 1-3 consist of novel 2D arm-shaped layers based on the 1D {l_brace}M(COO){r_brace}{sub n}{sup n+} chains. Black-Right-Pointing-Pointer Compounds 4 and 5 are two novel 2D layers based on tetranuclear Mn or Co clusters with kgd topology. Black-Right-Pointing-Pointer Compound 6 is the first example of metal-quinolone complexes with 2D bilayer structure. Black-Right-Pointing-Pointer Compounds 1-6 represent six unusual

  4. Luminescent pH sensor of a novel imidazole-containing hexanuclear Ru(II) polypyridyl complex

    Science.gov (United States)

    Cheng, Feixiang; Tang, Ning; Chen, Jishu; Chen, Guang

    2013-10-01

    Hexapodal ligand H6L containing imidazole rings has been prepared by the reaction of 1,10-phenanthroline-5,6-dione with 1,2,3,4,5,6-hexakis[(3-formylphenoxy)methyl]benzene. The Ru(II) polypyridyl complex [{Ru(bpy)2}6(μ6-H6L)](PF6)12 (bpy = 2,2'-bipyridine) has been synthesized by the reaction of Ru(bpy)2Cl2·2H2O with ligand H6L. The pH effects on the UV-vis absorption and emission spectra of the complex have been studied. The ground- and excited-state ionization constants of the acid-base equilibria have been calculated according to the absorbance and emission data. The complex acts as an off-on-off luminescent pH sensor through two successive deprotonation processes of imidazole rings, with a maximum on-off ratio of 5 in buffer solution.

  5. Luminescent single-ion magnets from Lanthanoid(III) complexes with monodentate ketone ligands

    Energy Technology Data Exchange (ETDEWEB)

    Kanetomo, Takuya; Ishida, Takayuki, E-mail: takayuki.ishida@uec.ac.jp [Department of Engineering Science, The University of Electro-Communications, Tokyo (Japan)

    2016-02-01

    We synthesized [Ln{sup III}(hfac){sub 3}(H{sub 2}O)(L)] (abbreviated as Ln-L; Ln = Gd, Tb, Eu; L = DTBK (di-t-butyl ketone), BP (benzophenone)), in which the carbonyl oxygen atom was coordinated to the Ln ion center, despite of such bulky substituents. Their crystal structures were determined by means of X-ray diffraction study. Gd-DTBK is completely isomorphous to the di-t-butyl nitroxide derivative and accordingly can be regarded as a model with the ligand spin masked. The ac magnetic susceptibility measurements on Tb-DTBK and -BP showed frequency dependence, characteristic of single-ion magnets. They also displayed photoluminescence in the solid state at room temperature. The quantum yields of the luminescence of Tb-DTBK and -BP (λ{sub ex} = 360 nm) were improved to 57 and 35%, respectively, from that of the starting material [TbI{sup III}(hfac){sub 3}(H{sub 2}O){sub 2}] (28% at λ{sub ex} = 370 nm). Similarly, the quantum yields for Eu-DTBK and -BP were 8 and 15%, respectively, with λ{sub ex} = 400 nm, while that of the starting material [EuI{sup III}(hfac){sub 3}(H{sub 2}O){sub 2}] was 4% at λ{sub ex}=400 nm.

  6. Spectroscopic investigation on europium doped heavy metal borate glasses for red luminescent application

    Energy Technology Data Exchange (ETDEWEB)

    Hegde, Vinod; Wagh, Akshatha; Kamath, Sudha D. [Manipal University, Department of Physics, Manipal Institute of Technology, Manipal (India); Hegde, Hemanth [Manipal University, Department of Chemistry, Manipal Institute of Technology, Manipal (India); Vishwanath, C.S.D. [Sri Venkateswara University, Department of Physics, Tirupati (India)

    2017-05-15

    The present study explores a new borate family glasses based on 10ZnO-5Na{sub 2}O-10Bi{sub 2}O{sub 3}-(75 - x) B{sub 2}O{sub 3}-xEu{sub 2}O{sub 3} (x = 0, 0.1, 0.5, 1, 1.5, 2, 3 mol%) composition, synthesized by rapid melt quench technique. Prepared glasses were subjected to the density and refractive index measurements and their values were used to calculate other physical properties of the glass matrix as a function of Eu{sup 3+} concentration. XRD confirmed amorphous nature of the glasses. FTIR spectra in the absorption mode were recorded in the 400-4000 cm{sup -1} region to identify different functional groups in the glass matrix. Deconvoluted FTIR spectra showed increase in BO{sub 4} units with rise in europium content which confirmed the 'network strengthener' role of europium ions by creating bridging oxygens (BOs). Optical properties were investigated for their luminescence behavior through various spectroscopic techniques such as UV-Vis-NIR absorption, excitation, emission, decay profiles, and color measurements at room temperature. Lasing properties of the glasses like total radiative life time, branching ratio, emission cross section, and optical gain were obtained from the calculated Judd-Ofelt (Ω{sub 2},Ω{sub 4}) intensity parameters. From the measured values of emission, cross sections, branching ratios, life times, strong photoluminescence features, and CIE chromaticity coordinates, 0.5 mol% of Eu{sup 3+} ions doped ZnNaBiB glasses showed optimum performance and are potential candidate for red light generation at 613 nm. (orig.)

  7. Selective recognition of 6-mercaptopurine based on luminescent metal-organic frameworks Fe-MIL-88NH₂.

    Science.gov (United States)

    Sun, Zhengjuan; Liu, Yali; Li, Yuanfang

    2015-03-15

    A novel and rapid spectrofluorometry method for the recognition of 6-mercaptopurine (6-MP) has been developed based on luminescent metal-organic frameworks Fe-MIL-88NH2 as fluorescent probe. The strong fluorescence of Fe-MIL-88NH2 at 430 nm could be quenched by 6-MP directly, and the Fe-MIL-88NH2 shows high selectivity for 6-MP compared to other thiol-containing amino acids such as homocysteine (Hcy), cysteine (Cys), glutathione (GSH), etc. Under optimal conditions, the relative fluorescence intensity was linearly proportional to the concentration of 6-MP in the range of 5-600 μM with the detection limit at 1.17 μM (S/N=3). Furthermore, the present approach has been successfully applied to the determination of 6-MP in human serum samples. The possible fluorescence quenching mechanism has also been investigated, where it is revealed that the quenching was attributed to competition of absorption of the light source energy as well as electron transfer between Fe-MIL-88NH2 and 6-MP. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Temperature and pressure variations of d-d luminescence band maxima of bis(pyridylalkenolato)palladium(II) complexes with different ligand substituents: opposite-signed trends.

    Science.gov (United States)

    Poirier, Stéphanie; Czympiel, Lisa; Bélanger-Desmarais, Nicolas; Mathur, Sanjay; Reber, Christian

    2016-04-21

    Luminescence spectra of two d(8)-configured bis(pyridylalkenolato)palladium(ii) complexes, [Pd{PyCHC(C3F7)O}2] and [Pd{PyCHC(CH3)O}2], are presented at variable temperature and pressure. Bands are assigned as d-d transitions. The heptafluoropropyl and methyl substituents on the ligands have different steric demands, influencing luminescence spectra. Broad bands with maxima at approximately 12 700 cm(-1) (790 nm) for ligands with heptafluoropropyl substituents and 12,100 cm(-1) (830 nm) for ligands with methyl substituents and widths of approximately 2100 cm(-1) for both complexes are observed at 80 K. Quenching of the luminescence is observed as temperature increases. The maxima of [Pd{PyCHC(C3F7)O}2] show a shift of -0.9 ± 0.1 cm(-1) K(-1) due to broadening of the spectra to lower energy. The luminescence maxima of [Pd{PyCHC(CH3)O}2] shift in the opposite direction by +7.2 ± 0.7 cm(-1) K(-1). Shifts with different signs are also obtained from variable-pressure luminescence spectra, with values of +13 ± 2 cm(-1) kbar(-1) and -15 ± 7 cm(-1) kbar(-1) for [Pd{PyCHC(C3F7)O}2] and [Pd{PyCHC(CH3)O}2], respectively. The pressure-induced decrease is unusual and likely caused by intermolecular interactions involving the palladium(ii) center and a vinylic proton of a neighboring complex.

  9. Reactivity of monoolefin ligand in transition metal complexes

    International Nuclear Information System (INIS)

    Rybinskaya, M.I.

    1978-01-01

    The main tendencies in the coordinated olefin ligand property changes are discussed in the transition metal complexes in comparison with free olefins. The review includes the papers published from 1951 up to 1976. It has been shown that in complexes with transition metal cations olefin π-base acquires the ability to react with nucleophylic reagents. Olefin π-acids in complexes with zero valent metals are easily subjected to electrophylic reagent action. At coordination with transition metal cations the olefin properties are generally preserved, while in the zero-valent metal complexes the nonsaturated ligand acquires the properties of a saturated compounds. The ability of transition metal cations in complexes to intensify reactions of nucleophylic bimolecular substitution of vinyl halogen is clearly detected in contrast to the zero valent metal complexes. It has been shown that investigations of the coordinated olefin ligand reactivity give large possibilities in the further development of the organic synthesis. Some reactions are taken as the basis of important industrial processes

  10. Surface polyPEGylation of Eu{sup 3+} doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Guangjian; Liu, Meiying [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Heng, Chunning [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Huang, Qiang; Mao, Liucheng; Huang, Hongye [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Hui, Junfeng [Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and The Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China)

    2017-03-31

    Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu{sup 3+} doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu{sup 3+} doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface

  11. Surface polyPEGylation of Eu"3"+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-01-01

    Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu"3"+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu"3"+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated

  12. Selective fluorescence sensors for detection of nitroaniline and metal Ions based on ligand-based luminescent metal-organic frameworks

    International Nuclear Information System (INIS)

    Yu, Zongchao; Wang, Fengqin; Lin, Xiangyi; Wang, Chengmiao; Fu, Yiyuan; Wang, Xiaojun; Zhao, Yongnan; Li, Guodong

    2015-01-01

    Metal-organic frameworks (MOFs) are porous crystalline materials with high potential for applications in fluorescence sensors. In this work, two solvent-induced Zn(II)–based metal-organic frameworks, Zn_3L_3(DMF)_2 (1) and Zn_3L_3(DMA)_2(H_2O)_3 (2) (L=4,4′-stilbenedicarboxylic acid), were investigated as selective sensing materials for detection of nitroaromatic compounds and metal ions. The sensing experiments show that 1 and 2 both exhibit selective fluorescence quenching toward nitroaniline with a low detection limit. In addition, 1 exhibits high selectivity for detection of Fe"3"+ and Al"3"+ by significant fluorescence quenching or enhancement effect. While for 2, it only exhibits significant fluorescence quenching effect for Fe"3"+. The results indicate that 1 and 2 are both promising fluorescence sensors for detecting and recognizing nitroaniline and metal ions with high sensitivity and selectivity. - Graphical abstract: Two MOFs have been selected as the fluorescence sensing materials for selectively sensing mitroaromatic compounds and metal ions. The high selectivity makes them promising fluorescence sensors for detecting and recognizing nitroaniline and Fe"3"+ or Al"3"+.

  13. N-acyl thioureas - selective ligands for complexing of heavy metals and noble metals

    International Nuclear Information System (INIS)

    Schuster, M.

    1992-01-01

    Acyl thioureas are complexing agents for heavy metals that are easily produced and very stable. Their favourable toxicological data make them particularly suitable for industrial applications, e.g. detoxification of metallic process solutions or solvent extraction of metals. (orig.) [de

  14. Alkylation and arylation of alkenes by transition metal complexes

    International Nuclear Information System (INIS)

    Volkova, L.G.; Levitin, I.Ya.; Vol'pin, M.E.

    1975-01-01

    In this paper are reviewed methods of alkylation and irylation of unsaturated compounds with complexes of transition metals (Rh, Pd). Analysis of alkylation and arylation of olefines with organic derivatives of transition metals, obtained as a result of exchange reactions between organic compounds of transition metals and salts of metals of the 8th group of the periodic system, allows a conclusion as to the wide possibilities of these reactions in the synthesis of various derivatives of unsaturated compounds. In all the reactions under consideration, intermediate formation of sigma-complexes is assumed. Also considered are alkylation and arylation of olefines with organic derivatives of halogens in the presence of compounds of metals of the 8th group of the periodic system, as well as arylation of olefines with aromatic compounds in the presence of salts of transition metals

  15. Kinetics of the reactions of hydrated electrons with metal complexes

    International Nuclear Information System (INIS)

    Korsse, J.

    1983-01-01

    The reactivity of the hydrated electron towards metal complexes is considered. Experiments are described involving metal EDTA and similar complexes. The metal ions studied are mainly Ni 2+ , Co 2+ and Cu 2+ . Rates of the reactions of the complexes with e - (aq) were measured using the pulse radiolysis technique. It is shown that the reactions of e - (aq) with the copper complexes display unusually small kinetic salt effects. The results suggest long-range electron transfer by tunneling. A tunneling model is presented and the experimental results are discussed in terms of this model. Results of approximate molecular orbital calculations of some redox potentials are given, for EDTA chelates as well as for series of hexacyano and hexaquo complexes. Finally, equilibrium constants for the formation of ternary complexes are reported. (Auth./G.J.P.)

  16. Luminescence and Electronic Spectral Studies of Some Synthesized Lanthanide Complexes Using Benzoic Acid Derivative and o-Phenanthroline.

    Science.gov (United States)

    Wankar, Sneha; Limaye, S N

    2015-07-01

    Lanthanide complexes of p-nitrobenzoic acid(p-NBA) and o-phenanthroline(o-phen) namely [Ln2(Phen)2(p-NBA)3(NO3)2].2H2O where, Ln = Sm(III),Tb(III),Dy(III) and [Eu2(Phen)2(p-NBA)3].4H2O were synthesized and further characterized by Elemental analysis, UV spectroscopy, IR spectroscopy, (1)HNMR spectroscopy. Luminescence measurements were performed on all compounds in ethanolic solution. These complexes have showed narrow emission indicating that the organic ligands are better energy absorber and capable of transferring energy to the Ln (III) ion. Furthermore, we reported electronic spectral studies on [Eu2 (Phen)2 (p-NBA)3].4H2O in order to calculate following parameters, viz: Oscillator strength (f), Judd-Ofelt parameters Ωλ (λ = 2,4,6) and Radiative parameters. [Eu2 (o-Phen)2 (p-NBA)3].4H2O showed the strongest emission at 613 nm corresponds to (5)D0→(7)F2 hypersensitive transition, this emission is very sensitive to the environment. However, the larger value of Ω2 supports the presence of the hypersensitive transition (5)D0→(7)F2 which strictly depends on the nature of ligand. All electronic spectral parameters were calculated systemically.

  17. Luminescence behaviors of Eu- and Dy-codoped alkaline earth metal aluminate phosphors through potassium carbonate coprecipitation

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Chen-Jui, E-mail: cjliang@fcu.edu.tw; Siao, Hao-Yi

    2016-07-01

    An electronic energy mechanism of activator and sensitizer was established to describe the luminescence behaviors of Eu- and Dy-codoped M(II)Al{sub 2}O{sub 4} (M(II) = Ba, Sr, Ca, Mg) phosphors through potassium carbonate coprecipitation. Experimental results demonstrated that the prepared phosphors exhibited superior crystallinity at a temperature lower than 950 °C. The phosphors are ordered according to emission intensity as follows Ca- > Ba- > Sr- > Mg-containing phosphors. The energy level for Eu{sup 2+} 4f{sup 6}5d{sup 1} → 4f{sup 7}, Eu{sup 3+4}D{sub 0} → {sup 7}F, and Dy{sup 3+4}F{sub 9/2} → {sup 6}H transitions and the effects of nephelauxetic and crystal field in Ba-, Sr-, and Ca-containing phosphors were discussed. The energy gap, (hv){sub em}, between 5d and 4f of Eu{sup 2+} ion is strongly affected by host composition, crystal field strength, and nephelauxetic effect. The infrared emission of 4f{sub 9/2} → 6h for Dy{sup 3+} is merely depend on the transfer of energy from Eu{sup 2+} upon excited. Ca-containing phosphor with maximum (hv){sub em} is attributed to the lowest bond length of Ca−O and highest ionization potential of Ca{sup 2+} ion, which leads to the effects of crystal field and nephelauxetic greater than that in the other phosphors. - Highlights: • The list of the collected figure captions: • Develop a new coprecipitation method to prepare high efficiency phosphors. • Obtain superior crystallinity with lower calcination temperature. • Luminescence behavior of Eu- and Dy-codoped on aluminate phosphors is discussed. • Investigate the effects of alkaline earth metal containing on crystal field and nephelauxetic.

  18. Assembly of a water-insoluble strontium metal-organic framework with luminescent properties

    Czech Academy of Sciences Publication Activity Database

    Lo, S.-H.; Liu, H.-K.; Zhan, J.-X.; Lin, W.-Ch.; Kao, Ch.-Ch.; Lin, Ch.-H.; Zima, Vítězslav

    2011-01-01

    Roč. 14, č. 10 (2011), 1602-1605 ISSN 1387-7003 R&D Projects: GA ČR GA203/08/0208 Institutional research plan: CEZ:AV0Z40500505 Keywords : structure * strontium * metal -organic Subject RIV: CA - Inorganic Chemistry Impact factor: 1.972, year: 2011

  19. Luminescent properties and structure of multicomponent naphthalene-{beta}-cyclodextrin complexes. 1. Effect of adding third parties, o-carborane or/and adamantane

    Energy Technology Data Exchange (ETDEWEB)

    Nazarov, Valery B. [Institute of Problems of Chemical Physics of Russian Academy of Sciences, 142432 Moscow region, Chernogolovka (Russian Federation); Avakyan, Vitaly G., E-mail: avak@photonics.ru [Photochemistry Center of Russian Academy of Sciences, 119421 Moscow, Novatorov 7a (Russian Federation); Rudyak, Vladimir Y.; Alfimov, Michail V. [Photochemistry Center of Russian Academy of Sciences, 119421 Moscow, Novatorov 7a (Russian Federation); Vershinnikova, Tatiana G. [Institute of Problems of Chemical Physics of Russian Academy of Sciences, 142432 Moscow region, Chernogolovka (Russian Federation)

    2011-09-15

    Luminescence spectra of water solution of {beta}-cyclodextrin ({beta}-CD) inclusion complexes with naphthalene have been studied in the presence of carcass compounds (CC), adamantane and ocarborane, added in solution as the third parties. It was observed that the CC structure completely determines luminescence type displayed by the three-component complex. Adding adamantane to the solution leads to the disappearance of the spontaneous excimer fluorescence observed usually along with a monomer fluorescence of naphthalene and the appearance of the long lived phosphorescence at room temperature. At the same time, introducing o-carborane in solution of {beta}-CD inclusion complexes with naphthalene results in the dramatic growth of intensity of the excimer band at the expense of lowering intensity of monomer fluorescence. These phenomena were explained using results of the quantum-chemical calculation of the structure and complexation energies at the semi-empirical PM3 and DFT levels of theory. - Highlights: > Structure of carcass compounds determines luminescence types for naphthalene - betaCD complex. > Adding o-carborane leads to the growth of excimer fluorescence at low naphthalene concentrations. > Adding adamantane leads to the room temperature phosphorescence without deoxygenation.

  20. Solid state luminescence of CuI and CuNCS complexes with phenanthrolines and a new tris (aminomethyl) phosphine derived from N-methyl-2-phenylethanamine

    International Nuclear Information System (INIS)

    Starosta, Radosław; Komarnicka, Urszula K.; Puchalska, Małgorzata

    2014-01-01

    A new tris (aminomethyl) phosphine derived from N-methyl-2-phenylethanamine P(CH 2 N(CH 3 )CH 2 CH 2 Ph) 3 (1) has been synthesized and characterized by the NMR spectra. Also, three new copper(I) iodide or isothiocyanate complexes with 1 1,10-phenanthroline (phen) and 2,9-dimethyl-1,10-phenanthroline (dmp) [CuI(phen)P(CH 2 N(CH 3 )CH 2 CH 2 Ph) 3 ] (1P) CuI(dmp)P(CH 2 N(CH 3 )CH 2 CH 2 Ph) 3 ] (1I) and [CuNCS(dmp)P(CH 2 N(CH 3 )CH 2 CH 2 Ph) 3 ] (1T), have been synthesized and characterized by elemental analysis as well as studied by NMR, UV–vis, IR and luminescence spectroscopies. An X-ray structure of 1P complex revealed that the geometry around Cu(I) center in this complex is distorted pseudo-tetrahedral. Investigated complexes exhibit orange, rather weak photoluminescence in the solid state. This relatively low intensity may be related to the high flattening deformations of the molecular geometries in the excited triplet states On the basis of TDDFT calculations we confirmed that the absorbance and luminescence bands of (MX,MPR 3 )LCT as well as of (MX)LCT types result mainly from the transitions from the copper–iodine (or isothiocyanate) bonds and a small admixture of copper–phosphine bonds to antibonding orbitals of phen or dmp diimines. -- Highlights: • A novel tris(aminomethyl)phosphine is obtained from N-methyl-2-phenylethanamine. • Three new CuI and CuNCS complexes with phen or dmp and a novel phosphine are presented. • The obtained complexes are luminescent in the solid state. • Main absorbance and luminescence bands are of (MX,MPR 3 )LCT as well as (MX)LCT types

  1. Thiosemicarbazone complexes of the platinum metals. A story of ...

    Indian Academy of Sciences (India)

    Unknown

    Thiosemicarbazone complexes; platinum metals; variable coordination; ... carbonylic carbon via one or two intervening atoms, D,N,S tricoordination usually takes .... modelling studies show that in this coordination mode, the phenyl ring of the.

  2. 3d-METAL COMPLEXES WITH BARBITURIC ACID DERIVATIVES

    Directory of Open Access Journals (Sweden)

    T. V. Koksharova

    2015-04-01

    Full Text Available The various aspects of the 3d-metal complexes with barbiturates and uric acid chemistry such as composition, structure, physicochemical properties, possible fields of application – have been illustrated in this review

  3. Structural systematics of some metal complexes with 4,5 ...

    Indian Academy of Sciences (India)

    study reveals that each metal(II) centre in the four complexes adopts distorted octahedral geometry with MN6 ... potassium permanganate (E Merck, India), potassium. 717 ... The final reaction solu- ..... ble in water, methanol, acetonitrile, etc.

  4. Sub-chronic toxicological studies of transition metal complexes of ...

    African Journals Online (AJOL)

    Md. Sharif Hasan

    2017-01-18

    Jan 18, 2017 ... naproxen showed more side effects than metal complexes which ..... Fosslein E. Adverse effects of nonsteroidal anti-inflammatory drugs on the ... association increases the anti-inflammatory and analgesic activity of ibuprofen.

  5. Synthesis and characterization of some metal complexes of a Schiff ...

    African Journals Online (AJOL)

    KEY WORDS: Metal complexes, Schiff base, Ninhydrin, α,L-Alanine, .... Buck Scientific Infrared Spectrophotometer Model 500 in the range of 4000 .... Assignments based on Nakamoto [35], ν - stretching vibration, δ - bending or deformation.

  6. Bovine Serum Albumin Metal Complexes for Mimic of SOD

    Indian Academy of Sciences (India)

    Key Lab. Eco-Environment-Related Polymer Materials of Ministry of Education, Key Lab. ... scaffold and the metal complex functioned as the catalytic active center. ... small molecule.22 It is found that the antioxidative ... and absence, respectively, of the measured compound. ... monitor the interaction of metal ions with BSA.

  7. Inkjet Printing of 3D Metallic Silver Complex Microstructures

    NARCIS (Netherlands)

    Wits, Wessel Willems; Sridhar, Ashok; Dimitrov, D.

    2010-01-01

    To broaden the scope of inkjet printing, this paper focuses on printing of an organic silver complex ink on glass substrates towards the fabrication of metallic 3D microstructures. The droplet formation sequence of the inkjet printer is optimised to print continuous layers of metal. A brief

  8. Revisited: the conception of lability of metal complexes

    NARCIS (Netherlands)

    Leeuwen, van H.P.

    2001-01-01

    Starting from the original reaction layer concept, the voltammetric properties of electroinactive metal complexes are critically reviewed in terms of their finite rates of dissociation into electroactive free metal ions. The limiting conditions for the reaction layer-based flux expressions are made

  9. Compartmentation and complexation of metals in hyperaccumulator plants

    Directory of Open Access Journals (Sweden)

    Barbara eLeitenmaier

    2013-09-01

    Full Text Available Hyperaccumulators are being intensely investigated. They are not only interesting in scientific context due to their strange behaviour in terms of dealing with high concentrations of metals, but also because of their use in phytoremediation and phytomining, for which understanding the mechanisms of hyperaccumulation is crucial. Hyperaccumulators naturally use metal accumulation as a defence against herbivores and pathogens, and therefore deal with accumulated metals in very specific ways of complexation and compartmentation, different from non-hyperaccumulator plants and also non-hyperaccumulated metals. For example, in contrast to non-hyperaccumulators, in hyperaccumulators even the classical phytochelatin-inducing metal, cadmium, is predominantly not bound by such sulfur ligands, but only by weak oxygen ligands. This applies to all hyperaccumulated metals investigated so far, as well as hyperaccumulation of the metalloid arsenic. Stronger ligands, as they have been shown to complex metals in non-hyperaccumulators, are in hyperaccumulators used for transient binding during transport to the storage sites. This confirmed that enhanced active metal transport, and not metal complexation, is the key mechanism of hyperaccumulation. Hyperaccumulators tolerate the high amount of accumulated heavy metals by sequestering them into vacuoles, usually in large storage cells of the epidermis. This is mediated by strongly elevated expression of specific transport proteins in various tissues from metal uptake in the shoots up to the storage sites in the leaf epidermis. However, this mechanism seems to be very metal specific. Non-hyperaccumulated metals in hyperaccumulators seem to be dealt with like in non-hyperaccumulator plants, i.e. detoxified by binding to strong ligands such as metallothioneins.

  10. Synthesis, Crystal Structure and Luminescent Property of Cd (II Complex with N-Benzenesulphonyl-L-leucine

    Directory of Open Access Journals (Sweden)

    Xishi Tai

    2012-09-01

    Full Text Available A new trinuclear Cd (II complex [Cd3(L6(2,2-bipyridine3] [L = N-phenylsulfonyl-L-leucinato] has been synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. The results show that the complex belongs to the orthorhombic, space group P212121 with a = 16.877(3 Å, b = 22.875(5 Å, c = 29.495(6 Å, α = β = γ = 90°, V = 11387(4 Å3, Z = 4, Dc= 1.416 μg·m−3, μ = 0.737 mm−1, F (000 = 4992, and final R1 = 0.0390, ωR2 = 0.0989. The complex comprises two seven-coordinated Cd (II atoms, with a N2O5 distorted pengonal bipyramidal coordination environment and a six-coordinated Cd (II atom, with a N2O4 distorted octahedral coordination environment. The molecules form one dimensional chain structure by the interaction of bridged carboxylato groups, hydrogen bonds and p-p interaction of 2,2-bipyridine. The luminescent properties of the Cd (II complex and N-Benzenesulphonyl-L-leucine in solid and in CH3OH solution also have been investigated.

  11. A visible-light-excited europium(III) complex-based luminescent probe for visualizing copper ions and hydrogen sulfide in living cells

    Science.gov (United States)

    Wang, Yiren; Wang, Huan; Yang, Mei; Yuan, Jingli; Wu, Jing

    2018-01-01

    Development of visible-light-excited lanthanide (III) complex-based luminescent probes is highly appealing due to their superiority of less damage to the living biosystems over the conventional UV-light-excited ones. In this work, a visible-light-excited europium (III) complex-based luminescent probe, BPED-BHHCT-Eu3+-BPT, has been designed and synthesized by conjugating the Cu2+-binding N,N-bis(2-pyridylmethyl)ethanediamine (BPED) to a tetradentate β-diketone ligand 4,4‧-bis(1″,1″,1″,2″,2″,3″,3″-heptafluoro-4″,6″-hexanedione-6″-yl)chlorosulfo-o-terphenyl (BHHCT) and coordinating with a coligand 2-(N,N-diethylanilin-4-yl)-4,6-bis(pyrazol-1-yl)-1,3,5-triazine) (BPT) for the time-gated luminescence detection of Cu2+ ions and hydrogen sulfide (H2S) in living cells. BPED-BHHCT-Eu3+-BPT exhibited a sharp excitation peak at 407 nm and a wide excitation window extending to beyond 460 nm. Upon its reaction with Cu2+ ions, the luminescence of BPED-BHHCT-Eu3+-BPT was efficiently quenched, which could be reversibly restored by the addition of H2S due to the strong affinity between Cu2+ ions and H2S. The "on-off-on" type luminescence behavior of BPED-BHHCT-Eu3+-BPT towards Cu2+ ions and H2S enabled the sensing of the two species with high sensitivity and selectivity. The performances of BPED-BHHCT-Eu3+-BPT for visualizing intracellular Cu2+ ions and H2S were investigated, and the results have demonstrated the practical applicability of the probe for molecular imaging of cells.

  12. Synthesis, structures, and luminescent properties of lanthanide complexes with triphenylphospine oxide

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Yan; Xu, Shan; Wang, Xin; Li, Yue-Xue; Jin, Qiong-Hua [Department of Chemistry, Capital Normal University, Beijing (China); Liu, Min [The College of Materials Science and Engineering, Beijing University of Technology (China); Xin, Xiu-Lan [School of Food and Chemical Engineering, Beijing Technology and Business University (China)

    2017-07-03

    Seven lanthanide complexes [Ln(OPPh{sub 3}){sub 3}(NO{sub 3}){sub 3}] (1-3) (OPPh{sub 3} = triphenylphosphine oxide, Ln = Nd, Sm, Gd), [Dy(OPPh{sub 3}){sub 4}(NO{sub 3}){sub 2}](NO{sub 3}) (4), [Ln(OPPh{sub 3}){sub 3}(NO{sub 3}){sub 3}]{sub 2} (5-7) (Ln = Pr, Eu, Gd) were synthesized by the reactions of different lanthanide salts and OPPh{sub 3} ligand in the air. These complexes were characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR and fluorescence spectra. Structure analysis shows that complexes 1-4 are mononuclear complexes formed by OPPh{sub 3} ligands and nitrates. The asymmetric units of complexes 5-7 consist of two crystallographic-separate molecules. Complex 1 is self-assembled to construct a 2D layer-structure of (4,4) net topology by hydrogen bond interactions. The other complexes show a 1D chain-like structure that was assembled by OPPh{sub 3} ligands and nitrate ions through C-H..O interactions. Solid emission spectra of compounds 4 and 6 are assigned to the characteristic fluorescence of Tb{sup 3+} (λ{sub em} = 480, 574 nm) and Eu{sup 3+} (λ{sub em} = 552, 593, 619, 668 nm). (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Synthesis, characterization and biological profile of metal and azo-metal complexes of embelin

    Directory of Open Access Journals (Sweden)

    R. Aravindhan

    2014-12-01

    Full Text Available The present study emphasizes synthesis and bioprofiling of embelin, embelin-metal (EM and embelin-azo-metal (EAM complexes in detail. EM complexes were prepared using pure embelin and d-block transition elements, namely Mn, Fe, Co, Ni, Cu, and Zn. Similarly, EAM complexes were synthesized using phenyl azo-embelin with the said transition metals. Embelin, EM, and EAM complexes were subjected to ultra violet visible spectroscopy, Fourier transform infrared spectroscopy, nuclear magnetic resonance, electrospray ionization mass spectrometry, thermogravimetric analysis, carbon hydrogen nitrogen sulfur analysis. With regard to bioprofiling, the test complexes were studied for the antioxidant and antimicrobial activities. Results revealed that the prepared EM and EAM complexes form octahedral complexes with embelin with the yield in the range of 45–75%. All the instrumental analyses authenticate the interaction of metals with bidentate embelin through its enolic and quinonic oxygen atoms as [M(Emb2(H2O2]H2O and [M(Emb-Azo2(H2O2]. The antioxidant profile studies suggested that upon complexation with metals, the free radical scavenging activity of embelin reduced significantly. But, with regard to antimicrobial activity, cobalt and nickel embelin complexes displayed>80% growth inhibition in comparison with embelin alone. The hemolytic activity studies suggested that both embelin and the metal complexes are non-hemolytic. The reason for the reduction in antioxidant and an increase in antimicrobial activities were discussed in detail.

  14. A label-free luminescent switch-on assay for ATP using a G-quadruplex-selective iridium(III) complex.

    Science.gov (United States)

    Leung, Ka-Ho; Lu, Lihua; Wang, Modi; Mak, Tsun-Yin; Chan, Daniel Shiu-Hin; Tang, Fung-Kit; Leung, Chung-Hang; Kwan, Hiu-Yee; Yu, Zhiling; Ma, Dik-Lung

    2013-01-01

    We report herein the G-quadruplex-selective property of a luminescent cyclometallated iridium(III) complex for the detection of adenosine-5'-triphosphate (ATP) in aqueous solution. The ATP-binding aptamer was employed as the ATP recognition unit, while the iridium(III) complex was used to monitor the formation of the G-quadruplex structure induced by ATP. The sensitivity and fold enhancement of the assay were higher than those of the previously reported assay using the organic dye crystal violet as a fluorescent probe. This label-free luminescent switch-on assay exhibits high sensitivity and selectivity towards ATP with a limit of detection of 2.5 µM.

  15. A label-free luminescent switch-on assay for ATP using a G-quadruplex-selective iridium(III complex.

    Directory of Open Access Journals (Sweden)

    Ka-Ho Leung

    Full Text Available We report herein the G-quadruplex-selective property of a luminescent cyclometallated iridium(III complex for the detection of adenosine-5'-triphosphate (ATP in aqueous solution. The ATP-binding aptamer was employed as the ATP recognition unit, while the iridium(III complex was used to monitor the formation of the G-quadruplex structure induced by ATP. The sensitivity and fold enhancement of the assay were higher than those of the previously reported assay using the organic dye crystal violet as a fluorescent probe. This label-free luminescent switch-on assay exhibits high sensitivity and selectivity towards ATP with a limit of detection of 2.5 µM.

  16. Synthesis, characterization, and near-infrared luminescent properties of the ternary thulium complex covalently bonded to mesoporous MCM-41

    International Nuclear Information System (INIS)

    Feng Jing; Song Shuyan; Xing Yan; Zhang Hongjie; Li Zhefeng; Sun Lining; Guo Xianmin; Fan Weiqiang

    2009-01-01

    The crystal structure of a ternary Tm(DBM) 3 phen complex (DBM=dibenzoylmethane; phen=1, 10-phenanthroline) and the synthesis of hybrid mesoporous material in which the complex covalently bonded to mesoporous MCM-41 are reported. Crystal data: Tm(DBM) 3 phen C 59 H 47 N 2 O 7 Tm, monoclinic, P21/c, a=19.3216(12) A, b=10.6691(7) A, c=23.0165(15) A, α=90 deg., β=91.6330(10) deg., γ=90 deg., V=4742.8(5) A 3 , Z=4. The properties of the Tm(DBM) 3 phen complex and the corresponding hybrid mesoporous material [Tm(DBM) 3 phen-MCM-41] have been studied. The results reveal that the Tm(DBM) 3 phen complex is successfully covalently bonded to MCM-41. Both Tm(DBM) 3 phen complex and Tm(DBM) 3 phen-MCM-41 display typical near-infrared (NIR) luminescence upon excitation at the maximum absorption of the ligands, which contributes to the efficient energy transfer from the ligands to the Tm 3+ ion, an antenna effect. The full width at half maximum (FWHM) centered at 1474 nm in the emission spectrum of Tm(DBM) 3 phen-MCM-41 is 110 nm, which is the potential candidate of broadening amplification band from C band (1530-1560 nm) to S + band (1450-1480 nm) in optical area. - Graphical abstract: The crystal structure of Tm(DBM) 3 phen complex (DBM=dibenzoylmethane; phen=1, 10-phenanthroline). The complex is successfully covalently bonded to MCM-41 (Tm(DBM) 3 phen-MCM-41). After ligand-mediated excitation, the emission spectrum of Tm(DBM) 3 phen-MCM-41 shows the bands 802 and 1474 nm. The FWHM of the 1474-nm band for Tm(DBM) 3 phen-MCM-41 is 110 nm, such a broad spectrum enables a wide gain bandwidth for optical amplification

  17. Colorimetric and luminescent bifunctional iridium(III) complexes for the sensitive recognition of cyanide ions

    Science.gov (United States)

    Chen, Xiudan; Wang, Huili; Li, Jing; Hu, Wenqin; Li, Mei-Jin

    2017-02-01

    Two new cyclometalated iridium(III) complexes [(ppy)2Irppz]Cl (1) and [(ppy)2Irbppz]Cl (2) (where ppy = 2-phenylpyridine, ppz = 4,7-phenanthrolino-5,6:5,6-pyrazine, bppz = 2.3-di-2-pyridylpyrazine), were designed and synthesized. The structure of [(ppy)2Irppz]Cl was determined by single crystal X-ray diffraction. Their photophysical properties were also studied. This kind of complexes could coordinate with Cu2 +, the photoluminescence (PL) of the complex was quenched, and the color changed from orange-red to green. The forming M-Cu (M: complexes 1 and 2) ensemble could be further utilized as a colorimetric and emission ;turn-on; bifunctional detection for CN-, especially for complex 1-Cu2 + showed a high sensitivity toward CN- with a limit of diction is 97 nM. Importantly, this kind of iridium(III) complexes shows a unique recognition of cyanide ions over other anions which makes it an eligible sensing probe for cyanide ions.

  18. Demonstration of metallic implants by means of digital luminescence radiography (DLR)

    International Nuclear Information System (INIS)

    Wiesmann, W.; Reiser, M.; Fiebich, M.; Bick, U.; Peters, P.E.

    1990-01-01

    DLR makes it possible to integrate conventional radiography into digital communication and storage methods (PACS) into radiology. The use of DLR has been compared with conventional film methods in the demonstration of hip prostheses. The high contrast differences at the edge of the metal implant leads to artifacts, which could result in erroneous interpretation. Suitable image manipulation makes it possible, however, to eliminate these artifacts almost completely. DLR leads to an improvement in diagnosis in those complications not specifically related to the prostheses. (orig.) [de

  19. Lability of nanoparticulate metal complexes in electrochemical speciation analysis

    DEFF Research Database (Denmark)

    van Leeuwen, Herman P.; Town, Raewyn M.

    2016-01-01

    Lability concepts are elaborated for metal complexes with soft (3D) and hard (2D) aqueous nanoparticles. In the presence of a non-equilibrium sensor, e.g. a voltammetric electrode, the notion of lability for nanoparticulate metal complexes, M-NP, reflects the ability of the M-NP to maintain...... equilibrium with the reduced concentration of the electroactive free M2+ in its diffusion layer. Since the metal ion binding sites are confined to the NP body, the conventional reaction layer in the form of a layer adjacent to the electrode surface is immaterial. Instead an intraparticulate reaction zone may...... of the electrochemical technique is crucial in the lability towards the electrode surface. In contrast, for nanoparticulate complexes it is the dynamics of the exchange of the electroactive metal ion with the surrounding medium that governs the effective lability towards the electrode surface....

  20. Luminescence nanothermometry

    Science.gov (United States)

    Jaque, Daniel; Vetrone, Fiorenzo

    2012-07-01

    The current status of luminescence nanothermometry is reviewed in detail. Based on the main parameters of luminescence including intensity, bandwidth, bandshape, polarization, spectral shift and lifetime, we initially describe and compare the different classes of luminescence nanothermometry. Subsequently, the various luminescent materials used in each case are discussed and the mechanisms at the root of the luminescence thermal sensitivity are described. The most important results obtained in each case are summarized and the advantages and disadvantages of these approaches are discussed.The current status of luminescence nanothermometry is reviewed in detail. Based on the main parameters of luminescence including intensity, bandwidth, bandshape, polarization, spectral shift and lifetime, we initially describe and compare the different classes of luminescence nanothermometry. Subsequently, the various luminescent materials used in each case are discussed and the mechanisms at the root of the luminescence thermal sensitivity are described. The most important results obtained in each case are summarized and the advantages and disadvantages of these approaches are discussed. This work was supported by the Universidad Autónoma de Madrid and Comunidad Autónoma de Madrid (Project S2009/MAT-1756), by the Spanish Ministerio de Educacion y Ciencia (MAT2010-16161) and by Caja Madrid Foundation.

  1. 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...

  2. Mixed metal complexes of isoniazid and ascorbic acid: chelation ...

    African Journals Online (AJOL)

    Novel mixed complexes of isoniazid and ascorbic acid have been synthesized and characterized using infrared, electronic absorption data, elemental analysis, molar conductivity, melting point, thin layer chromatography and solubility. The metal ions involved in the complex formation are Cu2+, Zn2+ and Cd2+. The melting ...

  3. Metal complex catalysis in the synthesis of organoaluminium compounds

    International Nuclear Information System (INIS)

    Dzhemilev, Usein M; Ibragimov, Askhat G

    2000-01-01

    The published data on the synthesis of organoaluminium compounds involving metal complex catalysts are generalised and systematised. Hydro-, carbo- and cycloalumination reactions of alkenes, conjugated dienes and alkynes catalysed by Ti and Zr complexes are considered in detail. The use of organoaluminium reagents in organic synthesis and novel reactions involving these compounds are discussed. The bibliography includes 240 references.

  4. An Experiment on Isomerism in Metal-Amino Acid Complexes.

    Science.gov (United States)

    Harrison, R. Graeme; Nolan, Kevin B.

    1982-01-01

    Background information, laboratory procedures, and discussion of results are provided for syntheses of cobalt (III) complexes, I-III, illustrating three possible bonding modes of glycine to a metal ion (the complex cations II and III being linkage/geometric isomers). Includes spectrophotometric and potentiometric methods to distinguish among the…

  5. Enhanced luminescence of rare-earth complexes Tb(1-x)Eu(x)(m-NBA)3Phen in ZnS.

    Science.gov (United States)

    Lv, Yuguang; Zhang, Jingchang; Cao, Weiliang; Song, Lin; Xu, Zheng

    2008-07-01

    Rare-earth ternary complexes Tb(1-x)Eu(x)(m-NBA)(3)Phen (X=1, 0.25, 0.5, 0.75, 1.0) were synthesized and characterized by IR, DTA-TG, UV, fluorescent spectra and elemental analysis. It was found that luminescence of Eu(3+) complex was enhanced by doped with Tb(3+). It is proved by TG curve that the complexes are stable, ranging from ambient temperature to 360 degrees C in air. The organic-inorganic combined structural device was fabricated, and the electroluminescence intensity of the combined structural device was improved compared with the device of the purely organic components.

  6. Enhanced luminescence of rare-earth complexes Tb 1- xEu x( m-NBA) 3Phen in ZnS

    Science.gov (United States)

    Lv, Yuguang; Zhang, Jingchang; Cao, Weiliang; Song, Lin; Xu, Zheng

    2008-07-01

    Rare-earth ternary complexes Tb 1- xEu x( m-NBA) 3Phen ( X = 1, 0.25, 0.5, 0.75, 1.0) were synthesized and characterized by IR, DTA-TG, UV, fluorescent spectra and elemental analysis. It was found that luminescence of Eu 3+ complex was enhanced by doped with Tb 3+. It is proved by TG curve that the complexes are stable, ranging from ambient temperature to 360 °C in air. The organic-inorganic combined structural device was fabricated, and the electroluminescence intensity of the combined structural device was improved compared with the device of the purely organic components.

  7. A highly selective and non-reaction based chemosensor for the detection of Hg2+ ions using a luminescent iridium(III complex.

    Directory of Open Access Journals (Sweden)

    Daniel Shiu-Hin Chan

    Full Text Available We report herein a novel luminescent iridium(III complex with two hydrophobic carbon chains as a non-reaction based chemosensor for the detection of Hg(2+ ions in aqueous solution (<0.002% of organic solvent attributed to the probe solution. Upon the addition of Hg(2+ ions, the emission intensity of the complex was significantly enhanced and this change could be monitored by the naked eye under UV irradiation. The iridium(III complex shows high specificity for Hg(2+ ions over eighteen other cations. The system is capable of detecting micromolar levels of Hg(2+ ions, which is within the range of many chemical systems.

  8. Investigation of the luminescent properties of terbium-anthranilate complexes and application to the determination of anthranilic acid derivatives in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Arnaud, N.; Georges, J

    2003-01-10

    The luminescent properties of terbium complexes with furosemide (FR), flufenamic (FF) acid, tolfenamic (TF) acid and mefenamic (MF) acid have been investigated in aqueous solutions. For all four compounds, complexation occurs when the carboxylic acid of the aminobenzoic group is dissociated and is greatly favoured in the presence of trioctylphosphine oxide as co-ligand and Triton X-100 as surfactant. Under optimum conditions, luminescence of the lanthanide ion is efficiently sensitised and the lifetime of the {sup 5}D{sub 4} resonance level of terbium in the complex is ranging between 1 and 1.9 ms, against 0.4 ms for the aqua ion. The sensitivity of the method for the determination of anthranilic acid derivatives is improved by one to two orders of magnitude with respect to that achieved using native fluorescence or terbium-sensitised luminescence in methanol. The limits of detection are 2x10{sup -10}, 5x10{sup -10} and 2x10{sup -9} mol l{sup -1} for flufenamic acid, furosemide and tolfenamic acid, and mefenamic acid, respectively, with within-run RSD values of less than 1%. The method has been applied to the determination of flufenamic acid in spiked calf sera with and without sample pretreatment. Depending on the method and the analyte concentration, the recovery was ranging between 83 and 113% and the lowest concentration attainable in serum samples was close to 1x10{sup -7} mol l{sup -1}.

  9. DFT study on metal-mediated uracil base pair complexes

    Directory of Open Access Journals (Sweden)

    Ayhan Üngördü

    2017-11-01

    Full Text Available The most stable of metal-mediated uracil base pair complexes were determined. Method was used density functional theory, B3LYP. The calculations of systems containing C, H, N, O were described by 6-311++G(d,p and cc-PVTZ basis sets and LANL2DZ and SDD basis sets was used for transition metals. Then Egap values of complexes were calculated and the electrical conductivity of the complexes for single nanowires was studied by band theory. Metal-mediated uracil base pair complexes which will be used as conductive wires in nanotechnology were predicted. In nanoworld, this study is expected to show a way for practical applications.

  10. Luminescent Organometallic Nanomaterials with Aggregation-Induced Emission.

    Science.gov (United States)

    Shu, Tong; Wang, Jianxing; Su, Lei; Zhang, Xueji

    2018-07-04

    Recent researches in metal nanoclusters (NCs) have prompted their promising practical applications in biomedical fields as novel inorganic luminophores. More recently, to further improve the photoluminescence (PL) performance of NCs, the aggregation-induced emission (AIE) effect has been introduced to develop highly luminescent metal NCs and metal complex materials. In this review, we start our discussion from recent progresses on AIE materials developments. Then, we address our understandings on the PL properties of thiolated metal NCs. Subsequently, we link thiolated metal NCs with AIE effect. We also highlight some recent advances in synthesizing the AIE-type metal complex nanomaterials. We finally discuss visions and directions for future development of AIE-type metal complex nanomaterials.

  11. Preparation and Characterization of Double Metal Cyanide Complex Catalysts

    Directory of Open Access Journals (Sweden)

    Weilin Guo

    2003-01-01

    Full Text Available A series of double metal cyanide (DMC complex catalysts were prepared in two different methods by using ß-cyclodextrin, PEG-1000 and Tween-60 as an additional complex ligands respectively. It was showed that a mixture of crystalline and amorphous DMC was synthesized by using traditional method in which the additional complex ligand was added after the precipitation of DMC. Amorphous and dispersed DMC with higher activity could be obtained when the additional complex ligand was added in the reactant solution before reaction. The effect of additional complex ligand and preparation method on the crystalline state and catalytic property of DMC were also investigated.

  12. High pressure study of viscosity effects on the luminescence of tetracyanobenzene EDA complexes

    Science.gov (United States)

    Thomas, Michele Moisio; Drickamer, H. G.

    1981-03-01

    High pressure fluorescence studies fron 0-10 kbar have been performed on electron donor-acceptor (EDA) complexes of s-tetracyanobenzene (TCNB) with a series of aromatic hydrocarbons. Four solvents were used, 2,2,4,4,6,8,8 heptamethylnonane (HMN), methylcyclohexane (MCH), 2,6,10,14 tetramethylpentadecane (TMPD), and a mixture of MCH and HMN. A viscosity range from 0.006 to 10 000 poise was covered at constant temperature. As pressure (viscosity) increased the fluorescence spectrum shifted from one dominated by emission from the equilibrium (EQ) excited singlet state to one dominated by Franck-Condon (FC) singlet emission. Lifetime measurements for the complexes of o-xylene and p-xylene with TCNB as well as one mesitylene complex yielded the two radiative rates (kEQ and kFC) as well as the rate of internal conversion from FC to the EQ excited state to (kIC). The results are discussed in terms of the rate of relaxation of the solvent compared with the rate kFC. It was found that kIC correlated very well with the solvent viscosity.

  13. Ultrafast water sensing and thermal imaging by a metal-organic framework with switchable luminescence

    Science.gov (United States)

    Chen, Ling; Ye, Jia-Wen; Wang, Hai-Ping; Pan, Mei; Yin, Shao-Yun; Wei, Zhang-Wen; Zhang, Lu-Yin; Wu, Kai; Fan, Ya-Nan; Su, Cheng-Yong

    2017-06-01

    A convenient, fast and selective water analysis method is highly desirable in industrial and detection processes. Here a robust microporous Zn-MOF (metal-organic framework, Zn(hpi2cf)(DMF)(H2O)) is assembled from a dual-emissive H2hpi2cf (5-(2-(5-fluoro-2-hydroxyphenyl)-4,5-bis(4-fluorophenyl)-1H-imidazol-1-yl)isophthalic acid) ligand that exhibits characteristic excited state intramolecular proton transfer (ESIPT). This Zn-MOF contains amphipathic micropores (behaviour. The interconversion between the hydrated and dehydrated phases can turn the ligand ESIPT process on or off, resulting in sensitive two-colour photoluminescence switching over cycles. Therefore, this Zn-MOF represents an excellent PL water-sensing material, showing a fast (on the order of seconds) and highly selective response to water on a molecular level. Furthermore, paper or in situ grown ZnO-based sensing films have been fabricated and applied in humidity sensing (RH<1%), detection of traces of water (<0.05% v/v) in various organic solvents, thermal imaging and as a thermometer.

  14. Improving the SMM and luminescence properties of lanthanide complexes with LnO9 cores in the presence of ZnII: an emissive Zn2Dy single ion magnet.

    Science.gov (United States)

    Fondo, Matilde; Corredoira-Vázquez, Julio; Herrera-Lanzós, Antía; García-Deibe, Ana M; Sanmartín-Matalobos, Jesús; Herrera, Juan Manuel; Colacio, Enrique; Nuñez, Cristina

    2017-12-12

    Mononuclear complexes of stoichiometry [Ln(H 3 L)(H 2 O)(NO 3 )](NO 3 ) 2 (Ln = Tb, 1; Dy, 2, Er, 3), which crystallise with different solvates, and the heterotrinuclear compound [Zn 2 Dy(L)(NO 3 ) 3 (OH)] (4) can be obtained with the same H 3 L compartmental ligand. The single X-ray crystal structure of the mononuclear complexes shows a LnO 9 core with a muffin-like disposition while the geometry of the DyO 9 core in 4 seems to be closer to spherical capped square antiprism. The analysis of the magnetic properties of all the complexes demonstrates that the mononuclear lanthanide compounds do not show slow relaxation of the magnetization, even when the samples are diluted with a diamagnetic matrix and subjected to a dc applied field of 1000 Oe. Nevertheless, the heterotrinuclear dysprosium complex 4·3H 2 O is a field-induced single ion magnet, with an estimated U eff barrier of 59 K. The luminescence characterisation of all the metal complexes in methanol solution at 298 K also shows a notable increase in the fluorescence emission of the heterotrinuclear complex with respect to the mononuclear ones, in such a way that 4 can be defined as a fluorescent single ion magnet.

  15. Metal Complexes for Organic Optoelectronic Applications

    Science.gov (United States)

    Huang, Liang

    Organic optoelectronic devices have drawn extensive attention by over the past two decades. Two major applications for Organic optoelectronic devices are efficient organic photovoltaic devices(OPV) and organic light emitting diodes (OLED). Organic Solar cell has been proven to be compatible with the low cost, large area bulk processing technology and processed high absorption efficiencies compared to inorganic solar cells. Organic light emitting diodes are a promising approach for display and solid state lighting applications. To improve the efficiency, stability, and materials variety for organic optoelectronic devices, several emissive materials, absorber-type materials, and charge transporting materials were developed and employed in various device settings. Optical, electrical, and photophysical studies of the organic materials and their corresponding devices were thoroughly carried out. In this thesis, Chapter 1 provides an introduction to the background knowledge of OPV and OLED research fields presented. Chapter 2 discusses new porphyrin derivatives- azatetrabenzylporphyrins for OPV and near infrared OLED applications. A modified synthetic method is utilized to increase the reaction yield of the azatetrabenzylporphyrin materials and their photophysical properties, electrochemical properties are studied. OPV devices are also fabricated using Zinc azatetrabenzylporphyrin as donor materials. Pt(II) azatetrabenzylporphyrin were also synthesized and used in near infra-red OLED to achieve an emission over 800 nm with reasonable external quantum efficiencies. Chapter 3, discusses the synthesis, characterization, and device evaluation of a series of tetradentate platinum and palladium complexesfor single doped white OLED applications and RGB white OLED applications. Devices employing some of the developed emitters demonstrated impressively high external quantum efficiencies within the range of 22%-27% for various emitter concentrations. And the palladium complex, i

  16. New luminescence ages for the Galería Complex archaeological site: resolving chronological uncertainties on the acheulean record of the Sierra de Atapuerca, northern Spain.

    Science.gov (United States)

    Demuro, Martina; Arnold, Lee J; Parés, Josep M; Pérez-González, Alfredo; Ortega, Ana I; Arsuaga, Juan L; Bermúdez de Castro, José M; Carbonell, Eudald

    2014-01-01

    The archaeological karstic infill site of Galería Complex, located within the Atapuerca system (Spain), has produced a large faunal and archaeological record (Homo sp. aff. heidelbergensis fossils and Mode II lithic artefacts) belonging to the Middle Pleistocene. Extended-range luminescence dating techniques, namely post-infrared infrared stimulated luminescence (pIR-IR) dating of K-feldspars and thermally transferred optically stimulated luminescence (TT-OSL) dating of individual quartz grains, were applied to fossil-bearing sediments at Galería. The luminescence dating results are in good agreement with published chronologies derived using alternative radiometric dating methods (i.e., ESR and U-series dating of bracketing speleothems and combined ESR/U-series dating of herbivore teeth), as well as biochronology and palaeoenvironmental reconstructions inferred from proxy records (e.g., pollen data). For the majority of samples dated, however, the new luminescence ages are significantly (∼50%) younger than previously published polymineral thermoluminescence (TL) chronologies, suggesting that the latter may have overestimated the true burial age of the Galería deposits. The luminescence ages obtained indicate that the top of the basal sterile sands (GIb) at Galería have an age of up to ∼370 thousand years (ka), while the lowermost sub-unit containing Mode II Acheulean lithics (base of unit GIIa) was deposited during MIS 9 (mean age = 313±14 ka; n = 4). The overlying units GIIb-GIV, which contain the richest archaeopalaeontological remains, were deposited during late MIS 8 or early MIS 7 (∼240 ka). Galería Complex may be correlative with other Middle Pleistocene sites from Atapuerca, such as Gran Dolina level TD10 and unit TE19 from Sima del Elefante, but the lowermost archaeological horizons are ∼100 ka younger than the hominin-bearing clay breccias at the Sima de los Huesos site. Our results suggest that both pIR-IR and single-grain TT

  17. Highly luminescent pure-red-emitting fluorinated β-diketonate europium(III) complex for full solution-processed OLEDs

    Energy Technology Data Exchange (ETDEWEB)

    Martins, Joao P. [CEMDRX, Physics Department, Universidade de Coimbra, Rua Larga, Coimbra P-3004-516 (Portugal); Serviço de Medicina Nuclear, SESARAM E.P.E., Avenida Luís de Camões 57, Funchal 9004-514, Madeira (Portugal); Martín-Ramos, Pablo [CEMDRX, Physics Department, Universidade de Coimbra, Rua Larga, Coimbra P-3004-516 (Portugal); Higher Technical School of Telecommunications Engineering, Universidad de Valladolid, Campus Miguel Delibes, Paseo Belén 15, Valladolid 47011 (Spain); Coya, Carmen, E-mail: carmen.coya@urjc.es [Escuela Superior de Ciencias Experimentales y Tecnología (ESCET), Universidad Rey Juan Carlos, Madrid 28933 (Spain); Silva, Manuela Ramos [CEMDRX, Physics Department, Universidade de Coimbra, Rua Larga, Coimbra P-3004-516 (Portugal); Eusebio, M. Ermelinda S. [Chemistry Department, Faculdade de Ciências e Tecnologia, Universidade de Coimbra, Coimbra P-3004-535 (Portugal); Andrés, Alicia de [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas (CSIC), Cantoblanco, Madrid 28049 (Spain); Álvarez, Ángel L. [Escuela Superior de Ciencias Experimentales y Tecnología (ESCET), Universidad Rey Juan Carlos, Madrid 28933 (Spain); Martín-Gil, Jesús [Advanced Materials Laboratory, ETSIIAA, Universidad de Valladolid, Avenida de Madrid 44, Palencia 34004 (Spain)

    2015-03-15

    Current manufacturing technologies for OLEDs involve the use of expensive high vacuum techniques and call for thermal stability requirements which are not fulfilled by many materials. These problems disappear when the OLED films are deposited directly from solution. In this study, we have designed, synthesized and characterized a novel octacoordinated complex, Tris(1-(4-chlorophenyl)-4,4,4-trifluoro-1, 3-butanedionate)mono(bathophenanthroline) europium(III), to be used as a “complex-only” emissive layer in wet-processed OLEDs. Upon excitation in the UV region, very efficient energy transfer from the ligands to Eu{sup 3+} takes place, giving rise to intense red emission with very high monochromaticity (R=19), both in powder and as a thin film. The decay times of 754 µs (powder) and 620 µs (thin film) are comparable to those of the most efficient Eu{sup 3+} β-diketonate complexes reported to date. The same energy transfer leading to saturated red and narrow emission is also observed in the OLED device (glass/ITO/PEDOT:PSS/[Eu(cbtfa){sub 3}(bath)]/Ca/Al) when biased at >5.2 V. Its high quantum efficiency (∼60%), good thermal stability up to 200 °C and adequate thin film forming properties make this material a promising chromophore for cost-effective OLEDs. - Highlights: • A highly fluorinated europium(III) octacoordinated complex, [Eu(cbtfa)3(bath)], has been synthesized and its structure elucidated by single crystal X-ray diffraction. • The chosen coordination environment is well-suited for sensitizing the luminescence of the Eu{sup 3+} ion, achieving very efficient energy transfer from the organic ligands (excited in the UV region) to the rare earth ion, leading to highly efficient (Q∼60% in crystalline powder and Q∼50% in thin film) and saturated red photoluminescence. • The material has also been integrated into a single active layer, full solution-processed OLED, with ITO/PEDOT:PSS/[Eu(cbtfa)3(bath)]/ Ca/Al structure.

  18. Homogeneous Catalysis with Metal Complexes Fundamentals and Applications

    CERN Document Server

    Duca, Gheorghe

    2012-01-01

    The book about homogeneous catalysis with metal complexes deals with the description of the reductive-oxidative, metal complexes  in a liquid phase (in polar solvents, mainly in water, and less in nonpolar solvents). The exceptional importance of the redox processes in chemical systems, in the reactions occuring in living organisms, the environmental processes, atmosphere, water, soil, and in industrial technologies (especially in food-processing industries) is discussed. The detailed practical aspects of the established regularities are explained for solving the specific practical tasks in various fields of industrial chemistry, biochemistry, medicine, analytical chemistry and ecological chemistry. The main scope of the book is the survey and systematization of the latest advances in homogeneous catalysis with metal complexes. It gives an overview of the research results and practical experience accumulated by the author during the last decade.

  19. Complexation-induced supramolecular assembly drives metal-ion extraction.

    Science.gov (United States)

    Ellis, Ross J; Meridiano, Yannick; Muller, Julie; Berthon, Laurence; Guilbaud, Philippe; Zorz, Nicole; Antonio, Mark R; Demars, Thomas; Zemb, Thomas

    2014-09-26

    Combining experiment with theory reveals the role of self-assembly and complexation in metal-ion transfer through the water-oil interface. The coordinating metal salt Eu(NO3)3 was extracted from water into oil by a lipophilic neutral amphiphile. Molecular dynamics simulations were coupled to experimental spectroscopic and X-ray scattering techniques to investigate how local coordination interactions between the metal ion and ligands in the organic phase combine with long-range interactions to produce spontaneous changes in the solvent microstructure. Extraction of the Eu(3+)-3(NO3(-)) ion pairs involves incorporation of the "hard" metal complex into the core of "soft" aggregates. This seeds the formation of reverse micelles that draw the water and "free" amphiphile into nanoscale hydrophilic domains. The reverse micelles interact through attractive van der Waals interactions and coalesce into rod-shaped polynuclear Eu(III) -containing aggregates with metal centers bridged by nitrate. These preorganized hydrophilic domains, containing high densities of O-donor ligands and anions, provide improved Eu(III) solvation environments that help drive interfacial transfer, as is reflected by the increasing Eu(III) partitioning ratios (oil/aqueous) despite the organic phase approaching saturation. For the first time, this multiscale approach links metal-ion coordination with nanoscale structure to reveal the free-energy balance that drives the phase transfer of neutral metal salts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Physicochemical and biological properties of new steroid metal complexes

    International Nuclear Information System (INIS)

    Huber, R.

    1980-04-01

    The aim of this investigation was to prepare stable steroid metal chelates by chemical conversion of the natural steroid hormones testerone, 5α-dihydrotestosterone (5α-DHT) and estradiol and to characterize these by means of their spectroscopic and other physico-chemical properties. In addition, various measuring techniques for the qualitative and quantitative study of complex stabilities and hydrolytic properties were employed. The distribution of some tritiated steroid metal complexes in the tissues of rats was tested using whole animal autoradiography, mainly with a view to identifying whether selective concentration occurs in certain organs. (orig.) [de

  1. Complex Metal Hydrides for Hydrogen, Thermal and Electrochemical Energy Storage

    DEFF Research Database (Denmark)

    Moller, Kasper T.; Sheppard, Drew; Ravnsbaek, Dorthe B.

    2017-01-01

    Hydrogen has a very diverse chemistry and reacts with most other elements to form compounds, which have fascinating structures, compositions and properties. Complex metal hydrides are a rapidly expanding class of materials, approaching multi-functionality, in particular within the energy storage...... inspiration to solve the great challenge of our time: efficient conversion and large-scale storage of renewable energy....... field. This review illustrates that complex metal hydrides may store hydrogen in the solid state, act as novel battery materials, both as electrolytes and electrode materials, or store solar heat in a more efficient manner as compared to traditional heat storage materials. Furthermore, it is highlighted...

  2. THE THEORY OF DEVELOPMENT OF SUPPORTED METAL-COMPLEX CATALYSTS

    Directory of Open Access Journals (Sweden)

    T. L. Rakitskaya

    2015-06-01

    Full Text Available Some results of the investigations for the purpose of development of supported metal-complex catalysts for phosphine and carbon monoxide oxidation as well as for ozone decomposition are summarized. The activity of such catalysts has been found to depend not only on a nature of a central atom and ligands but also on a nature of supports. The theoretical model explaining mechanisms of surface complex formation taking into account the influence of physicochemical and structural-adsorption properties of the supports (SiO2, Al2O3, carbon materials, zeolites, dispersed silicas, lamellar aluminosilicates, etc. has been proposed. For quantitative description of the support effect, such a thermodynamic parameter as the adsorbed water activity assignable with the help of water vapor adsorption isotherms has been introduced. Successive stability constants of the surface metal complexes have been calculated by the kinetic method and, hence, compositions and partial catalytic activity of the latter have been determined. Taking into account the competitive adsorption of metal ions on the supports, some schemes of formation of surface bimetallic complexes have been suggested. The compositions of the supported metal-complex catalysts have been optimized to meet requirements of their use in respirators and plants for air purification from foregoing gaseous toxicants.

  3. Properties- and applications of quasicrystals and complex metallic alloys.

    Science.gov (United States)

    Dubois, Jean-Marie

    2012-10-21

    This article aims at an account of what is known about the potential for applications of quasicrystals and related compounds, the so-called family of Complex Metallic Alloys (CMAs‡). Attention is focused at aluminium-based CMAs, which comprise a large number of crystalline compounds and quasicrystals made of aluminium alloyed with transition metals (like Fe or Cu) or normal metals like Mg. Depending on composition, the structural complexity varies from a few atoms per unit cell up to thousands of atoms. Quasicrystals appear then as CMAs of ultimate complexity and exhibit a lattice that shows no periodicity anymore in the usual 3-dimensional space. Properties change dramatically with lattice complexity and turn the metal-type behaviour of simple Al-based crystals into a far more complex behaviour, with a fingerprint of semi-conductors that may be exploited in various applications, potential or realised. An account of the ones known to the author is given in the light of the relevant properties, namely light absorption, reduced adhesion and friction, heat insulation, reinforcement of composites for mechanical devices, and few more exotic ones. The role played by the search for applications of quasicrystals in the development of the field is briefly addressed in the concluding section.

  4. Luminescence dating

    International Nuclear Information System (INIS)

    Rieser, U.

    2009-01-01

    The luminescence techniques have evolved over the last 40 years to a powerful dating instrument in archaeology and geoscience. Depending on how the luminescence is stimulated, one distinguishes the phenomena of thermoluminescence (TL), optically stimulated luminescence (OSL) and infrared stimulated luminescence (IRSL). Each of these phenomena has its specific potential for dating various archaeological materals in the time range from medieval back to palaeolithic periods, or, speaking in geological terms, for dating of Holocene and late Pleistocene objects. The OSL and IRSL techniques are sometimes treated together as 'optical dating'. The luminescence techniques differ from other major dating techniques, such as 14 C, essentially by their applicability to inorganic materials, their wide age-range from about 100 years to more than 100,000 years and the kind of datable events which are the last exposure to heat or to light. (author). 10 refs., 3 figs.

  5. Luminescence dating

    International Nuclear Information System (INIS)

    Rieser, U.

    2008-01-01

    The luminescence techniques have evolved over the last 40 years to a powerful dating instrument in archaeology and geoscience. Depending on how the luminescence is stimulated, one distinguishes the phenomena of thermoluminescence (TL), optically stimulated luminescence (OSL) and infrared stimulated luminescence (IRSL). Each of these phenomena has its specific potential for dating various archaeological materals in the time range from medieval back to palaeolithic periods, or, speaking in geological terms, for dating of Holocene and late Pleistocene objects. The OSL and IRSL techniques are sometimes treated together as 'optical dating'. The luminescence techniques differ from other major dating techniques, such as 14 C, essentially by their applicability to inorganic materials, their wide age-range from about 100 years to more than 100,000 years and the kind of datable events which are the last exposure to heat or to light. (author). 10 refs., 3 figs

  6. Luminescence dating

    International Nuclear Information System (INIS)

    Rieser, U.

    2012-01-01

    The luminescence techniques have evolved over the last 40 years to a powerful dating instrument in archaeology and geoscience. Depending on how the luminescence is stimulated, one distinguishes the phenomena of thermoluminescence (TL), optically stimulated luminescence (OSL) and infrared stimulated luminescence (IRSL). Each of these phenomena has its specific potential for dating various archaeological materials in the time range from medieval back to palaeolithic periods, or, speaking in geological terms, for dating of Holocene and late Pleistocene objects. The OSL and IRSL techniques are sometimes treated together as 'optical dating'. The luminescence techniques differ from other major dating techniques, such as 14 C, essentially by their applicability to inorganic materials, their wide age-range from about 100 years to more than 100,000 years and the kind of datable events which are the last exposure to heat or to light. (author). 10 refs., 3 figs.

  7. Luminescence dating

    International Nuclear Information System (INIS)

    Rieser, U.

    2009-01-01

    The luminescence techniques have evolved over the last 40 years to a powerful dating instrument in archaeology and geoscience. Depending on how the luminescence is stimulated, one distinguishes the phenomena of thermoluminescence (TL), optically stimulated luminescence (OSL) and infrared stimulated luminescence (IRSL). Each of these phenomena has its specific potential for dating various archaeological materals in the time range from medieval back to palaeolithic periods, or, speaking in geological terms, for dating of Holocene and late Pleistocene objects. The OSL and IRSL techniques are sometimes treated together as 'optical dating'. The luminescence techniques differ from other major dating techniques, such as 14 C, essentially by their applicability to inorganic materials, their wide age-range from about 100 years to more than 100,000 years and the kind of datable events which are the last exposure to heat or to light. (author). 10 refs., 3 figs

  8. Luminescence dating

    International Nuclear Information System (INIS)

    Rieser, U.

    2013-01-01

    The luminescence techniques have evolved over the last 40 years to a powerful dating instrument in archaeology and geoscience. Depending on how the luminescence is stimulated, one distinguishes the phenomena of thermoluminescence (TL), optically stimulated luminescence (OSL) and infrared stimulated luminescence (IRSL). Each of these phenomena has its specific potential for dating various archaeological materials in the time range from medieval back to palaeolithic periods, or, speaking in geological terms, for dating of Holocene and late Pleistocene objects. The OSL and IRSL techniques are sometimes treated together as 'optical dating'. The luminescence techniques differ from other major dating techniques, such as 14 C, essentially by their applicability to inorganic materials, their wide age-range from about 100 years to more than 100,000 years and the kind of datable events which are the last exposure to heat or to light. (author). 10 refs., 3 figs.

  9. An unsymmetrical porphyrin and its metal complexes: synthesis, spectroscopy, thermal analysis and liquid crystal properties

    Directory of Open Access Journals (Sweden)

    CHANGFU ZHUANG

    2009-09-01

    Full Text Available The synthesis and characterization of a new unsymmetrical porphyrin liquid crystal, 5-(4-stearoyloxyphenylphenyl-10,15,20-triphenylporphyrin (SPTPPH2 and its transition metal complexes (SPTPPM, M(II = Zn, Fe, Co, Ni, Cu or Mn are reported. Their structure and properties were studied by elemental analysis, and UV–Vis, IR, mass and 1H-HMR spectroscopy. Their luminescent properties were studied by excitation and emission spectroscopy. The quantum yields of the S1 ® S0 fluorescence were measured at room temperature. According to thermal studies, the complexes have a higher thermal stability (no decomposition until 200 °C. Differential scanning calorimetry (DSC data and an optical textural photograph, obtained using a polarizing microscope (POM, indicate that the porphyrin ligand had liquid crystalline character and that it exhibited more than one mesophase and a low-lying phase transition temperature, with transition temperatures of 19.3 and 79.4 °C; the temperature range of the liquid crystal (LC phase of the ligand was 70.1 °C.

  10. Luminescent lanthanide coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Ma, L.; Evans, O.R.; Foxman, B.M.; Lin, W.

    1999-12-13

    One-dimensional lanthanide coordination polymers with the formula Ln(isonicotinate){sub 3}(H{sub 2}O){sub 2} (Ln = Ce, Pr, Nd, Sm, Eu, Tb; 1a-f) were synthesized by treating nitrate or perchlorate salts of Ln(III) with 4-pyridinecarboxaldehyde under hydro(solvo)thermal conditions. Single-crystal and powder X-ray diffraction studies indicate that these lanthanide coordination polymers adopt two different structures. While Ce(III), Pr(III), and Nd(III) complexes adopt a chain structure with alternating Ln-(carboxylate){sub 2}-Ln and Ln-(carboxylate){sub 4}-Ln linkages, Sm(III), Eu(III), and Tb(III) complexes have a doubly carboxylate-bridged infinite-chain structure with one chelating carboxylate group on each metal center. In both structures, the lanthanide centers also bind to two water molecules to yield an eight-coordinate, square antiprismatic geometry. The pyridine nitrogen atoms of the isonicotinate groups do not coordinate to the metal centers in these lanthanide(III) complexes; instead, they direct the formation of Ln(III) coordination polymers via hydrogen bonding with coordinated water molecules. Photoluminescence measurements show that Tb(isonicotinate){sub 3}(H{sub 2}O){sub 2} is highly emissive at room temperature with a quantum yield of {approximately}90%. These results indicate that highly luminescent lanthanide coordination polymers can be assembled using a combination of coordination and hydrogen bonds. Crystal data for 1a: monoclinic space group P2{sub 1}/c, a = 9.712(2) {angstrom}, b = 19.833(4) {angstrom}, c = 11.616(2) {angstrom}, {beta} = 111.89(3){degree}, Z = 4. Crystal data for 1f: monoclinic space group C2/c, a = 20.253(4) {angstrom}, b = 11.584(2) {angstrom}, c = 9.839(2) {angstrom}, {beta} = 115.64(3){degree}, Z = 8.

  11. Zeolites as supports for transition-metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    Le Van Mao, R

    1979-01-01

    The unique structural characteristics of the zeolites, including the presence of molecular-size cages and channels and of an internal electrostatic field, make them promising as supports for converting homogeneous to heterogeneous catalysts. The acidic sites on the zeolites may also contribute to catalysis of reactions, such as hydrocracking; may stabilize metal complexes in a highly disperse state; and may improve activity or selectivity. Recent studies on the synthesis of new types of zeolite-supported complexes of transition metals (TM), such as Co, Cu, Ag, Fe, Mo, Ru, Rh, Re, and Os, suggest the feasibility of the direct introduction of some TM complexes into the zeolitic cages during zeolite synthesis, especially during the crystallization phase. This method may considerably reduce the structural limitations associated with the incorporation of TM complexes into zeolites by conventional methods.

  12. New Transition metal assisted complex borohydrides for hydrogen storage

    International Nuclear Information System (INIS)

    Sesha Srinivasan; Elias Lee Stefanakos; Yogi Goswami

    2006-01-01

    High capacity hydrogen storage systems are indeed essential for the on-board vehicular application that leads to the pollution free environment. Apart from the various hydrogen storage systems explored in the past, complex hydrides involving light weight alkali/alkaline metals exhibits promising hydrogenation/ dehydrogenation characteristics. New transition metal assisted complex borohydrides [Zn(BH 4 ) 2 ] have been successfully synthesized by an inexpensive mechano-chemical process. These complex hydrides possesses gravimetric hydrogen storage capacity of ∼8.4 wt.% at around 120 C. We have determined the volumetric hydrogen absorption and desorption of these materials for a number of cycles. Another complex borohydride mixture LiBH 4 /MgH 2 catalyzed with ZnCl 2 has been synthesized and characterized using various analytical techniques. (authors)

  13. Mineralizer-assisted high-pressure high-temperature synthesis and characterization of novel phosphorus nitride imides and luminescent alkaline earth metal (oxo)nitridophosphates

    International Nuclear Information System (INIS)

    Marchuk, Alexey

    2016-01-01

    The main objectives of this thesis were the synthesis, identification and structural characterization of new alkaline earth metal (oxo)nitridophopshates and phosphorus nitrides. Furthermore, luminescence properties of the resulting materials should be investigated and a connection between these properties and the respective structures should be established. For this purpose, a range of synthesis strategies was employed, including conventional solid-state syntheses in silica ampoules and high-pressure high-temperature syntheses using the multianvil technique. The emphasis of the synthetic part of this thesis lies on the development of new synthetic strategies in order to increase crystallinity of alkaline earth metal (oxo)nitridophosphates and thus accelerate their structure determination. This involves the selection of a suitable mineralizer and the investigation of its interaction with the respective starting materials. In addition, the analytical methods applied in this thesis in order to identify and characterize the compounds are just as essential as the synthesis strategies. X-ray diffraction on single crystals and on powders was carried out as the main analytical method while being supported by quantitative and qualitative 1 H and 31 P solid-state NMR measurements, FTIR and energy-dispersive X-ray (EDX) spectroscopy, as well as electron microscopy methods including both imaging and diffraction techniques. Implied by the large number of novel structures investigated, theoretical studies including topological analysis, calculations of lattice energies and bond-valence sums also played a major role in this thesis. Optical analysis methods such as reflectance spectroscopy, luminescence microscopy and photoluminescence measurements helped to determine the luminescence properties of some of the presented compounds.

  14. Synthesis, density functional theory calculations and luminescence of lanthanide complexes with 2,6-bis[(3-methoxybenzylidene)hydrazinocarbonyl] pyridine Schiff base ligand.

    Science.gov (United States)

    Taha, Ziyad A; Ababneh, Taher S; Hijazi, Ahmed K; Abu-Salem, Qutaiba; Ajlouni, Abdulaziz M; Ebwany, Shroq

    2018-02-01

    A pyridine-diacylhydrazone Schiff base ligand, L = 2,6-bis[(3-methoxy benzylidene)hydrazinocarbonyl]pyridine was prepared and characterized by single crystal X-ray diffraction. Lanthanide complexes, Ln-L, {[LnL(NO 3 ) 2 ]NO 3 .xH 2 O (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy and Er)} were prepared and characterized by elemental analysis, molar conductance, thermal analysis (TGA/DTGA), mass spectrometry (MS), Fourier transform infra-red (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy. Ln-L complexes are isostructural with four binding sites provided by two nitro groups along with four coordination sites for L. Density functional theory (DFT) calculations on L and its cationic [LnL(NO 3 ) 2 ] + complexes were carried out at the B3LYP/6-31G(d) level of theory. The FT-IR vibrational wavenumbers were computed and compared with the experimentally values. The luminescence investigations of L and Ln-L indicated that Tb-L and Eu-L complexes showed the characteristic luminescence of Tb(III) and Eu(III) ions. Ln-L complexes show higher antioxidant activity than the parent L ligand. Copyright © 2017 John Wiley & Sons, Ltd.

  15. The metallic ratios as limits of complex valued transformations

    International Nuclear Information System (INIS)

    Falcon, Sergio; Plaza, Angel

    2009-01-01

    We study the presence of the metallic ratios as limits of two complex valued transformations. These complex variable functions are introduced and related with the two geometric antecedents for each triangle in a particular triangle partition, the four-triangle longest-edge (4TLE) partition. In this way, the fractality of a geometric diagram for the classes of dissimilar generated triangles is also explained.

  16. Study of the luminescence of tris(2-thenoyltrifluoroacetonato)lanthanide(III) complexes covalently linked to 1,10-phenanthroline-functionalized hybrid sol-gel glasses

    International Nuclear Information System (INIS)

    Lenaerts, Philip; Ryckebosch, Eline; Driesen, Kris; Deun, Rik van; Nockemann, Peter; Goerller-Walrand, Christiane; Binnemans, Koen

    2005-01-01

    The solubility and uniform distribution of lanthanide complexes in sol-gel glasses can be improved by covalently linking the complexes to the sol-gel matrix. In this study, several lanthanide β-diketonate complexes (Ln=Nd, Sm, Eu, Tb, Er, Yb) were immobilized on a 1,10-phenanthroline functionalized sol-gel glass. For the europium(III) complex, a sol-gel material of diethoxydimethylsilane (DEDMS) with polymer-like properties was derived. For the other lanthanide complexes, the sol-gel glass was prepared by using a matrix of tetramethoxysilane (TMOS) and DEDMS. Both systems were prepared under neutral reaction conditions. High-resolution emission and excitation spectra were recorded. The luminescence lifetimes were measured

  17. Anticancer Activity of Metal Complexes: Involvement of Redox Processes

    Science.gov (United States)

    Jungwirth, Ute; Kowol, Christian R.; Keppler, Bernhard K.; Hartinger, Christian G.; Berger, Walter; Heffeter, Petra

    2012-01-01

    Cells require tight regulation of the intracellular redox balance and consequently of reactive oxygen species for proper redox signaling and maintenance of metal (e.g., of iron and copper) homeostasis. In several diseases, including cancer, this balance is disturbed. Therefore, anticancer drugs targeting the redox systems, for example, glutathione and thioredoxin, have entered focus of interest. Anticancer metal complexes (platinum, gold, arsenic, ruthenium, rhodium, copper, vanadium, cobalt, manganese, gadolinium, and molybdenum) have been shown to strongly interact with or even disturb cellular redox homeostasis. In this context, especially the hypothesis of “activation by reduction” as well as the “hard and soft acids and bases” theory with respect to coordination of metal ions to cellular ligands represent important concepts to understand the molecular modes of action of anticancer metal drugs. The aim of this review is to highlight specific interactions of metal-based anticancer drugs with the cellular redox homeostasis and to explain this behavior by considering chemical properties of the respective anticancer metal complexes currently either in (pre)clinical development or in daily clinical routine in oncology. PMID:21275772

  18. The role of metal complexes in nuclear reactor decontamination

    Energy Technology Data Exchange (ETDEWEB)

    Prince, A.A.M.; Raghavan, P.S.; Gopalan, R. [Madras Christian College, Tambaram, Chennai (India); Velmurugan, S.; Narasimhan, S.V. [Bhabha Atomic Research Center (BARC) (IN). Water and Steam Chemistry Lab. (WSCL)

    2006-07-15

    Chemical decontamination is the process of removal of radioactivity from corrosion products formed on structural materials in the nuclear reactors. These corrosion products cause problems for the operation and maintenance of the plants. Removal of the radioactive contaminants can be achieved by dissolving the oxide from the system surface using organic complexing agents in low concentrations known as dilute chemical decontamination (DCD) formulations. These organic complexing agents attack the oxide surface and form metal complexes, which further accelerate the dissolution process. The stability of the complexes plays an important role in dissolving the radioactive contaminated oxides. In addition, the DCD process is operated through ion exchange resins for the removal of the dissolved metal ions and radioactive nuclides. In the present study, the kinetics of dissolution of various model corrosion products such as magnetite (Fe{sub 3}O{sub 4}), hematite ({alpha}-Fe{sub 2}O{sub 3}) and maghemite ({gamma}-Fe{sub 2}O{sub 3}) have been studied in the presence of complexing agents such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), hydroxyethylethylenediaminepentaacetic acid (HEEDTA), and 2,6 pyridinedicarboxylic acid (PDCA). The reductive roles of metal complexes and organic reducing agents are discussed. (orig.)

  19. Biodegradation of metal citrate complexes and implications for toxic-metal mobility

    International Nuclear Information System (INIS)

    Francis, A.J.; Dodge, C.J.; Gillow, J.B.

    1992-01-01

    The presence of synthetic and naturally occurring chelating agents in nuclear and toxic-metal wastes is a major concern because of their potential to enhance mobilization of metal ions away from the disposal sites. Of particular interest is citric acid, which is present in low-level and transuranic radioactive wastes and in domestic and industrial wastes (as washing fluids, for instance), as well as being found naturally. Citrate ions form multidentate, stable complexes with a variety of toxic metals and radionuclides; but biodegradation of these complexes, precipitating the metal ions as insoluble hydroxides, oxides or other salts, may retard migration. Here we report a study of the biodegradation of citrate complexes of Ca, Fe(II), Fe(III), Cd, Cu, Ni, Pb and U. Several of these complexes were not readily degraded by bacteria, and the biodegradability depended on the chemical nature of the complex, not on the toxicity of the metal to the bacteria. This resistance to biodegradation implies that citrate complexation may play an important part in migration of these hazardous wastes. (author)

  20. Method for synthesizing metal bis(borano) hypophosphite complexes

    Science.gov (United States)

    Cordaro, Joseph G.

    2013-06-18

    The present invention describes the synthesis of a family of metal bis(borano) hypophosphite complexes. One procedure described in detail is the syntheses of complexes beginning from phosphorus trichloride and sodium borohydride. Temperature, solvent, concentration, and atmosphere are all critical to ensure product formation. In the case of sodium bis(borano) hypophosphite, hydrogen gas was evolved upon heating at temperatures above 150.degree. C. Included in this family of materials are the salts of the alkali metals Li, Na and K, and those of the alkaline earth metals Mg and Ca. Hydrogen storage materials are possible. In particular the lithium salt, Li[PH.sub.2(BH.sub.3).sub.2], theoretically would contain nearly 12 wt % hydrogen. Analytical data for product characterization and thermal properties are given.

  1. Metathesis synthesis and characterization of complex metal fluoride ...

    Indian Academy of Sciences (India)

    Administrator

    V MANIVANNAN*, P PARHI and JONATHAN W KRAMER. Department of Mechanical Engineering, Campus Delivery 1374, Colorado State University, Fort Collins,. CO 80523, USA. MS received 30 April 2008. Abstract. Metathesis synthesis of complex metal fluorides using mechanochemical activation has been reported.

  2. DNA interactions and biocidal activity of metal complexes of ...

    Indian Academy of Sciences (India)

    Narendrula Vamsikrishna

    The Schiff bases and metal complexes were characterized by analytical and spectral methods like elemental analysis, ... cleavages.8–10 Cisplatin and its second generation com- ..... in DMSO. The test microorganisms were grown on nutrient agar medium in ...... effects on polymer characteristics Appl. Organomet. Chem.

  3. Dimeric Complexes of Tryptophan with M2+ Metal Ions

    NARCIS (Netherlands)

    Dunbar, R. C.; Steill, J. D.; Polfer, N. C.; Oomens, J.

    2009-01-01

    IRMPD spectroscopy using the FELIX free electron laser and a Fourier transform ICR mass spectrometer was used to characterize the structures of electrosprayed dimer complexes M(2+)Trp(2) of tryptophan with a series of eight doubly charged metal ions, including alkaline earths Ca, Sr, and Ba, and

  4. Sub-chronic toxicological studies of transition metal complexes of ...

    African Journals Online (AJOL)

    However, Naproxen metal complexes showed comparatively lower side effects than naproxen. Hematological report suggested that naproxen was in process of initiating inflammation which was justified by decreasing the mean value hemoglobin and hematocrit level and increasing the white blood cells level. There were ...

  5. Lability criteria for metal complexes in micro-electrode voltammetry

    NARCIS (Netherlands)

    Leeuwen, van H.P.; Pinheiro, J.P.

    1999-01-01

    Theoretical expressions are derived for the voltammetric lability criteria of metal complexes in the micro-electrode regime. The treatment includes three limiting situations: (i) the macro-electrode limit, where both the diffusion layer and the dissociation reaction layer are linear; (ii) an

  6. Schiff base transition metal complexes for Suzuki–Miyaura cross

    Indian Academy of Sciences (India)

    Schiff base ligand and its complex with iron (Fe), cobalt (Co), nickel (Ni) and copper (Cu) ions were synthesized using 4-aminoacetophenone and salicylaldehyde and characterized. FTIR spectrum shows that bidentate coordination of metal ions with ligand where O, N are electron donating sites of azomethine group.

  7. Group 4 Metal Complexes of Chelating Cyclopentadienyl-ketimide Ligands

    Czech Academy of Sciences Publication Activity Database

    Večeřa, M.; Varga, Vojtěch; Císařová, I.; Pinkas, Jiří; Kucharczyk, P.; Sedlařík, V.; Lamač, Martin

    2016-01-01

    Roč. 35, č. 5 (2016), s. 785-798 ISSN 0276-7333 R&D Projects: GA ČR(CZ) GA14-08531S; GA MŠk(CZ) LO1504 Institutional support: RVO:61388955 Keywords : group 4 metal complexes * cyclopentadienyl-ketimide ligands * metallocenes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.862, year: 2016

  8. Metal-isonitrile adducts for preparing radionuclide complexes

    International Nuclear Information System (INIS)

    Carpenter, A.P.; Linder, K.E.; Maheu, L.J.; Patz, M.A.; Thompson, J.S.; Tulip, T.H.; Subramanyam, V.

    1988-01-01

    An method for preparing a coordination complex of isonitrile ligand and a radioisotope of Te, Ru, Co, Pt, Re, Os, Ir, W, Re, Cr, Mo, Mn, Ni, Rh, Nb and Ta from a non-radioactive metal adduct of the isonitrile

  9. Luminescent Hydrogel Particles Prepared by Self-Assembly of β-Cyclodextrin Polymer and Octahedral Molybdenum Cluster Complexes

    Czech Academy of Sciences Publication Activity Database

    Kirakci, Kaplan; Šícha, Václav; Holub, Josef; Kubát, Pavel; Lang, Kamil

    2014-01-01

    Roč. 53, č. 24 (2014), s. 13012-13018 ISSN 0020-1669 R&D Projects: GA ČR GA13-05114S Institutional support: RVO:61388980 ; RVO:61388955 Keywords : Octahedral Molybdenum Cluster * Hydrogel * Luminescence Subject RIV: CA - Inorganic Chemistry Impact factor: 4.762, year: 2014

  10. Structure and luminescent property of complexes of aryl carboxylic acid-functionalized polystyrene with Eu(III) and Tb(III) ions.

    Science.gov (United States)

    Gao, Baojiao; Shi, Nan; Qiao, Zongwen

    2015-11-05

    Via polymer reactions, naphthoic acid (NA) and benzoic acid (BA) were bonded onto the side chains of polystyrene (PS), respectively, and two aryl carboxylic acid-functionalized polystyrenes, PSNA and PSBA, were obtained. Using PSNA and PSBA as macromolecule ligands and Eu(3+) and Tb(3+) ions as central ions, various luminescent binary polymer-rare earth complexes were prepared. At the same time, with 1,10-phenanthroline (Phen) and 4,4'-bipyridine (Bipy) as small-molecule co-ligands, various ternary polymer-rare earth complexes were also prepared. On the basis of characterizing PSNA, PSBA and complexes, the relationship between structure and luminescent property for these prepared complexes were mainly investigated. The study results show that the macromolecule ligands PSNA and PSBA, or the bonded NA and BA ligands, can strongly sensitize the fluorescence emissions of Eu(3+) ion or Tb(3+) ion, but the sensitization effect is strongly dependent on the structure of the ligands and the property of the central ions, namely it is strongly dependent on the matching degree of energy levels. The fluorescence emission of the binary complex PS-(NA)3-Eu(III) is stronger than that PS-(BA)3-Eu(III), indicating ligand NA has stronger sensitization action for Eu(3+) ion than ligand BA; the binary complex PS-(BA)3-Tb(III) emit strong characteristic fluorescence of Tb(3+) ion, displaying that ligand BA can strongly sensitize Tb(3+) ion, whereas the binary complex PS-(NA)3-Tb(III) nearly does not emit the characteristic fluorescence of Tb(3+) ion, showing that ligand NA does not sensitize Tb(3+) ion. The fluorescence intensity of the ternary complexes is much stronger than that of the binary complexes in the same series. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Biotransformation of uranium and transition metal citrate complexes by clostridia

    International Nuclear Information System (INIS)

    Francis, A.J.; Joshi-Tope, G.A.; Dodge, C.J.; Gillow, J.B.

    2002-01-01

    Clostridium sphenoides, which uses citric acid as its sole carbon source, metabolized equimolar Fe(III)-citrate with the degradation of citric acid and the reduction of Fe(III) to Fe(II), but not the U(VI)-citrate complex. However, in the presence of excess citric acid or added glucose it was reduced to U(IV)-citrate. In contrast, Clostridium sp., which ferments glucose but not citrate, reduced Fe(III)-citrate to Fe(II)-citrate and U(VI)-citrate to U(IV)-citrate only when supplied with glucose. These results show that complexed uranium is readily accessible as an electron acceptor despite the bacterium's inability to metabolize the organic ligand complexed to the actinide. These results also show that the metabolism of the metal-citrate complex depends upon the type of complex formed between the metal and citric acid. Fe(III) forms a bidentate complex with citric acid and was metabolized, whereas U forms a binuclear complex with citric acid and was recalcitrant. (author)

  12. Intracellular distribution and stability of a luminescent rhenium(I) tricarbonyl tetrazolato complex using epifluorescence microscopy in conjunction with X-ray fluorescence imaging

    International Nuclear Information System (INIS)

    Wedding, Jason L.; Harris, Hugh H.; Bader, Christie A.; Plush, Sally E.; Mak, Rachel

    2016-01-01

    Optical fluorescence microscopy was used in conjunction with X-ray fluorescence microscopy to monitor the stability and intracellular distribution of the luminescent rhenium(I) complex fac-[Re(CO) 3 (phen)L], where phen = 1,10-phenathroline and L = 5-(4-iodophenyl)tetrazolato, in 22Rv1 cells. The rhenium complex showed no signs of ancillary ligand dissociation, a conclusion based on data obtained via X-ray fluorescence imaging aligning iodine and rhenium distributions. A diffuse reticular localisation was detected for the complex, in the nuclear/perinuclear region of cells, by either optical or X-ray fluorescence techniques. Furthermore, X-ray fluorescence also showed that the Re-I complex disrupted the homeostasis of some biologically relevant elements, such as chlorine, potassium and zinc.

  13. Intraparticulate Metal Speciation Analysis of Soft Complexing Nanoparticles. The Intrinsic Chemical Heterogeneity of Metal-Humic Acid Complexes

    DEFF Research Database (Denmark)

    Town, R. M.; van Leeuwen, Herman P.

    2016-01-01

    ion condensation potential for higher valency counterions within the intraparticulate double layer zone of the soft NP. The approach offers new insights into the intrinsic heterogeneity of the HA. complexes, as revealed by the intraparticulate speciation as a function of the true degree of inner......-sphere complexation, theta(M). The ensuing intrinsic heterogeneity parameters, Gamma, for CdHA and CuHA complexes are in very good agreement with those obtained from dynamic electrochemical stripping chronopotentiometric measurements. The overall intraparticulate metal ion speciation is found to depend on theta...

  14. Preparation, structure and luminescent characterization of a series of metal-organic frameworks based on flexible ligands with nitrogen heterocycles and carboxyl

    Science.gov (United States)

    Dai, Hai-yu; Tang, Yu-yuan; Wang, Cui-juan; Chen, Shuang; Tong, Yan; Zhang, Zhi-Bing

    2017-12-01

    Seven new compounds, [Zn(pypymba)2]n(1), [Co(pypymba)2]n(2), [Cd(pypymba)2]n(3), [Cd(Hpypymba)Cl2]n(4), {[Cd(pypymba)Cl]·C2H5OH·H2O}n(5), [Cd(pypyaa)Cl]n(6), {[Cd2(pyznpy)2Cl2H2O]·H2O}n(7) [Hpypymba = 4-((3-(pyrazin-2-yl)-1H-pyrazol-1-yl)methyl)benzoic acid, Hpyznpy = 4-((3-(pyridin-2-yl)-1H-pyrazol-1-yl)methyl)benzoic acid, Hpypyaa = 2-(3-pyridin-2-yl)-1H-pyrazol-1-yl)acetic acid], were hydrothermally synthesized by tuning the metal ion's species, counter anions, solvents and pH values and characterized by routine methods: XRD, elemental analysis, fluorescence properties analysis, TGA and crystal structure analysis and single-crystal X-ray crystallography. The main structures of the compounds 1, 2, and 3 are extended to similar 3D structures by C-H…N, C-H…O hydrogen bonds and π…π stacking under the same synthesis method. Each Cd(II) node of compound 4 has four chlorine bridges (two pairs of double chlorine); Each Cd(II) node of compounds 5, 6 has two chlorine bridges (a pair of double chlorine bridges), while their spatial structures are expanded in different ways. Compound 7 also contains chlorine atoms, but does not contain chlorine bridged structures. The luminescent properties of compound 7 and the ones immersed in various kinds of organic compounds and nitrate@EtOH solutions have been investigated. Importantly, 7 shows highly sensitive response to nitrobenzene and Fe3+ through luminescence quenching effects, making it a promising luminescent sensor for nitrobenzene and Fe3+.

  15. Goldenphilicity: Luminescent gold compounds

    International Nuclear Information System (INIS)

    Sansores, L.E.

    2002-01-01

    In the solids and molecules different types of bonds are presented depending on the involved atoms, covalent bonds are common among elements of open shell, where more bond orbitals are filled than anti bond orbitals. It is expected that ionic bonds among closed shell atoms which have charges of opposite sign. Bonds type Van der Waals are presented among molecules which have a bipolar moment. It would not be expected bonds among zero charge species, or more generally with the same nominal charge and in any case the attractive forces would be very small. In fact it is expected that two metallic cations to be repelled each other. There recently is evidence that in organic or organometallic compounds could exist attractive interactions between two cations of the d 8 -d 10 -s 2 families. These bonds are weak but stronger than those of Van der Waals. They are compared with the hydrogen bonds. In this work it was reviewed some examples in which the goldenphilicity plays an important role in the luminescence that the gold complexes present. Examples of mono, bi and trinuclear and the structures that these organometallic compounds could take are examined. (Author)

  16. 1,2,4-Triazines in the Synthesis of Bipyridine Bisphenolate ONNO Ligands and Their Highly Luminescent Tetradentate Pt(II) Complexes for Solution-Processable OLEDs.

    Science.gov (United States)

    Pander, Piotr; Bulmer, Rachel; Martinscroft, Ross; Thompson, Stuart; Lewis, Frank W; Penfold, Thomas J; Dias, Fernando B; Kozhevnikov, Valery N

    2018-04-02

    This article describes a convenient method for the synthesis of ONNO-type tetradentate 6,6'-bis(2-phenoxy)-2,2'-bipyridine (bipyridine bisphenolate, BpyBph) ligands and their platinum(II) complexes. The methodology includes the synthesis of 1,2,4-triazine precursors followed by their transformation to functionalized pyridines by the Boger reaction. Two complementary routes employing 3,3'- and 5,5'-bis-triazines allow a modification of the central pyridine rings in different positions, which was exemplified by the introduction of cyclopentene rings. The new ligands were used to prepare highly luminescent ONNO-type Pt(II) complexes. The position of the cyclopentene rings significantly influences the solubility and photophysical properties of these complexes. Derivatives with closely positioned cyclopentene rings are soluble in organic solvents and proved to be the best candidate for solution-processable organic light-emitting devices (OLEDs), showing efficient single-dopant candlelight electroluminescence.

  17. SYNTHESIS, CRYSTAL STRUCTURE AND LUMINESCENT PROPERTY OF A DINUCLEAR Tb(II COMPLEX WITH HOMOPHTHALIC ACID AND 2,2’-BIPYRIDYL

    Directory of Open Access Journals (Sweden)

    LI-HUA WANG

    2015-07-01

    Full Text Available A novel dinuclear Tb(III complex, [Tb(bpy2L2] (bpy = 2,2’-bipyridine, H2L = homophthalic acid, has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Tb(III complex is monoclinic, space group P21/c with a = 9.368(2 Å, b = 15.948(4 Å, c = 12.216(3 Å, β = 103.023(4º, V= 1778.2(7 Å3, Z = 2, Dc = 1.910 mg·m-3, μ = 4.011 mm-1, F(000 = 996, and final R1 = 0.0602, ωR2 = 0.2192. The result shows that the Tb(III center is seven-coordination with a N2O5 distorted pengonal bipyramidal geometry. The luminescent property of Tb(III complex was investigated.

  18. Synthesis and characterization of bright green terbium coordination complex derived from 1,4-bis(carbonylmethyl)terephthalate: Structure and luminescence properties

    Science.gov (United States)

    Ma, Mengjiao; Li, Congcong; Shu, Dengkun; Wang, Chaohua; Xi, Peng

    2018-02-01

    A photoluminescent terbium (Tb) complex involving a novel benzoic-acid compound with a unique coordinated structure, namely 1,4-bis(carbonylmethyl)terephthalate (BCMT), has been designed and synthesized. The new coordinate structure and energy-transfer mechanism between the ligand and Tb(III) ions were investigated in detail. The results demonstrated that the BCMT-Tb(III) complex shows strong fluorescence intensity (4 × 106 a.u.) and long fluorescence lifetime (1.302 ms), owing to the favorable degree of energy matching between the triplet excited level of the ligand and the resonant level of Tb(III) ions. Based on the analysis of three-dimensional luminescence spectra, the as-prepared Tb(III) complex can be effectively excited in the range of 250-310 nm, and it shows high color purity, with a bright green appearance.

  19. Ibandronate metal complexes: solution behavior and antiparasitic activity.

    Science.gov (United States)

    Demoro, Bruno; Rostán, Santiago; Moncada, Mauricio; Li, Zhu-Hong; Docampo, Roberto; Olea Azar, Claudio; Maya, Juan Diego; Torres, Julia; Gambino, Dinorah; Otero, Lucía

    2018-03-01

    To face the high costs of developing new drugs, researchers in both industry and academy are looking for ways to repurpose old drugs for new uses. In this sense, bisphosphonates that are clinically used for bone diseases have been studied as agents against Trypanosoma cruzi, causative parasite of Chagas disease. In this work, the development of first row transition metal complexes (M = Co 2+ , Mn 2+ , Ni 2+ ) with the bisphosphonate ibandronate (iba, H 4 iba representing the neutral form) is presented. The in-solution behavior of the systems containing iba and the selected 3d metal ions was studied by potentiometry. Mononuclear complexes [M(H x iba)] (2-x)- (x = 0-3) and [M(Hiba) 2 ] 4- together with the formation of the neutral polynuclear species [M 2 iba] and [M 3 (Hiba) 2 ] were detected for all studied systems. In the solid state, complexes of the formula [M 3 (Hiba) 2 (H 2 O) 4 ]·6H 2 O were obtained and characterized. All obtained complexes, forming [M(Hiba)] - species under the conditions of the biological studies, were more active against the amastigote form of T. cruzi than the free iba, showing no toxicity in mammalian Vero cells. In addition, the same complexes were selective inhibitors of the parasitic farnesyl diphosphate synthase (FPPS) enzyme showing poor inhibition of the human one. However, the increase of the anti-T. cruzi activity upon coordination could not be explained neither through the inhibition of TcFPPS nor through the inhibition of TcSPPS (T. cruzi solanesyl-diphosphate synthase). The ability of the obtained metal complexes of catalyzing the generation of free radical species in the parasite could explain the observed anti-T. cruzi activity.

  20. Controlling Magnetism of a Complex Metallic System Using Atomic Individualism

    Science.gov (United States)

    Mudryk, Y.; Paudyal, D.; Pecharsky, V. K.; Gschneidner, K. A., Jr.; Misra, S.; Miller, G. J.

    2010-08-01

    When the complexity of a metallic compound reaches a certain level, a specific location in the structure may be critically responsible for a given fundamental property of a material while other locations may not play as much of a role in determining such a property. The first-principles theory has pinpointed a critical location in the framework of a complex intermetallic compound—Gd5Ge4—that resulted in a controlled alteration of the magnetism of this compound using precise chemical tools.

  1. Charge transfers in complex transition metal alloys (Ti2Fe)

    International Nuclear Information System (INIS)

    Abramovici, G.

    1998-01-01

    We introduce a new non-orthogonal tight-binding model, for complex alloys, in which electronic structure is characterized by charge transfers. We give the analytic calculation of a charge transfer, in which overlapping two-center terms are rigorously taken into account. Then, we apply numerically this result to an approximant phase of a quasicrystal of Ti 2 Fe alloy. This model is more particularly adapted to transition metals, and gives realistic densities of states. (orig.)

  2. The dynamic behavior of the exohedral transition metal complexes ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 129; Issue 7. The dynamic behavior of the exohedral transition metal complexes of B₄₀ : η⁶- and η⁷-B₄₀Cr(CO) ₃ and Cr(CO) ₃η⁷-B₄η₀-Cr(CO) ₃. NAIWRIT KARMODAK ELUVATHINGAL D JEMMIS. REGULAR ARTICLE Volume 129 Issue 7 July 2017 pp ...

  3. The impact of metal transport processes on bioavailability of free and complex metal ions in methanogenic granular sludge

    NARCIS (Netherlands)

    Bartacek, J.; Fermoso, F.G.; Vergeldt, F.; Gerkema, E.; Maca, J.; As, van H.; Lens, P.N.L.

    2012-01-01

    Bioavailability of metals in anaerobic granular sludge has been extensively studied, because it can have a major effect on metal limitation and metal toxicity to microorganisms present in the sludge. Bioavailability of metals can be manipulated by bonding to complexing molecules such as

  4. Mechanics of metal-catecholate complexes: The roles of coordination state and metal types

    Science.gov (United States)

    Xu, Zhiping

    2013-01-01

    There have been growing evidences for the critical roles of metal-coordination complexes in defining structural and mechanical properties of unmineralized biological materials, including hardness, toughness, and abrasion resistance. Their dynamic (e.g. pH-responsive, self-healable, reversible) properties inspire promising applications of synthetic materials following this concept. However, mechanics of these coordination crosslinks, which lays the ground for predictive and rational material design, has not yet been well addressed. Here we present a first-principles study of representative coordination complexes between metals and catechols. The results show that these crosslinks offer stiffness and strength near a covalent bond, which strongly depend on the coordination state and type of metals. This dependence is discussed by analyzing the nature of bonding between metals and catechols. The responsive mechanics of metal-coordination is further mapped from the single-molecule level to a networked material. The results presented here provide fundamental understanding and principles for material selection in metal-coordination-based applications. PMID:24107799

  5. Protection of metal artefacts with the formation of metal-oxalates complexes by Beauveria bassiana.

    Directory of Open Access Journals (Sweden)

    Edith eJoseph

    2012-01-01

    Full Text Available Several fungi present high tolerance to toxic metals and some are able to transform metals into metal-oxalate complexes. In this study, the ability of Beauveria bassiana to produce copper oxalates was evaluated in vitro. Growth performance was tested on various copper-containing media. B. bassiana proved highly resistant to copper, tolerating concentrations of up to 20 g.L-1, and precipitating copper oxalates on all media tested. Chromatographic analyses showed that this species produced oxalic acid as sole metal chelator. The production of metal-oxalates can be used in the restoration and conservation of archaeological and modern metal artefacts. The production of copper-oxalates was confirmed directly using metallic pieces (both archaeological and modern. The conversion of corrosion products into copper oxalates was demonstrated as well. In order to assess whether the capability of B. bassiana to produce metal-oxalates could be applied to other metals, iron and silver were tested as well. Iron appears to be directly sequestered in the wall of the fungal hyphae forming oxalates and probably goethite. However, the formation of a homogeneous layer on the object is not yet optimal. Silver nitrate was extracellularly reduced into nanoparticles of elemental silver by an unknown mechanism. The production of copper oxalates is immediately applicable for the conservation of copper-based artefacts. For iron and silver this is not yet the case. However, the vast ability of B. bassiana to transform toxic metals using different immobilization mechanisms seems to offer considerable possibilities for industrial applications, such as the bioremediation of contaminated soils or the green synthesis of chemicals.

  6. 40 CFR Appendix B to Part 414 - Complexed Metal-Bearing Waste Streams

    Science.gov (United States)

    2010-07-01

    ... 414—Complexed Metal-Bearing Waste Streams Chromium Azo dye intermediates/Substituted diazonium salts + coupling compounds Vat dyes Acid dyes Azo dyes, metallized/Azo dye + metal acetate Acid dyes, Azo...

  7. Luminescent materials based on Tb, Eu-containing layered double hydroxides

    International Nuclear Information System (INIS)

    Zhuravleva, N.G.; Eliseev, A.A.; Lukashin, A.V.; Kinast, U.; Tret'yakov, Yu.D.

    2004-01-01

    Luminescent materials on the basis of magnesium-aluminium layered double hydroxides with intercalated anionic complexes of terbium and europium picolinates were synthesized. Relying on data of spectroscopy, elementary and X-ray phase analyses, the change in the rare earth complex structure and metal/ligand ratio, depending on the hydroxide layer charge, determined by Mg/Al ratio in the double hydroxide, were ascertained. The values of quantum yields of luminescence for terbium-containing samples amounted to 30-50% [ru

  8. Metal-organic and supramolecular networks driven by 5-chloronicotinic acid: Hydrothermal self-assembly synthesis, structural diversity, luminescent and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Zhu-Qing, E-mail: zqgao2008@163.com [School of Chemical and Biological Engineering, Taiyuan University of Science and Technology, Taiyuan 030021 (China); Li, Hong-Jin [School of Chemical and Biological Engineering, Taiyuan University of Science and Technology, Taiyuan 030021 (China); Gu, Jin-Zhong, E-mail: gujzh@lzu.edu.cn [College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Zhang, Qing-Hua [School of Chemical and Biological Engineering, Taiyuan University of Science and Technology, Taiyuan 030021 (China); Kirillov, Alexander M. [Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049–001 Lisbon (Portugal)

    2016-09-15

    Four new crystalline solids, namely [Co{sub 2}(µ{sub 2}-5-Clnic){sub 2}(µ{sub 3}-5-Clnic){sub 2}(µ{sub 2}-H{sub 2}O)]{sub n} (1), [Co(5-Clnic){sub 2}(H{sub 2}O){sub 4}]·2(5-ClnicH) (2), [Pb(µ{sub 2}-5-Clnic){sub 2}(phen)]{sub n} (3), and [Cd(5-Clnic){sub 2}(phen){sub 2}]·3H{sub 2}O (4) were generated by hydrothermal self-assembly methods from the corresponding metal(II) chlorides, 5-chloronicotinic acid (5-ClnicH) as a principal building block, and 1,10-phenanthroline (phen) as an ancillary ligand (optional). All the products 1–4 were characterized by IR spectroscopy, elemental analysis, thermogravimetric (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. Their structures range from an intricate 3D metal-organic network 1 with the 3,6T7 topology to a ladder-like 1D coordination polymer 3 with the 2C1 topology, whereas compounds 2 and 4 are the discrete 0D monomers. The structures of 2 and 4 are further extended (0D→2D or 0D→3D) by hydrogen bonds, generating supramolecular networks with the 3,8L18 and ins topologies, respectively. Synthetic aspects, structural features, thermal stability, magnetic (for 1) and luminescent (for 3 and 4) properties were also investigated and discussed. - Graphical abstract: A new series of crystalline solids was self-assembled and fully characterized; their structural, topological, luminescent and magnetic features were investigated. Display Omitted.

  9. Late transition metal m-or chemistry and D6 metal complex photoeliminations

    Energy Technology Data Exchange (ETDEWEB)

    Sharp, Paul [Univ. of Missouri, Columbia, MO (United States)

    2015-07-31

    With the goal of understanding and controlling photoreductive elimination reactions from d6 transition metal complexes as part of a solar energy storage cycle we have investigated the photochemistry of Pt(IV) bromo, chloro, hydroxo, and hydroperoxo complexes. Photoreductive elimination reactions occur for all of these complexes and appear to involve initial Pt-Br, Pt-Cl, or Pt-O bond fission. In the case of Pt-OH bond fission, the subsequent chemistry can be controlled through hydrogen bonding to the hydroxo group.

  10. Synthesis, 2D NMR, electrochemistry and luminescence of ruthenium (II) complexes with 2,2-bipyridine and 5-(ω-bromoalkylamido)-1, 10-phenanthroline

    International Nuclear Information System (INIS)

    Peng Wang; Xiangping Wang, Guoyi Zhu; Xiaoyan Jing; Jun Wang

    2000-01-01

    The efficient synthesis of 5-(5-bromovaleramido)-1, 10-phenanthroline, 5-(6-bromohexanamido)-1,10-phenanthroline, and 5-(11-bromoundecanamido)-1, 10-phenanthroline are described, which reacted with cis-Ru(bpy) 2 Cl 2 .2H 2 O and sodium hexafluorophosphate to form Ru(bpy) 2 [phen-NHCO(CH 2 ) n Br](PF 6 ) 2 (n=4, 5 or 10; phen=1,10-phenanthroline). The intricate 1 H NMR spectra at low field of these complexes were completely assigned in virtue of 1 H- 1 H COSY technique. Cyclic voltammetry was used to study electrochemical behaviours of these complexes, and their luminescent properties were investigated with fluorescent spectra. (author)

  11. Metal Complexation with Chitosan and its Grafted Copolymer

    International Nuclear Information System (INIS)

    Abo-Hussen, A.A.; Elkholy, S.S.; Elsabee, M.Z.

    2005-01-01

    The adsorption of M (II); Co (II), Ni (If), Cu (II), Zn (II) and Cd (II) from aqueous solutions by chitosan flakes and beads have been studied. The maximum up-take of M (II) ions on chitosan beads was greater than on flakes. Batch adsorption experiments were carried out as a function of ph, agitation period and initial concentration of the metal ions. A ph of 6.0 was found to be optimum for M (II) adsorption on chitosan flakes and beads. The uptake of the ions was determined from the changes in its concentration, as measured by ultraviolet and visible spectroscopy. The metal ions uptake of chitosan grafted with vinyl pyridine (VP) is higher than that of the chitosan. The experimental data of the adsorption equilibrium from M (II)-solutions correlated well with the Langmuir and Freundlich equations. Several spectroscopic methods have been used to study the formation of the polymer/metal cation complex. The cation coordination is accompanied by proton displacement off the polymer or by fixation of a hydroxide ion in aqueous solutions. The largest ionic displacement is observed with Cu (II) and Zn (II) demonstrating the largest affinity of chitosan for these ions. The FT-IR spectral of the complexes show that both the amino and hydroxyl groups of chitosan participated in the chelation process. The ESR spectra of Cu-complex show an absorption at gi 2.06, g// = 2.23, A// x 10-4 (cm-1) = 160 and G = 3.8 indicating the formation of square planar structure. The adsorption of M (II) ions followed the sequence Cu (II) > Zn (II) > Cd (II) > Ni (II) > Co (II), this order seems to be independent on the size and the physical form of chitosan. SEM shows small membranous structure on the surface of chitosan flakes as compared to Cu (Il)- chitosan complex. EDTA was used for the desorption studies

  12. Preparation and luminescent properties of the novel polymer-rare earth complexes composed of Poly(ethylene-co-acrylic acid) and Europium ions

    Science.gov (United States)

    Wu, Yuewen; Hao, Haixia; Wu, Qingyao; Gao, Zihan; Xie, Hongde

    2018-06-01

    A series of novel polymer-rare earth complexes with Eu3+ ions have been synthesized and investigated successfully, including the binary complexes containing the single ligand poly(ethylene-co-acrylic acid) (EAA) and the ternary complexes using 1,10-phenanthroline (phen), dibenzoylmethane (DBM) or thenoyltrifluoroacetone (TTA) as the second ligand. Their structures have been characterized by Fourier transform infrared spectroscopy (FT-IR), elemental analysis and X-ray diffraction (XRD), which confirm that both EAA and small molecules participate in the coordination reaction with rare earth ions, and they can disperse homogeneously in the polymer matrixes. Both ultraviolet-visible (UV-vis) absorption and photoluminescence tests for the complexes have been recorded. The relationship between fluorescence intensity of polymer-rare earth complexes and the quantity of ligand EAA has been studied and discussed. The films casted from the complexes solution can emit strong characteristic red light under UV light excitation. All these results suggest that the complexes possess potential application as luminescent materials.

  13. Organodioxygen complexes of some group 4B metal ions

    International Nuclear Information System (INIS)

    Tarafder, M.T.H.; Akhter Hossain; Gino Mariotto

    2003-09-01

    Organodioxygen complexes of some group 4B metal ions, viz., zirconium(IV), tin(IV) and lead(II) containing monodentate, bidentate and tridentate ligands were synthesized and characterized. The complexes have the compositions of [Zr(O)(O 2 )2C 5 H 5 N.H 2 O], [Zr(O)(O 2 - ) 2 .2OPPh 3 ], [Sn(O 2 )(C 9 H 6 NO) 2 ], [Sn(0 2 ) 2 .(CH 2 ) 2 (NH 2 ) 2 ], [Pb(O 2 - )(C 5 H 5 N) 2 NO 3 ], [Pb(O 2 )(C 8 H 6 NOH)], [Pb(O 2 - )(det)NO 3 ] and [PbO 2 - ) (C 5 H 4 NCOOH)NO 3 .H 2 O]. Because of apparent linearity of M- O 2 grouping, the V 1 (O-O) stretching modes were only Raman active, giving bands at 810- 841 cm 1 for the peroxo complexes (1, 3, ,4 and 6), while the bands in the superoxo complexes (2, 5, 7 and 8) appeared at 1020- 1100 cm -1 . The peroxo complex of Zr(IV) containing monodentate ligands were found to oxidize trans-stilbene to trans-stilbene oxide under stoichiometric conditions. The organoperoxo complexes of tin and lead were insensitive to oxidative processes. (author)

  14. Infrared Spectroscopy of Metal Ion Complexes: Models for Metal Ligand Interactions and Solvation

    Science.gov (United States)

    Duncan, Michael

    2006-03-01

    Weakly bound complexes of the form M^+-Lx (M=Fe, Ni, Co, etc.; L=CO2, C2H2, H2O, benzene, N2) are prepared in supersonic molecular beams by laser vaporization in a pulsed-nozzle cluster source. These species are mass analyzed and size-selected in a reflectron time-of-flight mass spectrometer. Clusters are photodissociated at infrared wavelengths with a Nd:YAG pumped infrared optical parametric oscillator/amplifier (OPO/OPA) laser or with a tunable infrared free-electron laser. M^+-(CO2)x complexes absorb near the free CO2 asymmetric stretch near 2349 cm-1 but with an interesting size dependent variation in the resonances. Small clusters have blue-shifted resonances, while larger complexes have additional bands due to surface CO2 molecules not attached to the metal. M^+(C2H2)n complexes absorb near the C-H stretches in acetylene, but resonances in metal complexes are red-shifted with repect to the isolated molecule. Ni^+ and Co^+ complexes with acetylene undergo intracluster cyclization reactions to form cyclobutadiene. Transition metal water complexes are studied in the O-H stretch region, and partial rotational structure can be measured. M^+(benzene) and M^+(benzene)2 ions (M=V, Ti, Al) represent half-sandwich and sandwich species, whose spectra are measured near the free benzene modes. These new IR spectra and their assignments will be discussed as well as other new IR spectra for similar complexes.

  15. 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.

  16. Chemical bonding of hydrogen molecules to transition metal complexes

    International Nuclear Information System (INIS)

    Kubas, G.J.

    1990-01-01

    The complex W(CO) 3 (PR 3 ) 2 (H 2 ) (CO = carbonyl; PR 3 = organophosphine) was prepared and was found to be a stable crystalline solid under ambient conditions from which the hydrogen can be reversibly removed in vacuum or under an inert atmosphere. The weakly bonded H 2 exchanges easily with D 2 . This complex represents the first stable compound containing intermolecular interaction of a sigma-bond (H-H) with a metal. The primary interaction is reported to be donation of electron density from the H 2 bonding electron pair to a vacant metal d-orbital. A series of complexes of molybdenum of the type Mo(CO)(H 2 )(R 2 PCH 2 CH 2 PR 2 ) 2 were prepared by varying the organophosphine substitutent to demonstrate that it is possible to bond either dihydrogen or dihydride by adjusting the electron-donating properties of the co-ligands. Results of infrared and NMR spectroscopic studies are reported. 20 refs., 5 fig

  17. Synthesis and Luminescence Properties of New Metal-Organic Frameworks Based on Zinc(II Ions and 2,5-Thiophendicarboxylate Ligands

    Directory of Open Access Journals (Sweden)

    Anna Lysova

    2017-12-01

    Full Text Available Six new metal-organic frameworks based on 2,5-thiophendicarboxylate (tdc2– and zinc(II ions were prepared in different reaction conditions, and their crystal structures were determined by XRD analysis. The compound [Zn(tdc(dabco(H2O]∙DMF (1 is based on mononuclear Zn(II ions connected by tdc2– and dabco linkers into square-grid layered nets. The compound [Zn3(tdc3(dabco2] (2 is a rare example of monocoordinated dabco ligands in the metal-organic framework chemistry. Its crystal structure contains trinuclear linear carboxylate building units, connected into a distorted primitive cubic net. Similar trinuclear units were also found in [Zn5(tdc4(Htdc2(dabco2]∙4DMF∙14H2O (3, although as a part of more complicated pentanuclear motives. The compound [Na2Zn(tdc2(DMF2] (4, quantitatively isolated by the addition of NaOH to the mixture of Zn(NO32 and H2tdc, is based on 1D chain motives, interconnected by tdc2– linkers into a three-dimensional framework. The compounds [Zn3(tdc3(DMF2]∙0.8DMF∙1.1H2O (5 and [Zn3(tdc3(DMF3]∙0.8DMF∙1.3H2O (6 were prepared in very similar reaction conditions, but with different times of heating, indirectly indicating higher thermodynamic stability of the three-dimensional metal-organic framework 6, compared to the two-dimensional metal-organic framework 5. The crystal structures of both 5 and 6 are based on the same trinuclear linear units as in 2. Luminescence properties of the compounds 4–6 were studied and compared with those for Na2tdc salt. In particular, the luminescence spectra of 4 practically coincide with those for the reference Na2tdc, while 5 and 6 exhibit coherent shifts of peaks to higher energies. Such hypsochromic shifts are likely associated with a different effective charge on the tdc2– anions in Na2tdc and sodium-containing 4, compared to zinc-based 5 and 6.

  18. Chemistry and Properties of Complex Intermetallics from Metallic Fluxes

    Energy Technology Data Exchange (ETDEWEB)

    Kanatzidis, Mercouri G. [Northwestern Univ., Evanston, IL (United States)

    2015-03-28

    This project investigated the reaction chemistry and synthesis of new intermetallic materials with complex compositions and structures using metallic fluxes as solvents. It was found that the metallic fluxes offer several key advantages in facilitating the formation and crystal growth of new materials. The fluxes mostly explored were liquid aluminum, gallium and indium. The main purpose of this project was to exploit the potential of metallic fluxes as high temperature solvent for materials discovery in the broad class of intermetallics. This work opened new paths to compound formation. We discovered many new Si (or Ge)-based compounds with novel structures, bonding and physicochemical properties. We created new insights about the reaction chemistry that is responsible for stabilizing the new materials. We also studied the structural and compositional relationships to understand their properties. We investigated the use of Group-13 metals Al, Ga and In as solvents and have generated a wide variety of new results including several new ternary and quaternary materials with fascinating structures and properties as well as new insights as to how these systems are stabilized in the fluxes. The project focused on reactions of metals from the rare earth element family in combination with transition metals with Si and Ge. For example molten gallium has serves both as a reactive and non-reactive solvent in the preparation and crystallization of intermetallics in the system RE/M/Ga/Ge(Si). Molten indium behaves similarly in that it too is an excellent reaction medium, but it gives compounds that are different from those obtained from gallium. Some of the new phase identified in the aluminide class are complex phases and may be present in many advanced Al-matrix alloys. Such phases play a key role in determining (either beneficially or detrimentally) the mechanical properties of advanced Al-matrix alloys. This project enhanced our basic knowledge of the solid state chemistry

  19. Fixation of metallic sulfosalicylate complexes on an anionic exchange resin

    International Nuclear Information System (INIS)

    Cahuzac, S.

    1969-06-01

    Since sulfosalicylate ions have acid-base properties, sulfosalicylate complexes have an apparent stability which varies with the ph. As a result, the fixation of sulfo-salicylates on an anionic exchange resin depends on the ph of the solution in equilibrium with the resin. This research has been aimed at studying the influence of the ph on the fixation on an anionic exchange resin (Dowex 1 x 4) of sulfosalicylate anions on the one hand, and of metallic sulfosalicylate complexes on the other hand. In the first part of this work, a determination has been made, by frontal analysis of the distribution of sulfosalicylate ions in the resin according to the total sulfosalicylate I concentration in the aqueous solution in equilibrium with the resin. The exchange constants of these ions between the resin and the solution have been calculated. In the second part, a study has been made of the fixation of anionic sulfosalicylate complexes of Fe(III), Al(III), Cr(III), Cu(II), Ni(II), Co(II), Zn(II), Mn(II), Cd(II), Fe(II) and UO 2 2+ . By measuring the partition coefficients of these different elements between the resin and the solution it has been possible to give interpretation for the modes of fixation of the metallic ions, and to calculate their exchange constant between the resin and the solution. The relationship has been established for each metallic element studied, between its partition coefficient, the ph and the total concentration of the complexing agent in solution. Such a relationship makes it possible to predict, for given conditions, the nature of the species in solution and in the resin, as well as the partition coefficient of a metallic, element. Finally, in the third part of the work, use has been made of results obtained previously, to carry out some separations (Ni 2+ - Co 2+ ; Ni 2+ - Co 2+ - Cu 2+ ; UO 2 2+ - Fe 3+ ; UO 2 2+ - Cr 3+ ; UO 2 2+ - Cu 2+ ; UO 2 2+ - Ni 2+ ; UO 2 2+ - Co 2+ ; UO 2 2+ - Mn 2+ and UO 2 2+ - Cd 2+ ), as well as the purification

  20. luminescence properties

    Indian Academy of Sciences (India)

    1Faculty of Science and Arts, Department of Chemistry, Bozok University, Yozgat 66900, Turkey. 2Faculty of Science, Department of Chemistry, Erciyes ... synthesized by the conventional solid-state reaction method, their crystal structures and luminescence properties were investigated. X-ray diffraction patterns (XRD) ...

  1. Synthesis and luminescence properties of two novel europium (III) perchlorate complexes with bis(benzylsulfinyl)methane and 1,10-phenanthroline

    Energy Technology Data Exchange (ETDEWEB)

    Li, Wen-Xian, E-mail: nmglwx@163.com [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Guo, Feng [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Zheng, Yu-Shan [Inner Mongolia Autonomous Region Product Quality Inspection Institute, Hohhot 010010 (China); Cao, Xiao-Fang; Feng, Shu-Yan; Bai, Juan; Xin, Xiao-Dong [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China)

    2014-09-15

    Two novel binary and ternary Europium (III) perchlorate complexes were synthesized. The binary complex was prepared with bis(benzylsulfinyl)methane as ligand, and the ternary complex was with bis(benzylsulfinyl)methane as first ligand and 1,10-Phenanthroline as second ligand. They were characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, {sup 1}HNMR and UV spectra. The results indicated that the composition of binary and ternary complexes was EuL{sub 2.5}·(ClO{sub 4}){sub 3}·3H{sub 2}O and Eu{sub 2}L{sub 4}·phen·(ClO{sub 4}){sub 6}·12H{sub 2}O (L=C{sub 6}H{sub 5}CH{sub 2}SOCH{sub 2}SOCH{sub 2}C{sub 6}H{sub 5}), respectively. The fluorescent spectra illustrated that the complexes displayed characteristic Europium (III) ion fluorescence in solid state, indicating the ligands favored energy transfer to the excitation state energy level of it. The strongest characteristic fluorescence emission intensity of the ternary system was 1.87 times as strong as that of the binary system. The fluorescent quantum yields of the Eu (III) ternary and binary complexes were also calculated. Additionally, the phosphorescence spectra and the luminescence mechanisms of the complexes were studied and explained. - Highlights: • Two rare earth complexes are new. And they are stabilized. • The intensities of the two rare earth complexes were all stronger and the lifetimes were longer. • The introduction of the second organic ligand1,10-Phenanthroline enhanced the fluorescence intensity. • The fluorescent quantum yields of two complexes being calculated are both very high.

  2. Complexation of metal ions with humic acid: charge neutralization model

    International Nuclear Information System (INIS)

    Kim, J.I.; Czerwinski, K.R.

    1995-01-01

    A number of different approaches are being used for describing the complexation equilibrium of actinide ions with humic or fulvic acid. The approach chosen and verified experimentally by Tu Muenchen will be discussed with notable examples from experiment. This approach is based on the conception that a given actinide ion is neutralized upon complexation with functional groups of humic or fulvic acid, e.g. carboxylic and phenolic groups, which are known as heterogeneously cross-linked polyelectrolytes. The photon energy transfer experiment with laser light excitation has shown that the actinide ion binding with the functional groups is certainly a chelation process accompanied by metal ion charge neutralization. This fact is in accordance with the experimental evidence of the postulated thermodynamic equilibrium reaction. The experimental results are found to be independent of origin of humic or fulvic acid and applicable for a broad range of pH. (authors). 23 refs., 7 figs., 1 tab

  3. Complexing agent and heavy metal removals from metal plating effluent by electrocoagulation with stainless steel electrodes.

    Science.gov (United States)

    Kabdaşli, Işik; Arslan, Tülin; Olmez-Hanci, Tuğba; Arslan-Alaton, Idil; Tünay, Olcay

    2009-06-15

    In the present study, the treatability of a metal plating wastewater containing complexed metals originating from the nickel and zinc plating process by electrocoagulation using stainless steel electrodes was experimentally investigated. The study focused on the effect of important operation parameters on electrocoagulation process performance in terms of organic complex former, nickel and zinc removals as well as sludge production and specific energy consumption. The results indicated that increasing the applied current density from 2.25 to 9.0 mA/cm(2) appreciably enhanced TOC removal efficiency from 20% to 66%, but a further increase in the applied current density to 56.25 mA/cm(2) did not accelerate TOC removal rates. Electrolyte concentration did not affect the process performance significantly and the highest TOC reduction (66%) accompanied with complete heavy metal removals were achieved at the original chloride content ( approximately 1500 mg Cl/L) of the wastewater sample. Nickel removal performance was adversely affected by the decrease of initial pH from its original value of 6. Optimum working conditions for electrocoagulation of metal plating effluent were established as follows: an applied current density of 9 mA/cm(2), the effluent's original electrolyte concentration and pH of the composite sample. TOC removal rates obtained for all electrocoagulation runs fitted pseudo-first-order kinetics very well (R(2)>92-99).

  4. Observation of metallic sphere–complex plasma interactions in microgravity

    International Nuclear Information System (INIS)

    Schwabe, M; Zhdanov, S; Hagl, T; Huber, P; Rubin-Zuzic, M; Zaehringer, E; Thomas, H M; Lipaev, A M; Molotkov, V I; Naumkin, V N; Fortov, V E; Vinogradov, P V

    2017-01-01

    The PK-3 Plus laboratory on board the International Space Station is used to study the interaction between metallic spheres and a complex plasma. We show that the metallic spheres significantly affect both the local plasma environment and the microparticle dynamics. The spheres charge under the influence of the plasma and repel the microparticles, forming cavities surrounding the spheres. The size of the cavity around a sphere is used to study the force balance acting on microparticles at the cavity edge. We show that the ion drag force and pressure force from other microparticles balances with the electric force acting from the sphere to within 20%. At intermediate distances from the sphere surface, the interaction between the microparticles and the metallic spheres is attractive due to the drag force stemming from the ions which are moving towards the highly charged spheres. The spheres thus strongly affect the plasma fluxes. This modification of the plasma flux can lead to an effective surface tension acting on the microparticles, and to the excitation of dust-density waves near the spheres, as the local electric field crosses a threshold. (paper)

  5. Sensing of phosphates by using luminescent Eu(III) and Tb(III) complexes: application to the microalgal cell Chlorella vulgaris.

    Science.gov (United States)

    Nadella, Sandeep; Sahoo, Jashobanta; Subramanian, Palani S; Sahu, Abhishek; Mishra, Sandhya; Albrecht, Markus

    2014-05-12

    Phenanthroline-based chiral ligands L(1) and L(2) as well as the corresponding Eu(III) and Tb(III) complexes were synthesized and characterized. The coordination compounds show red and green emission, which was explored for the sensing of a series of anions such as F(-), Cl(-), Br(-), I(-), NO3(-), NO2(-), HPO4(2-), HSO4(-), CH3COO(-), and HCO3(-). Among the anions, HPO4(2-) exhibited a strong response in the emission property of both europium(III) and terbium(III) complexes. The complexes showed interactions with the nucleoside phosphates adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP). Owing to this recognition, these complexes have been applied as staining agents in the microalgal cell Chlorella vulgaris. The stained microalgal cells were monitored through fluorescence microscopy and scanning electron microscopy. Initially, the complexes bind to the outer cell wall and then enter the cell wall through holes in which they probably bind to phospholipids. This leads to a quenching of the luminescence properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. A luminescent Cd(II)-based metal-organic framework for detection of Fe(III) ions in aqueous solution

    Science.gov (United States)

    Li, Fen-Fang; Zhu, Miao-Li; Lu, Li-Ping

    2018-05-01

    A novel Cd((II)-organic framework [Cd(Hcbic)]n (H3cbic = 1-(4-carboxybenz-yl)-1H-benzoim-idazole-5, 6-dicarboxylic acid) was assembled and characterized by X-ray single crystal analysis. The Cd-MOF features one-dimensional left and right-handed double helical chains with screw-pitch of about 4.727 Å and the 4-methyl benzoic acid groups of Hcbic2- ligands in MOF-1 play many ribbons distributing in the two sides of the 2D networks. It is found that MOF-1 shows high selectivity (KSV = 1.8 × 105 L / mol) for Fe3+ ions in water solution with luminescent quenching because of the existence of uncoordinated carboxyl groups within open frameworks, which indicates that MOF-1 is a simple and reliable detection sensing reagent for Fe3+ in practical applications.

  7. Synthesis, structure and luminescence properties of binary and ternary complexes of lanthanide (Eu{sup 3+}, Sm{sup 3+} and Tb{sup 3+}) with salicylic acid and 1,10-phenanthroline

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Chen-Qi; Yan, Tian-Lu; Wang, Yi-Ting; Ye, Zi-Jun; Xu, Cun-Jin, E-mail: cjxu@hznu.edu.cn; Zhou, Wen-Jun

    2017-04-15

    A series of binary and ternary complexes of lanthanide (Eu{sup 3+}, Sm{sup 3+} and Tb{sup 3+}) with salicylic acid (Hsal) and 1,10-phenanthroline (phen) were synthesized, and characterized by element analysis, coordination titration analysis, IR, UV and TG-DTA. Their compositions were (NH{sub 4})[Ln(sal){sub 4}(H{sub 2}O){sub 2}] (Ln=Eu (1), Sm (2), Tb (3)) and (NH{sub 4})[Ln(sal){sub 4}(phen){sub 2}] (Ln=Eu (4), Sm (5), Tb (6)), respectively. In particular, the ternary complex of Eu{sup 3+}, 4, was characterized by X-ray diffraction, and luminescence intensities of binary and ternary complexes were compared. In case of Eu{sup 3+} and Sm{sup 3+} complexes, ternary complexes emitted stronger luminescence than corresponding binary complexes of salicylic acid and Ln{sup 3+}. On the other hand, the ternary Tb{sup 3+} complex had weaker luminescence than the binary complex because of back energy transfer from Tb{sup 3+} to phen. The CIE coordinates of 1–6 were calculated as (0.65, 0.35), (0.52, 0.48), (0.33, 0.59), (0.67, 0.33), (0.62, 0.38) and (0.36, 0.58), respectively, which enable these complexes to be promising candidates for red, green, or yellow component in OLEDs.

  8. Crystal structures and luminescence properties of two Cd(II) complexes based on 2-(1H-imidazol-1methyl)-6-methyl-1H-benzimidazole

    International Nuclear Information System (INIS)

    Zhang, Yuhong; Meng, Xiangru; Wen, Yu; Li, Peng; Ma, Lin; Zhang, Qiuju

    2015-01-01

    Two new complexes, {[Cd(immb)I 2 ].DMF} n (1) and {[Cd 3 (immb)(btc) 2 ]. H 2 O} n (2) (immb = 2-(1H-imidazol- 1-methyl)-6-methyl-1H-benzimidazole, btc = 1,2,3-benzenetricarboxylate, DMF = dimethyl formamide), have been synthesized and characterized. Single crystal X-ray diffraction shows that 1 exhibits a chain structure constructed by immb ligands bridging Cd(II) ions. In 2, Cd(II) ions are linked by immb ligands with bridging mode and btc3- anions with the μ 2 -η 2 :η 1 bonding pattern leading to a 2D structure. Luminescent properties have been investigated in the solid state at room temperature.

  9. Zinc-coordinated MOFs complexes regulated by hydrogen bonds: Synthesis, structure and luminescence study toward broadband white-light emission

    Science.gov (United States)

    Duan, Hui; Dan, Wenyan; Fang, Xiangdong

    2018-04-01

    Two new compounds, namely {[Zn(apc)2]·H2O}n (1) and [Zn(apc)2(H2O)2] (2), have been designed and synthesized with a multi-functional ligand 2-aminopyrimidine-5-carboxylic acid (Hapc). Both compounds were characterized by single crystal X-ray diffraction analysis (SC-XRD), elemental analysis (EA), infrared spectroscopy (IR), and thermogravimetric analysis (TG). In solid-state structures, 1 features a two-fold interpenetrating pillared-layer 3D framework with point symbol {83}2{86}, referring to tfa topology; while 2 exhibits a 3D framework based on super unit of Zn(apc)2(H2O)2 interconnected via hydrogen bonds. Furthermore, the luminescent properties of 1 and 2 were discussed.

  10. IRMPD Action Spectroscopy of Alkali Metal Cation-Cytosine Complexes: Effects of Alkali Metal Cation Size on Gas Phase Conformation

    NARCIS (Netherlands)

    Yang, B.; Wu, R.R.; Polfer, N.C.; Berden, G.; Oomens, J.; Rodgers, M.T.

    2013-01-01

    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both

  11. Synthesis, structure, terahertz spectroscopy and luminescent properties of copper (I) complexes with bis(diphenylphosphino)methane and N-donor ligands

    Science.gov (United States)

    Fan, Wei-Wei; Li, Zhong-Feng; Li, Jiao-Bao; Yang, Yu-Ping; Yuan, Yuan; Tang, Han-Qin; Gao, Ling-Xiao; Jin, Qiong-Hua; Zhang, Zhen-Wei; Zhang, Cun-Lin

    2015-11-01

    The reactions of copper(I) salts CuX [X = Cl, OTf (OTf = CF3SO3) and ClO4] and bis(diphenylphosphino)methane (dppm) with 4,4-bipyridine (4,4-bipy), 2,2-bipyridine (2,2-bipy), isoquinoline (i-C9H7N) and 1,10-phenanthroline (phen) lead to five new copper(I) complexes: [CuCl(dppm)(i-C9H7N)]2 (1), {[CuCl(dppm)(phen)]2•5H2O}n (2), [Cu2Cl2(dppm)2(4,4-bipy)]•4CH3CN (3), [Cu(dppm)(2,2-bipy)]2(OTf)2 (4), {[Cu2Cl(dppm)2(4,4-bipy)](ClO4)}n (5). Complexes 1, 3 and 4 are of dinuclear structure with eight-membered Cu2P4C2 rings. The structure of compound 2 can be simplified as three-dimensional topology. Complex 5 is of infinite chain structure linked by 4,4-bipy. All these complexes are characterized by IR, elemental analyses, single-crystal X-ray diffraction analysis, luminescence, NMR and terahertz time-domain spectroscopy.

  12. Hydrogen storage and evolution catalysed by metal hydride complexes.

    Science.gov (United States)

    Fukuzumi, Shunichi; Suenobu, Tomoyoshi

    2013-01-07

    The storage and evolution of hydrogen are catalysed by appropriate metal hydride complexes. Hydrogenation of carbon dioxide by hydrogen is catalysed by a [C,N] cyclometalated organoiridium complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(OH(2))](2)SO(4) [Ir-OH(2)](2)SO(4), under atmospheric pressure of H(2) and CO(2) in weakly basic water (pH 7.5) at room temperature. The reverse reaction, i.e., hydrogen evolution from formate, is also catalysed by [Ir-OH(2)](+) in acidic water (pH 2.8) at room temperature. Thus, interconversion between hydrogen and formic acid in water at ambient temperature and pressure has been achieved by using [Ir-OH(2)](+) as an efficient catalyst in both directions depending on pH. The Ir complex [Ir-OH(2)](+) also catalyses regioselective hydrogenation of the oxidised form of β-nicotinamide adenine dinucleotide (NAD(+)) to produce the 1,4-reduced form (NADH) under atmospheric pressure of H(2) at room temperature in weakly basic water. In weakly acidic water, the complex [Ir-OH(2)](+) also catalyses the reverse reaction, i.e., hydrogen evolution from NADH to produce NAD(+) at room temperature. Thus, interconversion between NADH (and H(+)) and NAD(+) (and H(2)) has also been achieved by using [Ir-OH(2)](+) as an efficient catalyst and by changing pH. The iridium hydride complex formed by the reduction of [Ir-OH(2)](+) by H(2) and NADH is responsible for the hydrogen evolution. Photoirradiation (λ > 330 nm) of an aqueous solution of the Ir-hydride complex produced by the reduction of [Ir-OH(2)](+) with alcohols resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex, which can catalyse hydrogen evolution from alcohols in a basic aqueous solution (pH 11.9). The catalytic mechanisms of the hydrogen storage and evolution are discussed by focusing on the reactivity of Ir-hydride complexes.

  13. Frustration across the periodic table: heterolytic cleavage of dihydrogen by metal complexes.

    Science.gov (United States)

    Bullock, R Morris; Chambers, Geoffrey M

    2017-08-28

    This perspective examines frustrated Lewis pairs (FLPs) in the context of heterolytic cleavage of H 2 by transition metal complexes, with an emphasis on molecular complexes bearing an intramolecular Lewis base. FLPs have traditionally been associated with main group compounds, yet many reactions of transition metal complexes support a broader classification of FLPs that includes certain types of transition metal complexes with reactivity resembling main group-based FLPs. This article surveys transition metal complexes that heterolytically cleave H 2 , which vary in the degree that the Lewis pairs within these systems interact. Many of the examples include complexes bearing a pendant amine functioning as the base with the metal functioning as the hydride acceptor. Consideration of transition metal compounds in the context of FLPs can inspire new innovations and improvements in transition metal catalysis.This article is part of the themed issue 'Frustrated Lewis pair chemistry'. © 2017 The Author(s).

  14. Effect of heptadentate (N{sub 4}O{sub 3}) tripodal Schiff base ligand and its yttrium(III) complex on the luminescence and extraction of tris({beta}-diketonato)europium(III)

    Energy Technology Data Exchange (ETDEWEB)

    Hasegawa, Y. [Department of Chemistry, Faculty of Science, Science University of Tokyo, Tokyo 162-8601 (Japan)], E-mail: yhasegaw@rs.kagu.tus.ac.jp; Saitou, S.; Nagaoka, D.; Yajima, H. [Department of Chemistry, Faculty of Science, Science University of Tokyo, Tokyo 162-8601 (Japan); Kanesato, M. [National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8562 (Japan)

    2008-02-28

    In order to learn the effect of a Schiff base and the complex of Y{sup III} on the extraction of Eu{sup III} with {beta}-diketones and on the luminescence of the extracted species, the extraction of Eu{sup III} with 2-thenoyltrifluoroacetone (Htta) and/or these Schiff bases, tris(5-t-butyl)salicylidenaminoethyl amine (H{sub 3}L{sup 1}), and its Y{sup III} complex ([YL{sup 1}]) prepared, into CHCl{sub 3} was examined. Further, the luminescence and excited spectra of CHCl{sub 3} phases extracted Eu{sup III} complexes and the solutions containing tris({beta}-diketonato)Eu{sup III} and/or the Schiff bases were measured. On the measurement of the luminescence spectra, tris(pivaloyltrifluoroacetonato)Eu{sup III} (Eu(pta){sub 3}) as well as Eu(tta){sub 3} was used. Synergistic effect with Htta and these Schiff bases was observed. However, proper effect of Y{sup III} was not observed. The luminescence intensity of Eu(tta){sub 3} at 613 nm decreased with increasing concentration of H{sub 3}L{sup 1} or [YL{sup 1}], whereas that of Eu(pta){sub 3} increased with increasing concentration of the ligands, but no difference between both Schiff bases was observed, because of picking up of Y{sup III} from [YL{sup 1}] with the interaction between [YL{sup 1}] and water.

  15. Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

    Energy Technology Data Exchange (ETDEWEB)

    Steinberg, Simon; Zimmermann, Sina; Brühmann, Matthias; Meyer, Eva; Rustige, Christian; Wolberg, Marike; Daub, Kathrin; Bell, Thomas; Meyer, Gerd, E-mail: gerd.meyer@uni-koeln.de

    2014-11-15

    Comproportionation reactions of rare-earth metal trihalides (RX{sub 3}) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ((T{sub 3}R{sub 11})X{sub 15}-type, P6{sub 3}/m), tetramers ((T{sub 4}R{sub 16})X{sub 28}(R{sub 4}) (P-43m), (T{sub 4}R{sub 16})X{sub 20} (P4{sub 2}/nnm), (T{sub 4}R{sub 16})X{sub 24}(RX{sub 3}){sub 4} (I4{sub 1}/a) and (T{sub 4}R{sub 16})X{sub 23} (C2/m) types of structure) and pentamers ((Ru{sub 5}La{sub 14}){sub 2}Br{sub 39}, Cc) of (TR{sub r}){sub n} (n=2–5) clusters. These oligomers are further enveloped by inner (X{sup i}) as well as outer (X{sup a}) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of (TR{sub 6}) octahedra via common edges are more frequent than trimers and pentamers, in which the (TR{sub r}) clusters share common faces. - Graphical abstract: Rare earth-metal cluster complexes with endohedral transition metal atoms (TR{sub 6}) may connect via common edges or faces to form dimers, trimers, tetramers and pentamers of which the tetramers are the most prolific. Packing effects and electron counts play an important role. - Highlights: • Rare-earth metal cluster complexes encapsulate transition metal atoms. • Oligomers are built via connection of octahedral clusters via common edges or faces. • Dimers through pentamers with closed structures are known. • Tetramers including a tetrahedron of endohedral atoms are the most prolific.

  16. Regioselective aromatic substitution reactions of cyclometalated Ir(III) complexes: synthesis and photochemical properties of substituted Ir(III) complexes that exhibit blue, green, and red color luminescence emission.

    Science.gov (United States)

    Aoki, Shin; Matsuo, Yasuki; Ogura, Shiori; Ohwada, Hiroki; Hisamatsu, Yosuke; Moromizato, Shinsuke; Shiro, Motoo; Kitamura, Masanori

    2011-02-07

    In this manuscript, the regioselective halogenation, nitration, formylation, and acylation of Ir(tpy)(3) and Ir(ppy)(3) (tpy = 2-(4'-tolyl)pyridine and ppy = 2-phenylpyridine) and the subsequent conversions are described. During attempted bromination of the three methyl groups in fac-Ir(tpy)(3) using N-bromosuccinimide (NBS) and benzoyl peroxide (BPO), three protons at the 5'-position (p-position with respect to the C-Ir bond) of phenyl rings in tpy units were substituted by Br, as confirmed by (1)H NMR spectra, mass spectra, and X-ray crystal structure analysis. It is suggested that such substitution reactions of Ir complexes proceed via an ionic mechanism rather than a radical mechanism. UV-vis and luminescence spectra of the substituted Ir(III) complexes are reported. The introduction of electron-withdrawing groups such as CN and CHO groups at the 5'-position of tpy induces a blue shift of luminescence emission to about 480 nm, and the introduction of electron-donating groups such as an amino group results in a red shift to about 600 nm. A reversible change of emission for the 5'-amino derivative of Ir(tpy)(3), Ir(atpy)(3), between red and green occurs upon protonation and deprotonation.

  17. Structural and thermal characterization of ternary complexes of piroxicam and alanine with transition metals: Uranyl binary and ternary complexes of piroxicam. Spectroscopic characterization and properties of metal complexes

    Science.gov (United States)

    Mohamed, Gehad G.

    2005-12-01

    Ternary Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and UO 2(II) complexes with piroxicam (Pir) drug (H 2L 1) and dl-alanine (Ala) (HL 2) and also the binary UO 2(II) complex with Pir were studied. The structures of the complexes were elucidated using elemental, IR, molar conductance, magnetic moment, diffused reflectance and thermal analyses. The UO 2(II) binary complex was isolated in 1:2 ratio with the formula [UO 2(H 2L) 2](NO 3) 2. The ternary complexes were isolated in 1:1:1 (M:H 2L 1:L 2) ratios. The solid complexes were isolated in the general formulae [M(H 2L)(L 2)(Cl) n(H 2O) m]· yH 2O (M = Fe(III) ( n = 2, m = 0, y = 1), Co(II) ( n = 1, m = 1, y = 2) and Ni(II) ( n = 1, m = 1, y = 0)); [M(H 2L)(L 2)](X) z· yH 2O (M = Cu(II) (X = AcO, z = 1, y = 0), Zn(II) (X = AcO, z = 1, y = 3) and UO 2(II) (X = NO 3, z = 1, y = 2)). Pir behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine-N and carbonyl-O groups, while Ala behaves as a uninegatively bidentate ligand coordinated to the metal ions via the deprotonated carboxylate-O and amino-N. The magnetic and reflectance spectral data show that the complexes have octahedral geometry except Cu(II) and Zn(II) complexes have tetrahedral structures. The thermal decomposition of the complexes was discussed in relation to structure, and the thermodynamic parameters of the decomposition stages were evaluated.

  18. Neutron diffraction studies of transition metal hydride complexes

    International Nuclear Information System (INIS)

    Koetzle, T.F.; Bau, R.

    1976-01-01

    Investigations of H 3 Ta(C 5 H 5 ) 2 (III), HW 2 (CO) 9 (NO) (IV), and HW 2 (CO) 8 (NO) (P(OCH 3 ) 3 ) (V) have been completed. Preliminary results are available for HFeCo 3 (CO) 9 [P(OCH 3 ) 3 ] 3 (VII). This work, together with studies of HMo 2 (C 5 H 5 ) 2 (CO) 4 (P(CH 3 ) 2 ) (VI) and [(C 2 H 5 ) 4 N] + [HCr 2 (CO) 10 ] - carried out at Argonne has led to some general observations on the geometry and the nature of bonding in these compounds. For example, in the structures of IV and V, both of which have bent W--H--W linkages (less than W--H--W in the range 125-130 0 ), there is conclusive evidence for the existence of a closed three-center W--H--W bond with significant metal-metal interaction. Such is the case, because extensions of the axial W--C and W--N bonds trans to the hydride intersect at a point near the center of the W--H--W triangle. The geometry of VI, which also contains a bent M--H--M bond, is consistent with that of IV and V. Bridging M--H bonds in these second- and third-row hydrides range in length from 1.85 to 1.89 A, compared to 1.75 A in the first-row polynuclear complex VII. For metals of corresponding rows, bridging M--H bonds are about 0.1 A longer than terminal bonds, which are classified as single covalent bonds

  19. Energetic Surface Smoothing of Complex Metal-Oxide Thin Films

    International Nuclear Information System (INIS)

    Willmott, P.R.; Herger, R.; Schlepuetz, C.M.; Martoccia, D.; Patterson, B.D.

    2006-01-01

    A novel energetic smoothing mechanism in the growth of complex metal-oxide thin films is reported from in situ kinetic studies of pulsed laser deposition of La 1-x Sr x MnO 3 on SrTiO 3 , using x-ray reflectivity. Below 50% monolayer coverage, prompt insertion of energetic impinging species into small-diameter islands causes them to break up to form daughter islands. This smoothing mechanism therefore inhibits the formation of large-diameter 2D islands and the seeding of 3D growth. Above 50% coverage, islands begin to coalesce and their breakup is thereby suppressed. The energy of the incident flux is instead rechanneled into enhanced surface diffusion, which leads to an increase in the effective surface temperature of ΔT≅500 K. These results have important implications on optimal conditions for nanoscale device fabrication using these materials

  20. Derivatized Pentadentate Macrocyclic Ligands and Their Transition Metal Complexes

    Directory of Open Access Journals (Sweden)

    Muhammad S. Khan

    2002-06-01

    Full Text Available The reaction of the pendant hydroxyethyl group in the planar pentadentate macrocyclic ligand,1,11-bis(2’-hydroxyethyl-4,8;12,16;17,21-trinitrilo-1,2,10,11-tetraazacyclohenicosa- 2,4,6,9,12,14,18,20-octaene (L2, derived from the condensation of 2,6-pyridinedialdehyde with 6,6’-bis(2’ hydroxyethylhydrazino -2,2’-bipyridine (L1, has been investigated. Esterification reactions are facile, and the reaction of the hydroxyethyl-substituted macrocycle with thionyl chloride yields a chloroethyl derivative. Metal complexes of the new derivatized macrocyclic ligands L3-6having general formula ML3-6X2.nH2O (M = Mn, Fe, Co, Ni, Cu, Zn are readily prepared.

  1. Electron spin resonance of radicals and metal complexes

    International Nuclear Information System (INIS)

    1993-01-01

    The materials are a collection of extended synopsis of papers presented at the conference sessions. The broad area of magnetic techniques applications has been described as well as their spectra interpretation methods. The ESR, NMR, ENDOR and spin echo were applied for studying the radiation and UV induced radicals in chemical and biological systems. Also in the study of complexes of metallic ions (having the paramagnetic properties) and their interaction with the matrix, the magnetic techniques has been commonly used. They are also very convenient tool for the study of reaction kinetics and mechanism as well as interaction of paramagnetic species with themselves and crystal lattice or with the surface as for thee catalytic processes

  2. Friction and solid-solid adhesion on complex metallic alloys

    Science.gov (United States)

    Dubois, Jean-Marie; Belin-Ferré, Esther

    2014-01-01

    The discovery in 1987 of stable quasicrystals in the Al–Cu–Fe system was soon exploited to patent specific coatings that showed reduced friction in ambient air against hard antagonists. Henceforth, it was possible to develop a number of applications, potential or commercially exploited to date, that will be alluded to in this topical review. A deeper understanding of the characteristics of complex metallic alloys (CMAs) may explain why material made of metals like Al, Cu and Fe offers reduced friction; low solid–solid adhesion came later. It is linked to the surface energy being significantly lower on those materials, in which translational symmetry has become a weak property, that is determined by the depth of the pseudo-gap at the Fermi energy. As a result, friction is anisotropic in CMAs that builds up according to the translation symmetry along one direction, but is aperiodic along the other two directions. A review is given in this article of the most salient data found along these lines during the past two decades or so. PMID:27877675

  3. Magnetic, thermal and luminescence properties in room-temperature nanosecond electron-irradiated various metal oxide nanopowders

    Science.gov (United States)

    Sokovnin, S. Yu; Balezin, M. E.; Il’ves, V. G.

    2018-03-01

    By means of pulsed electron beam evaporation in vacuum of targets non-magnetic, in bulk state, Al2O3 and YSZ (ZrO2-8% Y2O3) oxides, magnetic nanopowders (NPs) with a high specific surface were produced. The NPs were subsequently irradiated in air by electrons with energy of 700 keV, using a URT-1 accelerator for 15 and 30 minutes. The magnetic, thermal, and pulsed cathodoluminescence (PCL) characteristics of NPs were measured before and after irradiation. It was established that the electron irradiation non-monotonically changes the magnetization of the pristine samples. To the contrary, a clear correlation between the intensity of PCL and the irradiation doses is found in the oxides. There was a decrease in the intensity of PCL after irradiation. Luminescent and thermal properties reflect the transformation of structural defects in NPs more strongly after the exposure to a pulsed electron beam in comparison with corresponding changes of the NPs magnetic response.

  4. Thiocyanate cadmium(II) complexes of 2,4,6-tri(2-pyridyl)-1,3,5-triazine – Synthesis, structure and luminescence properties

    International Nuclear Information System (INIS)

    Nawrot, I.; Machura, B.; Kruszynski, R.

    2014-01-01

    Two new thiocyanate cadmium(II) complexes of 2,4,6-tri(2-pyridyl)-1,3,5-triazine were synthesized and characterized. The resulted complexes [Cd(SCN)(NO 3 )(tptz)(H 2 O)] (1) and [Cd(SCN) 2 (tptz)(MeOH)] (2) were studied by IR, UV–vis spectroscopy and single crystal X-ray analysis. The luminescent properties of 1 and 2 were studied in solution and solid state and compared with the free ligand. To get detailed insight into the electronic structure and spectroscopic properties of [Cd(SCN)(NO 3 )(tptz)(H 2 O)] and [Cd(SCN) 2 (tptz)(MeOH)], the density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed. - Highlights: • Two novel thiocyanate cadmium(II) compounds of 2,4,6-tri(2-pyridyl)-1,3,5-triazine were synthesized. • The compounds were identified by IR, UV–vis spectroscopy and X-ray analysis. • The fluorescence properties of the complexes were examined and compared with the free ligand. • The electronic spectra were investigated at the TD-DFT level employing B3LYP/LANL2DZ

  5. Enhanced fluorescence of Tb(III), Dy(III) perchlorate by salicylic acid in bis(benzoylmethyl) sulfoxide complexes and luminescence mechanism

    International Nuclear Information System (INIS)

    Li Wenxian; Zheng Yushan; Sun Xiaojun; Chai Wenjuan; Ren Tie; Shi Xiaoyan

    2010-01-01

    Two novel ternary rare earth perchlorate complexes had been synthesized by using bis(benzoylmethyl) sulfoxide as first ligand (L=C 6 H 5 COCH 2 SOCH 2 COC 6 H 5 ), salicylic acid as second ligand (L ' =C 6 H 4 OHCOO - ). The compounds were characterized by elemental analysis, TG-DSC and molar conductivities in DMF solution. The composition was suggested as [REL 5 L'](ClO 4 ) 2 .nH 2 O (RE=Tb, Dy; n=6, 8 ). Based on IR, 1 HNMR and UV spectra, it showed that the first ligand, bis(benzoylmethyl) sulfoxide (L), bonded with Tb(III), Dy(III) ions by the oxygen atom of sulfinyl group. The second ligand, salicylic acid group (L'), not only bonded with RE(III) ions by one oxygen atom of carboxyl group but also bonded with RE(III) ions by oxygen atom of phenolic hydroxyl group. In bis(benzoylmethyl) sulfoxide system, fluorescent spectra of the complexes showed that the luminescence of Tb(III), Dy(III) ions was enhanced by the second ligand salicylic acid. The ternary complexes had stronger fluorescence than the binary ones where only bis(benzoylmethyl) sulfoxide acted as ligand. Phosphorescent spectra of the two ligands indicated that the coordination of salicylic acid resulted in the matching extent increasing between the triplet state of ligand and excited state of the rare earths. The relationship between fluorescence lifetime and fluorescence intensity was also discussed.

  6. A detailed in vitro study of naproxen metal complexes in quest of ...

    African Journals Online (AJOL)

    Md. Sharif Hasan

    2016-07-01

    Jul 1, 2016 ... possibilities of using Naproxen metal complexes for different therapeutic ..... FTIR spectra, scanning electron microscopy and HPLC study of Naproxen metal ..... aminobenzoic acid and 2-aminophenol and their coordination.

  7. Multifunctional material based on ionic transition metal complexes and gold-silica nanoparticles: synthesis and photophysical characterization for application in imaging and therapy.

    Science.gov (United States)

    Ricciardi, Loredana; Martini, Matteo; Tillement, Olivier; Sancey, Lucie; Perriat, Pascal; Ghedini, Mauro; Szerb, Elisabeta I; Yadav, Yogesh J; La Deda, Massimo

    2014-11-01

    A new combination of luminescent ionic transition-metal complexes (M = Ru(II) or Ir(III)) with gold silica-based nanoparticles (GSNPs) gives a promising nanomaterial for application in biomedical fields. Herein we report the synthesis and the photophysical properties of Ru(II) and Ir(III) complexes doped gold core-polysiloxane shell particles prepared by microemulsion method and characterized by Transmission Electron Microscopy, Dynamic Light Scattering and UV-Vis spectroscopy. The cytotoxicity and photodynamic activity of the obtained 50 nm-diameter nanoparticles were evaluated in vitro, providing noteworthy results. Furthermore, their intrinsic phosphorescence allows the localization of the photosensitizing nanoparticles into the cytosol of tumor cells by fluorescence confocal microscope. These valuable features designate them as multifunctional nanoplatforms for theranostic purposes.

  8. Stimulated X-Ray Emission Spectroscopy in Transition Metal Complexes

    Science.gov (United States)

    Kroll, Thomas; Weninger, Clemens; Alonso-Mori, Roberto; Sokaras, Dimosthenis; Zhu, Diling; Mercadier, Laurent; Majety, Vinay P.; Marinelli, Agostino; Lutman, Alberto; Guetg, Marc W.; Decker, Franz-Josef; Boutet, Sébastien; Aquila, Andy; Koglin, Jason; Koralek, Jake; DePonte, Daniel P.; Kern, Jan; Fuller, Franklin D.; Pastor, Ernest; Fransson, Thomas; Zhang, Yu; Yano, Junko; Yachandra, Vittal K.; Rohringer, Nina; Bergmann, Uwe

    2018-03-01

    We report the observation and analysis of the gain curve of amplified K α x-ray emission from solutions of Mn(II) and Mn(VII) complexes using an x-ray free electron laser to create the 1 s core-hole population inversion. We find spectra at amplification levels extending over 4 orders of magnitude until saturation. We observe bandwidths below the Mn 1 s core-hole lifetime broadening in the onset of the stimulated emission. In the exponential amplification regime the resolution corrected spectral width of ˜1.7 eV FWHM is constant over 3 orders of magnitude, pointing to the buildup of transform limited pulses of ˜1 fs duration. Driving the amplification into saturation leads to broadening and a shift of the line. Importantly, the chemical sensitivity of the stimulated x-ray emission to the Mn oxidation state is preserved at power densities of ˜1020 W /cm2 for the incoming x-ray pulses. Differences in signal sensitivity and spectral information compared to conventional (spontaneous) x-ray emission spectroscopy are discussed. Our findings build a baseline for nonlinear x-ray spectroscopy for a wide range of transition metal complexes in inorganic chemistry, catalysis, and materials science.

  9. Interaction of Cr (III), Ni (II), Pb (II) with DTPA complexes of essential metal ions

    International Nuclear Information System (INIS)

    Gulzar, S.; Zahida; Maqsood, T.; Naqvi, R.R.

    2002-01-01

    With the increase of anthropogenic activities in the environment, heavy metal toxicity (Chromium, Nickel and Lead) is more common now. DTPA (diethylene triamine pentaacetic acid) a polyamino carboxylic acid is widely used to form hydrophilic and stable complexes with most of the metal ions. In this spectrophotometric study, concentration of Cr(III), Ni(II) and Pb(II) (toxic metal ions) exchanged with Fe(III), Zn(II) and Ca(II) from their DTPA complexes were estimated at pH 4,7 and 9. Concentration of added metal was varied from 1-4 times to that of complexed metal. (author)

  10. Luminescent screens

    International Nuclear Information System (INIS)

    Lu, C.-I.

    1982-01-01

    Luminescent screens which are useful for such purposes as intensifying screens for radiographs are comprised of a support bearing a layer of finely divided particles of a phosphor dispersed in a cross-linked polymeric matrix formed by heat-curing of a coating composition comprising an unsaturated cross-linkable polymer, a polymerizable acrylic monomer, a thermoplastic polyurethane elastomer, and a heat-activatable polymerization initiator. The phosphor layer includes voids formed by evaporation of an evaporable component which is present in the coating composition from which such layer is formed. (author)

  11. Direct synthesis of metal complexes starting from zero-valent metals

    Energy Technology Data Exchange (ETDEWEB)

    Gojon-Zorrilla, Gabriel; Kharisov, Boris I. [Universidad Autonoma de Nuevo Leon, Monterrey, Nuevo Leon (Mexico); Garnovskii, Alexander D. [Institute of Physical and Organic Chemistry (Russian Federation)

    1996-06-01

    The recent (1980-1994) literature on metal-vapor synthesis of coordination and organometallic compounds is reviewed. An account is given of the high-and low-temperature reactions between free metal atoms and a large variety of substrates, mainly alkenes, alkynes, dienes, arenes, funtionalized arenes, alkyl halides {beta}-diketones and simple inorganic molecules. The main experimental methods are described, as well as the results obtained thereby. It is shown that in many instances these methods present significant advantages over conventional synthetic procedures, offering unique access to some metal complexes. [Spanish] Se reviso la literatura reciente (1980-1994) sobre la sintesis de compuestos de coordinacion y compuestos organometalicos a partir de vapores metalicos. Se examinan las reacciones de los atomos metalicos libres con una gran variedad de substratos, principalmente alquenos, alquinos, dienos, hidrocarburos aromaticos y sus derivados, haluros de alquilo y arilo, {beta}-dicetonas y moleculas inorganicas simples. Se presentan los principales metodos experimentales, asi como los resultados obtenidos; se concluye que la crisintesis presenta en muchos casos ventajas significativas sobre los procedimientos sinteticos tradicionales, constituyendo frecuentemente la unica opcion disponible.

  12. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Du, Guodong [Iowa State Univ., Ames, IA (United States)

    2003-01-01

    -, bis-alkoxo, and chelating diolato complexes, depending on the identity of diols and the stoichiometry employed. It was also found that tin porphyrin complexes promoted the oxidative cleavage of vicinal diols and the oxidation of α-ketols to α-diketones with dioxygen. In extending the chemistry of metalloporphyrins and analogous complexes, a series of chiral tetraaza macrocyclic ligands and metal complexes were designed and synthesized. Examination of iron(II) complexes showed that they were efficient catalysts for the cyclopropanation of styrene by diazo reagents. Good yields and high diastereoselectivity were obtained with modest enantioselectivity. A rationalization of the stereoselectivity was presented on the basis of structural factors in a carbene intermediate.

  13. Luminescent Oxygen Gas Sensors Based on Nanometer-Thick Hybrid Films of Iridium Complexes and Clay Minerals

    Directory of Open Access Journals (Sweden)

    Hisako Sato

    2014-01-01

    Full Text Available The use of Ir(III complexes in photo-responsive molecular devices for oxygen gas sensing is reviewed. Attention is focused on the immobilization of Ir(III complexes in organic or inorganic host materials such as polymers, silica and clays in order to enhance robustness and reliability. Our recent works on constructing nanometer-thick films comprised of cyclometalated cationic Ir(III complexes and clay minerals are described. The achievement of multi-emitting properties in response to oxygen pressure is demonstrated.

  14. Luminescence enhancement of uranyl ion by benzoic acid in acetonitrile

    International Nuclear Information System (INIS)

    Satendra Kumar; Maji, S.; Joseph, M.; Sankaran, K.

    2014-01-01

    Uranyl ion is known for its characteristic green luminescence and therefore luminescence spectroscopy is a suitable technique for characterizing different uranyl species. In aqueous medium, luminescence of uranyl ion is generally weak due to its quenching by water molecules and therefore in order to enhance the luminescence of uranyl ion in aqueous medium, luminescence enhancing reagents such as H 3 PO 4 , H 2 SO 4 , HCIO 4 have been widely used. The other method to enhance the uranyl luminescence is by ligand sensitized luminescence, a method well established for lanthanides. In this work, luminescence of uranyl ion is found to be enhanced by benzoic acid in acetonitrile medium. In aqueous medium benzoic acid does not enhance the uranyl luminescence although it forms 1:1 and 1:2 complexes with uranyl ion. Luminescence spectra of uranyl benzoate revealed that enhancement is due to sensitization of uranyl luminescence by benzoate ions. UV-Vis spectroscopy has been utilized to characterize the specie formed in the in acetonitrile medium. UV-Vis spectroscopy along with luminescence spectra revealed that the specie to be tribenzoate complex of uranyl (UO 2 (C 6 H 5 COO) 3 ) - having D 3 h symmetry. (author)

  15. Synthesis and Crystal Structures of Luminescent Mononuclear Ni(ii and Cd(ii Complexes with 1,10-phenanthroline

    Directory of Open Access Journals (Sweden)

    Ecaterina Tocana

    2017-12-01

    Full Text Available New supramolecular systems of Ni(II and Cd(II with 1,10-phenanthroline constructed by non-covalent interactions have been synthesized and characterized by single-crystal X-ray diffractometry. The smaller nickel(II ion forms a cis complex with outer-sphere perchlorates, while the cadmium(II ion forms a trans complex involving inner-sphere perchlorates. Both compoundsrevealintraligand-basedluminescentproperties.

  16. Hydrothermal synthesis, crystal structure, luminescent and magnetic properties of a new mononuclear GdIII coordination complex

    Science.gov (United States)

    Coban, Mustafa Burak

    2018-06-01

    A new GdIII coordination complex, {[Gd(2-stp)2(H2O)6].2(4,4'-bipy).4(H2O)}, complex 1, (2-stp = 2-sulfoterephthalate anion and 4,4'-bipy = 4,4'-bipyridine), has been synthesized by hydrothermal method and characterized by elemental analysis, solid state UV-Vis and FT-IR spectroscopy, single-crystal X-ray diffraction, solid state photoluminescence and variable-temperature magnetic measurements. The crystal structure determination shows that GdIII ions are eight coordinated and adopt a distorted square-antiprismatic geometry. Molecules interacting through intra- and intermolecular (O-H⋯O, O-H⋯N) hydrogen bonds in complex 1, give rise to 3D hydrogen bonded structure and the discrete lattice 4,4'-bipy molecules occupy the channel of the 3D structure. π-π stacking interactions also exist 4,4'-bipy-4,4'-bipy and 4,4'-bipy-2-stp molecule rings in 3D structures. Additionally, solid state photoluminescence properties of complex 1 at room temperature have been investigated. Under the excitation of UV light (at 349 nm), the complex 1 exhibited green emissions (at 505 nm) of GdIII ion in the visible region. Furthermore, Variable-temperature magnetic susceptibility and isothermal magnetization as function of external magnetic field studies reveal that complex 1 displays possible antiferromagnetic interaction.

  17. Synthesis, characterization, anti-microbial, DNA binding and cleavage studies of Schiff base metal complexes

    Directory of Open Access Journals (Sweden)

    Poomalai Jayaseelan

    2016-09-01

    Full Text Available A novel Schiff base ligand has been prepared by the condensation between butanedione monoxime with 3,3′-diaminobenzidine. The ligand and metal complexes have been characterized by elemental analysis, UV, IR, 1H NMR, conductivity measurements, EPR and magnetic studies. The molar conductance studies of Cu(II, Ni(II, Co(II and Mn(II complexes showed non-electrolyte in nature. The ligand acts as dibasic with two N4-tetradentate sites and can coordinate with two metal ions to form binuclear complexes. The spectroscopic data of metal complexes indicated that the metal ions are complexed with azomethine nitrogen and oxyimino nitrogen atoms. The binuclear metal complexes exhibit octahedral arrangements. DNA binding properties of copper(II metal complex have been investigated by electronic absorption spectroscopy. Results suggest that the copper(II complex bind to DNA via an intercalation binding mode. The nucleolytic cleavage activities of the ligand and their complexes were assayed on CT-DNA using gel electrophoresis in the presence and absence of H2O2. The ligand showed increased nuclease activity when administered as copper complex and copper(II complex behave as efficient chemical nucleases with hydrogen peroxide activation. The anti-microbial activities and thermal studies have also been studied. In anti-microbial activity all complexes showed good anti-microbial activity higher than ligand against gram positive, gram negative bacteria and fungi.

  18. Luminescence properties of uranyl-acetate species

    Energy Technology Data Exchange (ETDEWEB)

    Brinkmann, Hannes; Moll, Henry [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. of Resource Ecology; Stumpf, Thorsten [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry

    2017-06-01

    Time-resolved laser-induced fluorescence spectroscopy (TRLFS) was applied to characterize uranium(VI)- acetate species based on their luminescence properties. In contrast to previous interpretations, no indications were detected for the existence of the 1: 3 complex.

  19. Synthesis, crystal structure, theoretical study and luminescence ...

    Indian Academy of Sciences (India)

    and Material Engineering, Jiangnan University, Wuxi 214122, P. R. China. cChina-Australia Joint ... School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, P. R. China e-mail: ..... The title complex is luminescent.

  20. Hydrogen storage in metal hydrides and complex hydrides; Wasserstoffspeicherung in Metall- und komplexen Hydriden - Schlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Bielmann, M.; Zuettel, A.

    2007-07-01

    This final report for the Swiss Federal Office of Energy (SFOE), reports on work done in 2007 at the Swiss Federal Laboratories for Materials Science and Technology EMPA on the storage of hydrogen in metal hydrides and complex hydrides. In particular, the use of tetrahydroborates is noted. The potential of this class of materials is stressed. The structures at room-temperature were examined using neutron and X-ray diffraction methods. Thermodynamic methods helped determine the thermodynamic stability of the materials. Also, a complete energy diagram for the materials was developed. The use of silicon oxide to reduce activation energy and its catalytic effects are discussed. The challenges placed by desorption mechanisms are noted. The authors note that reversibility is basically proven.

  1. Studies on Oligomer Metal Complexes Derived from Bisamic Acid of Pyromellitic Dianhydride and 4-Bromoaniline.

    Science.gov (United States)

    Patel, Yogesh S

    2014-01-01

    Novel oligomer metal complexes (2a-f) of the ligand 2,5-bis((4-bromophenyl)carbamoyl) terephthalic acid (1) were prepared using transition metal salts and characterized by various spectroscopic techniques. The geometry of oligomer metal complexes was carried out by electronic spectral analysis and magnetic measurement studies. Polymeric properties have also been carried out. Ligand was synthesized using pyromellitic dianhydride and 4-bromoaniline. It was duly characterized. All novel synthesized compounds 1 and 2a-f were evaluated for their antibacterial and antifungal activity. The results showed significantly higher antibacterial and antifungal activity of oligomer metal complexes compared to the ligand.

  2. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    Energy Technology Data Exchange (ETDEWEB)

    Peresypkina, Eugenia V. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Samsonenko, Denis G. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Vostrikova, Kira E., E-mail: vosk@niic.nsc.ru [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); LMI, Université Claude Bernard Lyon 1, 69622 Villeurbanne Cedex (France)

    2015-04-15

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  3. On the possibility of removing of transition metal ions from sewage using polymeric complexes

    International Nuclear Information System (INIS)

    Tazhibaeva, S.M.; Abilov, Zh.A.; Musabekov, K.V.

    1997-01-01

    The possibility of using of complexation in the system polyethylene-imine transition metal ions (Cu 2+ , Ni 2+ , Co 2+ )-surface active substance for removing of metal ions from solution and sewage has been investigated. It is shown, that pH of medium, hydro-fugitive of system and ratio between component of the triply complex effect on purification of solution. (author)

  4. Complexation with dissolved organic matter and solubility control of heavy metals in sandy soil

    NARCIS (Netherlands)

    Weng, L.; Temminghoff, E.J.M.; Lofts, S.; Tipping, E.; Riemsdijk, van W.H.

    2002-01-01

    The complexation of heavy metals with dissolved organic matter (DOM) in the environment influences the solubility and mobility of these metals. In this paper, we measured the complexation of Cu, Cd, Zn, Ni, and Pb with DOM in the soil solution at pH 3.7-6.1 using a Donnan membrane technique. The

  5. Reactivity of olefin and allyl ligands in π-complexes of metals

    International Nuclear Information System (INIS)

    Kukushkin, Yu.N.

    1987-01-01

    The data on reactivity of olefin and allyl ligands in transition metal (Ru, W) π-complexes, published up to 1984 are presented. Metal ion coordination of olefins causes their appreciable reactivity change. Transformations of π-olefin ligands into σ-alkyl ones, interaction of π-complexes with oxygen nucleophilic reagents, amines, halogenides and pseudohalogenides are considered

  6. A series of luminescent Re(I) complexes with electron-donor/acceptor moieties: Synthesis, characterization, and photoluminescence

    International Nuclear Information System (INIS)

    Ge Hu; Qing She; Lei Guo

    2012-01-01

    In this paper, we synthesize three Re(I) complexes of Re(CO) 3 (PPO)Br, Re(CO) 3 (PTO)Br, and Re(CO) 3 (PBI)Br, where PPO=2-phenyl-5-(pyridin-2-yl)-1,3,4-oxadiazole, PTO=2-(pyridin-2-yl)-5-p-tolyl-1,3,4-oxadiazole, PBI=2-(pyridin-2-yl)-1H-benzo[d]imidazole. Their single crystals and photophysical properties are measured and discussed in detail. The correlation between ligand structure and corresponding PL characteristics of Re(I) complex has been investigated. It is found that a ligand with strong electron-donor can efficiently increase both absorption and emissive energy of Re(I) complex. In addition, electron-rich ligand can increase the electron density of the complex and thus enhance the oscillator strength of electronic transition, improving the photoluminescence performance. - Highlights: ► Three novel phosphorescent Re(I) complexes are synthesized. ► Molecular structures, photophysical, and electronic properties are studied. ► Strong electron-donor can increase emissive energy. ► Electron-rich ligand can enhance the oscillator strength of electronic transition.

  7. Metallic complexes with glyphosate: a review; Complexos metalicos com o herbicida glifosato: revisao

    Energy Technology Data Exchange (ETDEWEB)

    Coutinho, Claudia F.B.; Mazo, Luiz Henrique [Sao Paulo Univ., Sao Carlos, SP (Brazil). Inst. de Quimica]. E-mail: claudiabreda@iqsc.usp.br

    2005-11-15

    We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature. (author)

  8. Studies on Oligomer Metal Complexes Derived from Bisamic Acid of Pyromellitic Dianhydride and 4-Bromoaniline

    OpenAIRE

    Patel, Yogesh S.

    2014-01-01

    Novel oligomer metal complexes (2a–f) of the ligand 2,5-bis((4-bromophenyl)carbamoyl) terephthalic acid (1) were prepared using transition metal salts and characterized by various spectroscopic techniques. The geometry of oligomer metal complexes was carried out by electronic spectral analysis and magnetic measurement studies. Polymeric properties have also been carried out. Ligand was synthesized using pyromellitic dianhydride and 4-bromoaniline. It was duly characterized. All novel synthesi...

  9. Highly specific ''sensing'' of tryptophan by a luminescent europium(III) complex

    Energy Technology Data Exchange (ETDEWEB)

    Stubenrauch, Jan A.; Mevissen, Christian; Schulte, Marie F.; Bochenek, Steffen; Albrecht, Markus [RWTH Univ. Aachen (Germany). Inst. fuer Organische Chemie; Subramanian, Palani S. [Central Salt and Marine Chemicals, Research Institute (CSRI), Gujarat (India)

    2016-07-01

    The europium(III) complex 1-Cl{sub 3} (S,S-2,2{sup '}-(((1,10-phenanthroline-2,9-diyl)bis(methanylylidene))bis (azanylyliden e))bis(3-methylbutanamide)europiumtrichloride) undergoes, only in the presence of the amino acid tryptophan, a change of emission at 615 nm. In the presence of few equivalents of tryptophan, emission of the europium complex is enhanced while it disappears upon addition of large amounts. This behavior can be assigned to displacement of the sensitizing phenanthroline ligand of 1-Cl{sub 2} x Trp in the latter case.

  10. Colour interceptions, thermal stability and surface morphology of polyester metal complexes

    International Nuclear Information System (INIS)

    Zohdy, M.H.

    2005-01-01

    Chelating copolymers via grafting of acrylic acid (AAc) and acrylamide (AAm/AAc) comonomer mixture onto polyester micro fiber fabrics (PETMF) using gamma-radiation technique were prepared. The prepared graft chains (PETMF-g-AAc) and (PETMF-g-PAAc/PAAm) acted as chelating sites for some selected transition metal ions. The prepared graft copolymers and their metal complexes were characterized using thermogravimetric analysis (TGA), colour parameters and surface morphology measurements. The colour interception and strength measurements showed that the metal complexation is homogeneously distributed. The results showed that the thermal stability of PETMF was improved after graft copolymerization and metal complexes. Moreover, the degree of grafting enhanced the thermal stability values of the grafted and complexed copolymers up to 25% of magnitude, on the other hand the activation energy of the grafted-copolymer with acrylic acid increased up to 80%. The SEM observation gives further supports to the homogenous distribution of grafting and metal complexation

  11. Conformational locking by design: relating strain energy with luminescence and stability in rigid metal-organic frameworks.

    Science.gov (United States)

    Shustova, Natalia B; Cozzolino, Anthony F; Dincă, Mircea

    2012-12-05

    Minimization of the torsional barrier for phenyl ring flipping in a metal-organic framework (MOF) based on the new ethynyl-extended octacarboxylate ligand H(8)TDPEPE leads to a fluorescent material with a near-dark state. Immobilization of the ligand in the rigid structure also unexpectedly causes significant strain. We used DFT calculations to estimate the ligand strain energies in our and all other topologically related materials and correlated these with empirical structural descriptors to derive general rules for trapping molecules in high-energy conformations within MOFs. These studies portend possible applications of MOFs for studying fundamental concepts related to conformational locking and its effects on molecular reactivity and chromophore photophysics.

  12. Synthesis, Crystal Structure, Luminescence, Electrochemical and Antimicrobial Properties of Bis(salamo-Based Co(II Complex

    Directory of Open Access Journals (Sweden)

    Li Wang

    2017-09-01

    Full Text Available A newly designed Co(II complex, [Co3(L(OAc2(CH3OH2]·CH3OH, by the reaction of a bis(salamo-type tetraoxime ligand (H4L with Co(II acetate tetrahydrate was synthesized and characterized by elemental analyses, IR, UV-vis spectra and single-crystal X-ray crystallography. The UV-vis titration experiment manifested that a trinuclear (L:M = 1:3 complex was formed. It is worth noting that the two terminal Co(II (Co1 and Co3 atoms of the Co(II complex have different coordination modes and geometries unreported earlier. Furthermore, through intermolecular interactions (C–H···O, C–H···π and O–H···O, a 2D layer-like network is constructed. In addition, the fluorescence behaviors, antimicrobial activities and electrochemical properties of H4L and its Co(II complex were investigated.

  13. On the capacity to the complexing of alkaline earth metal and magnesium chromates

    International Nuclear Information System (INIS)

    Orekhov, O.L.

    1978-01-01

    Considered is the capacity to the complexing of magnesium chromates and alkaline earth metal chromates with ammonium chromates in aqueous solutions. It has been established that the complexing of alkaline earth metal and magnesium chromates is effected by a nature of initial salts as well as their solubilities and the presence of crystallization water. Capacity of magnesium ions and alkaline rare earth metals to the complexing decreases in a series of Mg-Ca-Sr-Ba. Ca complexes exceed magnesium derivatives in respect of stability

  14. Speciation Studies of Some Toxic Metal Complexes of Glycylglycine ...

    African Journals Online (AJOL)

    NICO

    mixtures apart from its established utility in understanding ... Chemical speciation of metals is important for an understand- ... Titrations with differ- ent ratios (1:2.5, 1:3.5 and 1:5) of metal-ligand were performed with 0.4 mol L–1 sodium hydroxide solution. The mixtures obtained from PG and water are non-ideal due.

  15. X-ray luminescent glasses

    International Nuclear Information System (INIS)

    Takahashi, T.; Yamada, O.

    1981-01-01

    X-ray luminescent glasses comprising a divalent cation such as an alkaline earth metal or other divalent cations such as pb, cd, or zn, and certain rare earth metaphosphates are suitable as vitreous, x-ray phosphors or x-ray luminescent glass fibers in an x-ray intensifying screen. The glasses have the composition n(Mo X p2o5)((1-y)tb2o3 X yce2o3 X 3p2o5) wherein N is greater than zero but less than or equal to 16, M is an alkaline earth metal or other divalent cation such as pb, cd, or zn, and Y is greater than or equal to zero but less than one

  16. Printable luminescent down shifter for enhancing efficiency and stability of organic photovoltaics

    OpenAIRE

    Kettle, J.; Bristow, N.; Gethin, D.T.; Tehrani, Z.; Moudam, O.; Li, B.; Katz, E.A.; Benatto, Gisele Alves dos Reis; Krebs, Frederik C

    2016-01-01

    The proof of concept of using luminescent down shifting (LDS) layers as alternative UV filters for P3HT:PCBM OPVs is demonstrated using a lanthanide-based metal complex. The results are verified using a combination of indoor light soaking, with single cell devices, and outdoor performance monitoring, using a 16-cell monolithically connected OPV module. By applying the LDS layer, a ~5% relative enhancement in photocurrent is observed for both sets of devices. More significantly, indoor light s...

  17. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes

    Science.gov (United States)

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M. Arif

    2016-05-01

    We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica.

  18. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes.

    Science.gov (United States)

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M Arif

    2016-05-15

    We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. The dynamic behavior of thin-film ionic transition metal complex-based light-emitting electrochemical cells

    Energy Technology Data Exchange (ETDEWEB)

    Meier, Sebastian B., E-mail: sebastian.meier@belectric.com, E-mail: wiebke.sarfert@siemens.com [Department of Materials Science VI: Materials for Electronics and Energy Technology, Friedrich-Alexander-University of Erlangen-Nuremberg, 91058 Erlangen (Germany); Siemens AG, Corporate Technology, CT RTC MAT IEC-DE, 91058 Erlangen (Germany); Hartmann, David; Sarfert, Wiebke, E-mail: sebastian.meier@belectric.com, E-mail: wiebke.sarfert@siemens.com [Siemens AG, Corporate Technology, CT RTC MAT IEC-DE, 91058 Erlangen (Germany); Winnacker, Albrecht [Department of Materials Science VI: Materials for Electronics and Energy Technology, Friedrich-Alexander-University of Erlangen-Nuremberg, 91058 Erlangen (Germany)

    2014-09-14

    Light-emitting electrochemical cells (LECs) have received increasing attention during recent years due to their simple architecture, based on solely air-stabile materials, and ease of manufacture in ambient atmosphere, using solution-based technologies. The LEC's active layer offers semiconducting, luminescent as well as ionic functionality resulting in device physical processes fundamentally different as compared with organic light-emitting diodes. During operation, electrical double layers (EDLs) form at the electrode interfaces as a consequence of ion accumulation and electrochemical doping sets in leading to the in situ development of a light-emitting p-i-n junction. In this paper, we comment on the use of impedance spectroscopy in combination with complex nonlinear squares fitting to derive key information about the latter events in thin-film ionic transition metal complex-based light-emitting electrochemical cells based on the model compound bis-2-phenylpyridine 6-phenyl-2,2´-bipyridine iridium(III) hexafluoridophosphate ([Ir(ppy)₂(pbpy)][PF₆]). At operating voltages below the bandgap potential of the ionic complex used, we obtain the dielectric constant of the active layer, the conductivity of mobile ions, the transference numbers of electrons and ions, and the thickness of the EDLs, whereas the transient thickness of the p-i-n junction is determined at voltages above the bandgap potential. Most importantly, we find that charge transport is dominated by the ions when carrier injection from the electrodes is prohibited, that ion movement is limited by the presence of transverse internal interfaces and that the width of the intrinsic region constitutes almost 60% of the total active layer thickness in steady state at a low operating voltage.

  20. Multiheteromacrocycles that Complex Metal Ions. Sixth Progress Report, 1 May 1979-30 April 1980

    Science.gov (United States)

    Cram, D. J.

    1980-01-15

    Objective is to design synthesize, and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; number of binding sites; character of binding sites; and valences. During this period, hemispherands based on an aryloxy or cyclic urea unit, spherands based on aryloxyl units only, and their complexes with alkali metals and alkaline earths were investigated. An attempt to separate {sup 6}Li and {sup 7}Li by gel permeation chromatography of lithiospherium chloride failed. (DLC)

  1. Structure and catalytic properties of metal β-diketonate complexes with oxygen-containing compounds

    International Nuclear Information System (INIS)

    Nizel'skij, Yu.N.; Ishchenko, S.S.; Lipatova, T.Eh.

    1985-01-01

    The results of researches published in recent 15-20 years of complexes of metal β-diketonates (including Cr 3+ , VO 2+ , MoOΛ2 2+ , Co 3+ , Mn 3+ , Ni 2+ , Fe 3+ ) with oxygen-containing compounds (alcohols, glycols, phenols, hydroperoxides, aldehydes, esters, etc.) playing an important role in catalytic processes of oxidation, addition, polymerization and copolymerization are reviewed. Data on the nature of chemical bond of oxygen-containing reacting agents with metal β-diketonates, on structure of metal β-diketonate complexes with oxygen-containing reacting agents and thermodynamics of complexing as well as on activation of reacting agents in complexes and catalytic properties of metal β-diketonates are discussed. Stored materials make it possible to exercise directed control of metal β-diketonate activity

  2. Cooperative loading of multisite receptors with lanthanide containers: an approach for organized luminescent metallopolymers.

    Science.gov (United States)

    Babel, Lucille; Guénée, Laure; Besnard, Céline; Eliseeva, Svetlana V; Petoud, Stéphane; Piguet, Claude

    2018-01-14

    Metal-containing (bio)organic polymers are materials of continuously increasing importance for applications in energy storage and conversion, drug delivery, shape-memory items, supported catalysts, organic conductors and smart photonic devices. The embodiment of luminescent components provides a revolution in lighting and signaling with the ever-increasing development of polymeric light-emitting devices. Despite the unique properties expected from the introduction of optically and magnetically active lanthanides into organic polymers, the deficient control of the metal loading currently limits their design to empirical and poorly reproducible materials. We show here that the synthetic efforts required for producing soluble multi-site host systems L k are largely overcome by the virtue of reversible thermodynamics for mastering the metal loading with the help of only two parameters: (1) the affinity of the luminescent lanthanide container for a single binding site and (2) the cooperative effect which modulates the successive fixation of metallic units to adjacent sites. When unsymmetrical perfluorobenzene-trifluoroacetylacetonate co-ligands (pbta - ) are selected for balancing the charge of the trivalent lanthanide cations, Ln 3+ , in six-coordinate [Ln(pbta) 3 ] containers, the explored anti-cooperative complexation processes induce nearest-neighbor intermetallic interactions twice as large as thermal energy at room temperature ( RT = 2.5 kJ mol -1 ). These values have no precedent when using standard symmetrical containers and they pave the way for programming metal alternation in luminescent lanthanidopolymers.

  3. studies on transition metal complexes of herbicidal compounds. ii

    African Journals Online (AJOL)

    a

    derivative of 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, atrazine (ATZ) --- a well known herbicide has ... development while the other is the metal ion associated degradation or deactivation of the herbicides .... Colour M.p./decomp.

  4. Feldspar, Infrared Stimulated Luminescence

    DEFF Research Database (Denmark)

    Jain, Mayank

    2014-01-01

    This entry primarily concerns the characteristics and the origins of infrared-stimulated luminescence in feldspars.......This entry primarily concerns the characteristics and the origins of infrared-stimulated luminescence in feldspars....

  5. Preparation and characterisation of some transition metal complexes of niacinamide (vitamin b3)

    International Nuclear Information System (INIS)

    Hasan, M.M.; Hossain, M.E.; Halim, M.E.

    2015-01-01

    Niacinamide forms metal complexes of general formula (M(C/sub 6/H/sub 6/N/sub 2/O)2)Cl/sub 2/; where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) in the aqueous medium. The complexes were formulated by comparing the experimental and calculated data for C, H, N and metal. The prepared complexes were characterized by different physicochemical methods. The UV-vis, FTIR spectral analysis and thermo gravimetric analysis (TGA). TGA of these complexes have been discussed. Magnetic susceptibility values indicate that all complexes except Zn complex are paramagnetic in nature. The redox properties of the metal ions in the Mn, Cu and Zn complexes have been discussed from the cyclic voltammetric studies. In all cases the systems are quasi reversible. (author)

  6. Synthesis, Structures and Luminescence Properties of Metal-Organic Frameworks Based on Lithium-Lanthanide and Terephthalate

    Directory of Open Access Journals (Sweden)

    Mohammed S. M. Abdelbaky

    2016-03-01

    Full Text Available Metal-organic frameworks assembled from Ln(III, Li(I and rigid dicarboxylate ligand, formulated as [LiLn(BDC2(H2O·2(H2O] (MS1-6,7a and [LiTb(BDC2] (MS7b (Ln = Tb, Dy, Ho, Er, Yb, Y0.96Eu0.04, Y0.93Tb0.07, and H2BDC = terephthalic acid, were obtained under hydrothermal conditions. The isostructural MS1-6 crystallize in monoclinic P21/c space group. While, in the case of Tb3+ a mixture of at least two phases was obtained, the former one (MS7a and a new monoclinic C2/c phase (MS7b. All compounds have been studied by single-crystal and powder X-ray diffraction, thermal analyses (TGA, vibrational spectroscopy (FTIR, and scanning electron microscopy (SEM-EDX. The structures of MS1-6 and MS7a are built up of inorganic-organic hybrid chains. These chains constructed from unusual four-membered rings, are formed by edge- and vertex-shared {LnO8} and {LiO4} polyhedra through oxygen atoms O3 (vertex and O6-O7 (edge. Each chain is cross-linked to six neighboring chains through six terephthalate bridges. While, the structure of MS7b is constructed from double inorganic chains, and each chain is, in turn, related symmetrically to the adjacent one through the c glide plane. These chains are formed by infinitely alternating {LiO4} and {TbO8} polyhedra through (O2-O3 edges to create Tb–O–Li connectivity along the c-axis. Both MS1-6,7a and MS7b structures possess a 3D framework with 1D trigonal channels running along the a and c axes, containing water molecules and anhydrous, respectively. Topological studies revealed that MS1-6 and MS7a have a new 2-nodal 3,10-c net, while MS7b generates a 3D net with unusual β-Sn topology. The photoluminescence properties Eu- and Tb-doped compounds (MS5-6 are also investigated, exhibiting strong red and green light emissions, respectively, which are attributed to the efficient energy transfer process from the BDC ligand to Eu3+ and Tb3+.

  7. Transition metal complexes with oxygen donor ligands: a synthesis, spectral, thermal and antimicrobial study

    Directory of Open Access Journals (Sweden)

    VAIBHAV N. PATANGE

    2008-10-01

    Full Text Available Transition metal complexes of chalcones derived from the conden¬sation of 3-acetyl-6-methyl-2H-pyran-2,4(3H-dione (dehydroacetic acid and p-methoxybenzaldehyde (HL1 or p-nitrobenzaldehyde (HL2 were synthesized and characterized by elemental analysis, conductometry, thermal analysis, magnetic measurements, IR, 1H-NMR, UV–Vis spectroscopy and a microbial study. From the analytical and thermal data, the stoichiometry of the complexes was found to be 1:2 (metal:ligand. The molar conductance data revealed that all the metal chelates were non-electrolytes. The thermal stability of the complexes was studied by thermogravimetry and the decomposition schemes of the complexes are given. The ligands and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli, and fungicidal activity against Aspergillus flavus, Curvularia lunata and Penicillium notatum.

  8. Determination of stability constants of aminoglycoside antibiotics with their metal complexes

    Science.gov (United States)

    Tiwow, Vanny M. A.

    2014-03-01

    One group of aminoglycoside antibiotics contains aminosugars. The aminosugar neomycin B with its derivate product neamine (2-Deoxy-4-0-(2,6-diamino-2,6-dideoxy-α-D-glucopyranosyl)-D-Streptamine) was identified as a free ligands and metal complexes. In particular, the stability constants of metal complexes by potentiometric titration techniques were investigated. Our previous study had determined the acid dissociation constants of these aminosugars with few metal complexes in fair depth. In this work, the complexation of two pyridine-containing amino alcohols and an amino sugar (neamine) have been measured potentiometrically. For instance, the stability constant of copper(II) complexation were determine and the model system generated an excellent fit. Stability constants with several metals have been determined and will be reported.

  9. A highly luminescent dinuclear Eu(III) complex based on 4,4'-bis (4'',4'',4''-trifluoro-1'',3''-dioxobutyl)-o-terphenyl for light-emitting diodes

    International Nuclear Information System (INIS)

    Liu Shenggui; He Pei; Wang Huihui; Shi Jianxin; Gong Menglian

    2009-01-01

    A dinuclear Eu(III) complex Eu 2 (btbt) 3 .4H 2 O.CH 3 CH 2 OH.N(CH 2 CH 3 ) 3 was synthesized, where H 2 (btbt) was 4,4'-bis (4'',4'',4'',-trifluoro-1'',3''-dioxobutyl)-o-terphenyl. The composition and structure of the complex were characterized by elemental analysis, IR, UV-vis and FAB-MS spectroscopy. The complex emits the characteristic red luminescence of Eu 3+ ion due to the 5 D 0 → 7 F J (J = 0-4) transitions under ∼395 nm-light excitation with good luminescent quantum efficiency (32%) and exhibits high thermal stability (337 deg. C). Bright red light-emitting diodes (LEDs) were fabricated by coating the complex onto a ∼395 nm-emitting InGaN chip. When the mass ratio of the red phosphor to the silicone is 1:30, the efficiency of the fabricated LEDs with the europium complex is 0.98 lm w -1 . The CIE chromaticity coordinates of the LEDs are x = 0.6057 and y = 0.3137, which are close to the National Television Standard Committee (NTSC) standard values for red color. The results indicate that the complex may act as a red component in the fabrication of near UV InGaN-based white light-emitting diodes with high color-rendering index.

  10. Dilution-triggered SMM behavior under zero field in a luminescent Zn2Dy2 tetranuclear complex incorporating carbonato-bridging ligands derived from atmospheric CO2 fixation.

    Science.gov (United States)

    Titos-Padilla, Silvia; Ruiz, José; Herrera, Juan Manuel; Brechin, Euan K; Wersndorfer, Wolfgang; Lloret, Francesc; Colacio, Enrique

    2013-08-19

    The synthesis, structure, magnetic, and luminescence properties of the Zn2Dy2 tetranuclear complex of formula {(μ3-CO3)2[Zn(μ-L)Dy(NO3)]2}·4CH3OH (1), where H2L is the compartmental ligand N,N',N″-trimethyl-N,N″-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine, are reported. The carbonate anions that bridge two Zn(μ-L)Dy units come from the atmospheric CO2 fixation in a basic medium. Fast quantum tunneling relaxation of the magnetization (QTM) is very effective in this compound, so that single-molecule magnet (SMM) behavior is only observed in the presence of an applied dc field of 1000 Oe, which is able to partly suppress the QTM relaxation process. At variance, a 1:10 Dy:Y magnetic diluted sample, namely, 1', exhibits SMM behavior at zero applied direct-current (dc) field with about 3 times higher thermal energy barrier than that in 1 (U(eff) = 68 K), thus demonstrating the important role of intermolecular dipolar interactions in favoring the fast QTM relaxation process. When a dc field of 1000 Oe is applied to 1', the QTM is almost fully suppressed, the reversal of the magnetization slightly slows, and U(eff) increases to 78 K. The dilution results combined with micro-SQUID magnetization measurements clearly indicate that the SMM behavior comes from single-ion relaxation of the Dy(3+) ions. Analysis of the relaxation data points out that a Raman relaxation process could significantly affect the Orbach relaxation process, reducing the thermal energy barrier U(eff) for slow relaxation of the magnetization.

  11. Metal-ion complexes of functionalised 1,10-Phenanthrolines as hydrolytic synzymes

    NARCIS (Netherlands)

    Weijnen, J.G.J.

    1993-01-01

    In this thesis metal-ion complexes of functionalised 1,10-phenanthroline derivatives have been studied as model systems for hydrolytic metallo-enzymes. Amphiphilic metallo- complexes incorporated into micelles or vesicles and water-soluble complexes in pure aqueous buffer solutions, have

  12. Synthesis, spectral, thermal, potentiometric and antimicrobial studies of transition metal complexes of tridentate ligand

    Directory of Open Access Journals (Sweden)

    Sarika M. Jadhav

    2014-01-01

    Full Text Available A series of metal complexes of Cu(II, Ni(II, Co(II, Fe(III and Mn(II have been synthesized with newly synthesized biologically active tridentate ligand. The ligand was synthesized by condensation of dehydroacetic acid (3-acetyl-6-methyl-(2H pyran-2,4(3H-dione or DHA, o-phenylene diamine and fluoro benzaldehyde and characterized by elemental analysis, molar conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, IR, 1H-NMR, UV–Vis spectroscopy and mass spectra. From the analytical data, the stoichiometry of the complexes was found to be 1:2 (metal:ligand with octahedral geometry. The molar conductance values suggest the non-electrolyte nature of metal complexes. The IR spectral data suggest that the ligand behaves as a dibasic tridentate ligand with ONN donor atoms sequence towards central metal ion. Thermal behaviour (TG/DTA and kinetic parameters calculated by the Coats–Redfern and Horowitz–Metzger method suggest more ordered activated state in complex formation. To investigate the relationship between stability constants of metal complexes and antimicrobial activity, the dissociation constants of Schiff bases and stability constants of their binary metal complexes have been determined potentiometrically in THF–water (60:40% solution at 25 ± 1 °C and at 0.1 M NaClO4 ionic strength. The potentiometric study suggests 1:1 and 1:2 complexation. Antibacterial and antifungal activities in vitro were performed against Staphylococcus aureus, Escherichia coli and Aspergillus niger, Trichoderma, respectively. The stability constants of the metal complexes were calculated by the Irving–Rosotti method. A relation between the stability constant and antimicrobial activity of complexes has been discussed. It is observed that the activity enhances upon complexation and the order of antifungal activity is in accordance with stability order of metal ions.

  13. Self-Assembly of Discrete Metal Complexes in Aqueous Solution via Block Copolypeptide Amphiphiles

    Directory of Open Access Journals (Sweden)

    Timothy J. Deming

    2013-01-01

    Full Text Available The integration of discrete metal complexes has been attracting significant interest due to the potential of these materials for soft metal-metal interactions and supramolecular assembly. Additionally, block copolypeptide amphiphiles have been investigated concerning their capacity for self-assembly into structures such as nanoparticles, nanosheets and nanofibers. In this study, we combined these two concepts by investigating the self-assembly of discrete metal complexes in aqueous solution using block copolypeptides. Normally, discrete metal complexes such as [Au(CN2]−, when molecularly dispersed in water, cannot interact with one another. Our results demonstrated, however, that the addition of block copolypeptide amphiphiles such as K183L19 to [Au(CN2]− solutions induced one-dimensional integration of the discrete metal complex, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Transmission electron microscopy (TEM showed a fibrous nanostructure with lengths and widths of approximately 100 and 20 nm, respectively, which grew to form advanced nanoarchitectures, including those resembling the weave patterns of Waraji (traditional Japanese straw sandals. This concept of combining block copolypeptide amphiphiles with discrete coordination compounds allows the design of flexible and functional supramolecular coordination systems in water.

  14. Efficient and selective singlet oxygen sensitized NIR luminescence of a neodymium(III) complex and its application in biological imaging

    Energy Technology Data Exchange (ETDEWEB)

    Lo, Wai-Sum [Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong Special Administrative Region (Hong Kong); Li, Hongguang [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Law, Ga-Lai, E-mail: ga-lai.law@polyu.edu.hk [Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong Special Administrative Region (Hong Kong); Wong, Wing-Tak, E-mail: bcwtwong@polyu.edu.hk [Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong Special Administrative Region (Hong Kong); Wong, Ka-Leung, E-mail: klwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong)

    2016-01-15

    A responsive neodymium NIR emission ({sup 4}F{sub 3/2}→{sup 4}I{sub 11/2,} {sub 9/2}) was recorded upon binding with singlet oxygen (K{sub B}=1.79×10{sup 6} M{sup −1}) via the anthracene moiety. The motif ytterbium analog served as a negative control with no significant NIR enhancement/quenching with the addition of the same amount of singlet oxygen. Our complex was also found to react with {sup 1}O{sub 2} generated by a known photosensitizer TMPyP inside HeLa cells without inducing cell death and display no significant cytotoxicity. - Highlights: • A turn-on NIR-emissive {sup 1}O{sub 2} probe has been synthesized for potential biological applications. • It has a binding constant of 1.9×10{sup 6} M{sup −1} and the emission intensity has a 5-fold increase upon binding. • The probe was also found to quench singlet oxygen in vitro generated by known photosensitizer TMPyP.

  15. Lanthanide Single-Molecule Magnets Framed by Alkali Metals & Magnetic and Spectroscopic Studies of 3d Transition Metal Complexes

    DEFF Research Database (Denmark)

    Konstantatos, Andreas

    -molecule magnets (SMMs). Starting from the archetype SMM Mn12 we present the details of the mechanisms governing the relaxation of the magnetization of these systems. In Chapter 2 we present our work on the coordination chemistry of lanthanides with a new Schiff-base ligand, H3L [(E)-3-((2-hydroxyphenyl...... complexes of M3+ or M2+ metal ions (M: 3d transition metal) with the preference to either approximate octahedral or trigonal prismatic coordination geometry. A detailed magnetic characterization for most of the complexes is presented where a trinuclear Co2+ cluster stands out for its pronounced SMM...

  16. Persistent luminescence of transition metal (Co, Ni...)-doped ZnGa2O4 phosphors for applications in the near-infrared range

    Science.gov (United States)

    Pellerin, Morgane; Castaing, Victor; Gourier, Didier; Chanéac, Corinne; Viana, Bruno

    2018-02-01

    Persistent luminescence materials present many applications including security lighting and bio-imaging. Many progresses have been made in the elaboration of persistent luminescent nanoparticles suitable for the first NIR partial transparency window (650 - 950 nm). Moving to the second and third near-infrared partial transparency windows (1000 nm - 1800 nm) allows further reducing of scattering, absorption and tissue autofluorescence effects. In this work, we present the synthesis of Co2+ and Ni2+ doped zinc-gallate nanoparticles with broad emission covering the NIR-II range. Site occupancy, energy levels, optical features and persistent phenomena are presented.

  17. Synthesis and characterization of transition metal complexes derived from some biologically active furoic acid hydrazones

    Directory of Open Access Journals (Sweden)

    P. Venkateswar Rao

    2007-04-01

    Full Text Available Two new physiologically active ligands, N’-2-[(E-1-hydroxy-4-methyl-2-oxo-2H-8-chromenyl ethylidene-2-furan carbohydrazide (HMCFCH and N’-2-[(Z-1-(4-hydroxy-6-methyl-2-oxo-2H-pyranyl ethylidene]-furan carbohydrazide (HMPFCH and their VO(II, Mn(II, Fe(II, Co(II, Ni(II and Cu(II complexes have been prepared. The ligands and the metal complexes have been characterized by elemental analyses, electrical conductance, magnetic susceptibility measurements, UV-Vis, IR, and ESR spectroscopic data. Basing on the above data, Fe(II and Co(II complexes of HMCFCH and HMPFCH have been assigned a dimeric octahedral geometry. VO(II complexes of HMCFCH and HMPFCH have been assigned sulfate bridged dimeric square pyramidal geometry. Mn(II complex of HMCFCH has been assigned a dimeric octahedral geometry, where as Mn(II complex of HMPFCH has been ascribed to monomeric octahedral geometry. Cu(II and Ni(II complexes of HMCFCH have been ascribed to a polymeric structure. Ni(II complex of HMPFCH has been assigned a dimeric square planar geometry. Cu(II complex of HMPFCH has been proposed an octahedral geometry. The ligands and their metal chelates were screened against S. aureus and P. aeruginosa. The ligands and the metal complexes have been found to be active against these microorganisms. The ligands show more activity than the metal complexes.

  18. Transition metal M(II complexes with isonicotinoylhydrazone-9-anthraldehyde

    Directory of Open Access Journals (Sweden)

    Dianu M.L.

    2010-01-01

    Full Text Available New complexes of isonicotinoylhydrazone-9-anthraldehyde with Cu(II, Co(II and Ni(II have been prepared and characterized by analytical and physico-chemical techniques, such as elemental and thermal analyses, magnetic susceptibility and conductivity measurements, and electronic, EPR and IR spectral studies. The infrared spectral studies revealed the bidentate or monodentate nature of the Schiff base in the complexes; the pyridine nitrogen does not participate in the coordination. A tetrahedral geometry is suggested for the nitrate-complexes and an octahedral geometry for the others. Thermal studies support the chemical formulation of these complexes.

  19. Effects of complexing compounds on sorption of metal ions to cement

    Energy Technology Data Exchange (ETDEWEB)

    Loevgren, Lars [Umeaa Univ. (Sweden). Inorganic chemistry

    2005-12-15

    This present report is a literature review addressing the effects of complexing ligands on the sorption of radionuclides to solid materials of importance for repositories of radioactive waste. Focus is put on laboratory studies of metal ion adsorption to cement in presence of chelating agents under strongly alkaline conditions. As background information, metal sorption to different mineral and cement phases in ligand free systems is described. Furthermore, surface complexation model (SCM) theories are introduced. According to surface complexation theories these interactions occur at specific binding sites at the particle/water interface. Adsorption of cationic metals is stronger at high pH, and the adsorption of anions occurs preferentially at low pH. The adsorption of ions to mineral surfaces is a result of both chemical bonding and electrostatic attraction between the ions and charged mineral surfaces. By combining uptake data with spectroscopic information the sorption can be explained on a molecular level by structurally sound surface complexation models. Most of the metal sorption studies reviewed are dealing with minerals exhibiting oxygen atoms at their surfaces, mainly oxides of Fe(II,III) and Al(III), and aluminosilicates. Investigations of radionuclides are focused on clay minerals, above all montmorillonite and illite. Which mechanism that is governing the metal ion adsorption to a given mineral is to a large extent depending on the metal adsorbed. For instance, sorption of Ni to montmorillonite can occur by formation of inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and by formation of a Ni phyllosilicate phase parallel to montmorillonite layers. Also metal uptake to cement materials can occur by different mechanisms. Cationic metals can both be attached to cement (calcium silicate hydrate, CSH) and hardened cement paste (HCP) by formation of inner-sphere complexes at specific surface sites and by

  20. Reactions of transition metal complexes with cyclic ethers

    International Nuclear Information System (INIS)

    Milstein, D.

    1977-02-01

    Three novel reactions of epoxides with homogeneous transition-metal catalysts have been explored: (a) the selective rearrangement of internal epoxides to ketones; (b) the cleavage of C-C bond in epoxides having electron-attracting substituents; (c) the transformation of terminal epoxides into esters. Based on an intensive kinetic study, a general mechanism for the transformations of epoxides is postulated

  1. Biological activities of some Fluoroquinolones-metal complexes

    African Journals Online (AJOL)

    McRoy

    Background: Metal ions play a vital role in the design of more biologically active drugs. Aim: The paper reviewed the .... 2H2O by direct reaction of copper(II) sulphate pentahydrate with ciprofloxacin in distilled water. ... membered ring and the chloride ion completes the seven coordination around the Ca2+ion.[37-39].

  2. Theoretical NMR spectroscopy of N-heterocyclic carbenes and their metal complexes

    KAUST Repository

    Falivene, Laura; Cavallo, Luigi

    2016-01-01

    Recent theoretical analysis of the NMR properties of free N-heterocyclic carbenes (NHC) and Metal-NHC complexes has complemented experiments, allowing the establishment of structure/property relationships and the rationalization of otherwise

  3. Basic deuteroexchange in complexes of transition metals with nitrogen-containing aromatic heterocycles

    International Nuclear Information System (INIS)

    Tupitsyn, I.F.

    1986-01-01

    A study was made of the kinetics of deuteroexchange in the methyl group in complexes of one metal [nickel(II)] with different methyl-substituted aromatic heterocycles and in isostructural complexes of one ligand (2-methylquinoline) with different central metal atoms (Mn 2+ , Ni 2+ , Cu 2+ , Zn 2+ ). The order in which the structures of the ligands influence the rate of deuteroexchange in the complexes does not correspond qualitatively with the order of increase in the rate of deuteroexchange in the noncoordinated ligands. The rate of deuteroexchange is only weakly influenced by change in the identity of the metal complex former. A deuteroexchange mechanism is proposed and discussed. A structure arising in the course of the exchange process with transfer of electron density from the heterocyclic ligand to the metal ion forms the transition state of the reaction

  4. Basic deuteroexchange in transition metal complexes with nitrogen-containing aromatic heterocycles

    International Nuclear Information System (INIS)

    Tupitsyn, I.F.

    1986-01-01

    Kinetics of deuteroexchange in the methyl group of nitrate complexes of a metal - nickel (2) - with different methyl-substituted aromatic heterocycles and isostructural complexes of a ligand - 2 - methyl quinoline - with different central metal atoms (Mn(2), Ni(2), Cu(2), Zn(2)) is studied. Series for influence of ligand structure on deuteroexchange rate in complexes doesn't correspond qualitatively to series for deuteroexchange rate increase in noncoordinated ligands. Deuteroexchange rate is weakly subjected to influence of exchange in metal-complexing agent. Deuteroexchange mechanism is suggested and discussed. According to this mechanism the structure developed in the course of the exchange process with electron density transfer from the heterocyclic ligand to a metal ion is a transition state of the reaction

  5. Multiheteromacrocycles that complex metal ions. Third progress report, 1 May 1976--30 April 1977

    International Nuclear Information System (INIS)

    Cram, D.J.

    1977-01-01

    The overall objective of this research is to design, synthesize and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes and clusters. Host organic compounds consist of strategically placed solvating, coordinating and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions, or metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; numbers of binding sites; characters of binding sites; and valences. The specific compounds synthesized and their complexing and lipophilizing properties are summarized

  6. Density functional study of isoguanine tetrad and pentad sandwich complexes with alkali metal ions.

    Science.gov (United States)

    Meyer, Michael; Steinke, Thomas; Sühnel, Jürgen

    2007-02-01

    Isoguanine tetraplexes and pentaplexes contain two or more stacked polyads with intercalating metal ions. We report here the results of a density functional study of sandwiched isoguanine tetrad and pentad complexes consisting of two polyads with Na(+), K(+) and Rb(+) ions at the B3LYP level. In comparison to single polyad metal ion complexes, there is a trend towards increased non-planarity of the polyads in the sandwich complexes. In general, the pentad sandwiches have relatively planar polyad structures, whereas the tetrad complexes contain highly non-planar polyad building blocks. As in other sandwich complexes and in metal ion complexes with single polyads, the metal ion-base interaction energy plays an essential role. In iG sandwich structures, this interaction energy is slightly larger than in the corresponding guanine sandwich complexes. Because the base-base interaction energy is even more increased in passing from guanine to isoguanine, the isoguanine sandwiches are thus far the only examples where the base-base interaction energy is larger than the base-metal ion interaction energy. Stacking interactions have been studied in smaller models consisting of two bases, retaining the geometry from the complete complex structures. From the data obtained at the B3LYP and BH&H levels and with Møller-Plesset perturbation theory, one can conclude that the B3LYP method overestimates the repulsion in stacked base dimers. For the complexes studied in this work, this is only of minor importance because the direct inter-tetrad or inter-pentad interaction is supplemented by a strong metal ion-base interaction. Using a microsolvation model, the metal ion preference K(+) approximately Rb(+) > Na(+) is found for tetrad complexes. On the other hand, for pentads the ordering is Rb(+) > K(+) > Na(+). In the latter case experimental data are available that agree with this prediction.

  7. Insights into aquatic toxicities of the antibiotics oxytetracycline and ciprofloxacin in the presence of metal: Complexation versus mixture

    International Nuclear Information System (INIS)

    Zhang Yu; Cai Xiyun; Lang Xianming; Qiao Xianliang; Li Xuehua; Chen Jingwen

    2012-01-01

    Co-contamination of ligand-like antibiotics (e.g., tetracyclines and quinolones) and heavy metals prevails in the environment, and thus the complexation between them is involved in environmental risks of antibiotics. To understand toxicological significance of the complex, effects of metal coordination on antibiotics' toxicity were investigated. The complexation of two antibiotics, oxytetracycline and ciprofloxacin, with three heavy metals, copper, zinc, and cadmium, was verified by spectroscopic techniques. The antibiotics bound metals via multiple coordination sites and rendered a mixture of various complexation speciations. Toxicity analysis indicated that metal coordination did modify the toxicity of the antibiotics and that antibiotic, metal, and their complex acted primarily as concentration addition. Comparison of EC 50 values revealed that the complex commonly was highest toxic and predominately correlated in toxicity to the mixture. Finally, environmental scenario analysis demonstrated that ignoring complexation would improperly classify environmental risks of the antibiotics. - Highlights: ► The complex of antibiotic with metal is a mixture of various complexation modes. ► Antibiotic and metal act as various combined interactions when their complexation is ignored. ► Antibiotic, metal, and their complex act as concentration addition interaction. ► Complex commonly is the highest toxicant. ► Neglecting complexation renders improper classification of risks for antibiotics. - Antibiotic, heavy metal and their complex act primarily as concentration addition interaction and the complex commonly is highest toxic.

  8. Insights into aquatic toxicities of the antibiotics oxytetracycline and ciprofloxacin in the presence of metal: Complexation versus mixture

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Zhang [Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Cai Xiyun, E-mail: xiyuncai@dlut.edu.cn [Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Xianming, Lang [Liaoning Academy of Environmental Sciences, Shenyang 110031 (China); Xianliang, Qiao; Xuehua, Li; Jingwen, Chen [Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China)

    2012-07-15

    Co-contamination of ligand-like antibiotics (e.g., tetracyclines and quinolones) and heavy metals prevails in the environment, and thus the complexation between them is involved in environmental risks of antibiotics. To understand toxicological significance of the complex, effects of metal coordination on antibiotics' toxicity were investigated. The complexation of two antibiotics, oxytetracycline and ciprofloxacin, with three heavy metals, copper, zinc, and cadmium, was verified by spectroscopic techniques. The antibiotics bound metals via multiple coordination sites and rendered a mixture of various complexation speciations. Toxicity analysis indicated that metal coordination did modify the toxicity of the antibiotics and that antibiotic, metal, and their complex acted primarily as concentration addition. Comparison of EC{sub 50} values revealed that the complex commonly was highest toxic and predominately correlated in toxicity to the mixture. Finally, environmental scenario analysis demonstrated that ignoring complexation would improperly classify environmental risks of the antibiotics. - Highlights: Black-Right-Pointing-Pointer The complex of antibiotic with metal is a mixture of various complexation modes. Black-Right-Pointing-Pointer Antibiotic and metal act as various combined interactions when their complexation is ignored. Black-Right-Pointing-Pointer Antibiotic, metal, and their complex act as concentration addition interaction. Black-Right-Pointing-Pointer Complex commonly is the highest toxicant. Black-Right-Pointing-Pointer Neglecting complexation renders improper classification of risks for antibiotics. - Antibiotic, heavy metal and their complex act primarily as concentration addition interaction and the complex commonly is highest toxic.

  9. Chromium(0), molybdenum(0), and tungsten(0) isocyanide complexes as luminophores and photosensitizers with long-lived excited states

    International Nuclear Information System (INIS)

    Bueldt, Laura A.; Wenger, Oliver S.

    2017-01-01

    Arylisocyanide complexes based on earth-abundant Group 6 d 6 metals are interesting alternatives to photoactive complexes made from precious metals such as Ru II , Re I , Os II , or Ir III . Some of these complexes have long-lived 3 MLCT excited states that exhibit luminescence with good quantum yields as well as nano- to microsecond lifetimes, and they are very strongly reducing. Recent studies have demonstrated that Cr 0 , Mo 0 , and W 0 arylisocyanide complexes have great potential for applications in luminescent devices, photoredox catalysis, and dye-sensitized solar cells. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes

    NARCIS (Netherlands)

    Armitt, D.J.; Bruce, M.I.; Gaudio, M.; Zaitseva, N.N.; Skelton, B.W.; White, A.H.; Le Guennic, B.; Halet, J.-F.; Fox, M.A.; Roberts, R.L.; Hartl, F.; Low, P.J.

    2008-01-01

    Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me3SiC CC6F5 and RuCl(dppe)Cp'[Cp' = Cp, Cp*] in the presence of

  11. Shrinking the Synchrotron : Tabletop Extreme Ultraviolet Absorption of Transition-Metal Complexes

    NARCIS (Netherlands)

    Zhang, Kaili; Lin, Ming Fu; Ryland, Elizabeth S.; Verkamp, Max A.; Benke, Kristin; De Groot, Frank M F; Girolami, Gregory S.; Vura-Weis, Josh

    2016-01-01

    We show that the electronic structure of molecular first-row transition-metal complexes can be reliably measured using tabletop high-harmonic XANES at the metal M2,3 edge. Extreme ultraviolet photons in the 50-70 eV energy range probe 3p → 3d transitions, with the same selection rules as soft X-ray

  12. Study of the competitive reaction ability of harmine and harmaline during complex formation with transition metals

    International Nuclear Information System (INIS)

    Chepulsky, S.A.; Kadirova, Z.Ch.; Parpiev, N.A.

    2006-01-01

    New coordination compounds of d-metals (Zn(II), Co(II), Mn(II), Mo(VI), Cr(VI)) β-carboline alkaloids were synthesized. The structure of obtained substances was established by IR, PMR spectroscopy. The quantum-chemical assessment of the harmine and harmaline reactivity in complexation reactions with d-metals was carried out. (author)

  13. Proton magnetic resonance spectra of metal ammine complexes, 8

    International Nuclear Information System (INIS)

    Taura, Toshiaki; Sakaguchi, Ushio; Yoneda, Hayami

    1976-01-01

    The rates of amine hydrogen isotopic exchange in the [Co(O) 2 (N) 4 ] + complex ions, where (O) 2 represents carbonate, oxalate, or malonate ions, and (N) 4 , tetraamine, bis(ethylenediamine), or bis(trimethylenediamine), were measured in D 2 O at 35 0 C by the PMR technique. It was found that: (1) the rates for trans (to oxygen) amines are faster than those for cis amines; (2) the rates, especially for trans amines, in the carbonato complexes are slower than those in the oxalato and malonato analogs, and (3) the difference between the rates for cis and trans amines is smaller in the bis(diamine) complexes than in the tetraammine complexes. These results are discussed in terms of the influence of the chelate geometry in the complex on the exchange reaction. (auth.)

  14. Chiral phosphites as ligands in asymmetric metal complex catalysis and synthesis of coordination compounds

    International Nuclear Information System (INIS)

    Gavrilov, Konstantin N; Bondarev, Oleg G; Polosukhin, Aleksei I

    2004-01-01

    The data published during the last five years on the application of chiral derivatives of phosphorous acid in coordination chemistry and enantioselective catalysis are summarised and discussed. The effect of the nature of these ligands on the structure of metal complexes and on the efficiency of catalytic organic syntheses is shown. Hydroformylation, hydrogenation, allylic substitution and conjugate addition catalysed by transition metal complexes with optically active phosphites and hydrophosphoranes are considered. The prospects for the development of this field of research are demonstrated.

  15. Synthesis, physico-chemical characterization and biological activity of 2-aminobenzimidazole complexes with different metal ions

    Directory of Open Access Journals (Sweden)

    Podunavac-Kuzmanović Sanja O.

    2004-01-01

    Full Text Available Complexes of 2-aminobenzimidazole (L with nitrates of cobalt(II nickel(II, copper (II, zinc(II and silver(I were synthesized. The molar ratio metal:ligand in the reaction of the complex formation was 1:2. It should be noticed, that the reaction of all the metal salts yielded bis(ligand complexes of the general formula M(L2(NO32 × nH2O (M=Co, Ni Cu, Zn or Ag; n=0, 1, 2 or 6. The complexes were characterized by elemental analysis of the metal, molar conductivity, magnetic susceptibility measurements and IR spectra. Co(II, Ni(II and Cu(II complexes behave as non-electrolytes, whilst Zn(II and Ag(I are 1:1 electrolytes. Cu(II complex has a square-planar stereochemistry, Ag(I complex is linear, whilst the Co(II, Ni(II and Zn(II complexes have a tetrahedral configuration. In all the complexes ligand is coordinated by participation of the pyridine nitrogen of the benzimidazole ring. The antimicrobial activity of the ligand and its complexes against Pseudomonas aeruginosa, Bacillus sp. Staphylococcus aureus and Saccharomyces cerevisiae was investigated. The effect of metal on the ligand antimicrobial activity is discussed.

  16. 3d/4f Metal Complexes of Phenolic Oximes New Binding Sites on Anderson Polyoxometalates Metal Complexes of the New THAME Ligand

    DEFF Research Database (Denmark)

    Sethi, Waqas

    to be coordinatedto SMMs as well as onto other transition metal complexes, via different synthetic strategies. These synthetic routes did not result in the crystallisation of any new compounds. A new hexadentate ligand tris(((2-hydroxyethyl)-amino)methyl)ethane (THAME) was synthesised and characterised. THAME...

  17. Near-infrared dichroism of a mesogenic transition metal complex and its solubility in nematic hosts

    International Nuclear Information System (INIS)

    Marshall, K.L.; Jacobs, S.D.

    1987-01-01

    A transition metal complex possessing the nematic phase, bis (p-n-butylstyryl-1, 2-dithiolato) nickel, was synthesized and its optical properties and solubility in the nematic hosts K15 and MBBA were investigated. The metal complex displayed a high solubility in both host materials (up to 10% wt/wt) and a strong near-infrared absorption band centered at 860 nm. A blocking extinction of greater than OD = 3 was obtained with a 100 micron pathlength of a 0.5% wt/wt mixture of the nematic metal complex in K15, suggesting its usefulness for passive blocking of near infrared radiation. A 24 micron thick, homogeneously aligned guest-host cell containing a 1% wt/wt mixture of the metal complex in K15 possessed a contrast ratio of nearly 5:1 and a blocking extinction of OD = 3.5 at 860 nm, demonstrating for the first time the existence of near-infrared dichroism in this class of materials. The solubility and blocking extinction of the mesogenic metal complex in K15 was considerably superior to the non-mesogenic near ir laser dye bis(dimethylaminodithiobenzil) nickel in the same host. An interaction of the nematic metal complex in mixtures with MBBA which resulted in the creation of a new absorption band at 1050 nm was also observed. 21 refs., 9 figs

  18. Dissolution of Fe(III) (hydr) oxides by metal-EDTA complexes

    Science.gov (United States)

    Ngwack, Bernd; Sigg, Laura

    1997-03-01

    The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA CaEDTA ≫ PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced.

  19. Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative.

    Science.gov (United States)

    Požar, Josip; Nikšić-Franjić, Ivana; Cvetnić, Marija; Leko, Katarina; Cindro, Nikola; Pičuljan, Katarina; Borilović, Ivana; Frkanec, Leo; Tomišić, Vladislav

    2017-09-14

    The medium effect on the complexation of alkali metal cations with a calix[4]arene ketone derivative (L) was systematically examined in methanol, ethanol, N-methylformamide, N,N-dimethylformamide, dimethyl sulfoxide, and acetonitrile. In all solvents the binding of Na + cation by L was rather efficient, whereas the complexation of other alkali metal cations was observed only in methanol and acetonitrile. Complexation reactions were enthalpically controlled, while ligand dissolution was endothermic in all cases. A notable influence of the solvent on NaL + complex stability could be mainly attributed to the differences in complexation entropies. The higher NaL + stability in comparison to complexes with other alkali metal cations in acetonitrile was predominantly due to a more favorable complexation enthalpy. The 1 H NMR investigations revealed a relatively low affinity of the calixarene sodium complex for inclusion of the solvent molecule in the calixarene hydrophobic cavity, with the exception of acetonitrile. Differences in complex stabilities in the explored solvents, apart from N,N-dimethylformamide and acetonitrile, could be mostly explained by taking into account solely the cation and complex solvation. A considerable solvent effect on the complexation equilibria was proven to be due to an interesting interplay between the transfer enthalpies and entropies of the reactants and the complexes formed.

  20. Features of proteolytic properties of tetraphenylporphyrin complex with lanthanide group metals

    Science.gov (United States)

    Tobolkina, Elena A.; Skripnikova, Tatiana A.; Starikova, Anna A.; Shumilova, Galina I.; Pendin, Andrey A.

    2018-01-01

    Demetallation of metalloporphyrin molecules is one of the essential degradation reactions in photosynthesis. The effect of metalloporphyrin nature on removal of central metals from tetraphenylporphyrin complexes based on lanthanide group metals (Dy, Er, Lu, Ho) has been studied. pH values, at which the metal ions leave the metalloporphyrin complex were established using two-phase spectrophotometric titration with potentiometric pH-control. The pH values decrease with the increase of atomic numbers of lanthanide groups, as well as with increase of 4f-electrons. The reaction of an extra ligand exchange for the hydroxide ion was studied. For Dy-, Er- and Ho-tetraphenylporphyrin complexes one particle of extra ligand coordinates with one porphyrin complex. A complex with dimeric particles can be formed for the system of Lu-tetraphenylporphyrin. Constants of the ion exchange reactions were calculated.

  1. Transition metal complexes of some biologically active ligands; synthesis characterization and bioactivities

    International Nuclear Information System (INIS)

    Rehman, S.; Ali, N.; Nisar, M.

    2009-01-01

    Transition/representative transition metals complexes of biologically active chelating agent 1,2-dipyrolodinoethane were synthesized and characterized through spectral and analytical data. The complexes are of the formula (M(L)X/sub 2/). Where (M = Co (II), Ni (II), Cu (II), Zn (II), Hg (II) and Cd (II) and X = CI, Br, NO/sub 3/). Tetrahedral geometry has been proposed to these-metal complexes with the help of magnetic measurements, elemental analysis, chemical stoichiometry and spectroscopic data Antibacterial activity of the ligand and its metal complexes were screened against Eschereschi coli, Klebsiello pneumonia, Proteus mirabilis, Proteus vulhari, Streptococcus pneumonia, Salmonella Iyphi, Bacilh,s anthrax, Streptococcus fecalis and Staphylococcus aureus. Complexes were found to be active against Eschereschi coli, Klebsiella pneumonia, Proteus mirabilis and Proteus vulharis. (author)

  2. Preparation of Palladium-Impregnated Ceria by Metal Complex Decomposition for Methane Steam Reforming Catalysis

    Directory of Open Access Journals (Sweden)

    Worawat Wattanathana

    2017-01-01

    Full Text Available Palladium-impregnated ceria materials were successfully prepared via an integrated procedure between a metal complex decomposition method and a microwave-assisted wetness impregnation. Firstly, ceria (CeO2 powders were synthesized by thermal decomposition of cerium(III complexes prepared by using cerium(III nitrate or cerium(III chloride as a metal source to form a metal complex precursor with triethanolamine or benzoxazine dimer as an organic ligand. Palladium(II nitrate was consequently introduced to the preformed ceria materials using wetness impregnation while applying microwave irradiation to assist dispersion of the dopant. The palladium-impregnated ceria materials were obtained by calcination under reduced atmosphere of 10% H2 in He stream at 700°C for 2 h. Characterization of the palladium-impregnated ceria materials reveals the influences of the metal complex precursors on the properties of the obtained materials. Interestingly, the palladium-impregnated ceria prepared from the cerium(III-benzoxazine dimer complex revealed significantly higher BET specific surface area and higher content of the more active Pdδ+ (δ > 2 species than the materials prepared from cerium(III-triethanolamine complexes. Consequently, it exhibited the most efficient catalytic activity in the methane steam reforming reaction. By optimization of the metal complex precursors, characteristics of the obtained palladium-impregnated ceria catalysts can be modified and hence influence the catalytic activity.

  3. High capacity hydrogen absorption in transition-metal ethylene complexes: consequences of nanoclustering

    International Nuclear Information System (INIS)

    Phillips, A B; Shivaram, B S

    2009-01-01

    We have recently shown that organo-metallic complexes formed by laser ablating transition metals in ethylene are high hydrogen absorbers at room temperature (Phillips and Shivaram 2008 Phys. Rev. Lett. 100 105505). Here we show that the absorption percentage depends strongly on the ethylene pressure. High ethylene pressures (>100 mTorr) result in a lowered hydrogen uptake. Transmission electron microscopy measurements reveal that while low pressure ablations result in metal atoms dispersed uniformly on a near atomic scale, high pressure ones yield distinct nanoparticles with electron energy-loss spectroscopy demonstrating that the metal atoms are confined solely to the nanoparticles.

  4. Complexes of 3.6 kDa Maltodextrin with Some Metals

    Directory of Open Access Journals (Sweden)

    Christopher H. Schilling

    2004-06-01

    Full Text Available Preparation of magnesium, lanthanum, and bismuth(III complexes of 3.6 kDa maltodextrin and some properties of the resulting materials are presented. The metal derivatives contain metals bound to the oxygen atoms of the hydroxyl groups of maltodextrin. Additionally, the metal atoms are coordinated to the hydroxyl groups of the D-glucose units of the macroligand. Such coordination stabilized the metal – oxygen bond against hydrolysis, even in boiling water. The presence of magnesium and lanthanum atoms increased the thermal stability of maltodextrin, whereas bismuth atoms decreased it.

  5. Quantitative Interpretation of Multifrequency Multimode EPR Spectra of Metal Containing Proteins, Enzymes, and Biomimetic Complexes.

    Science.gov (United States)

    Petasis, Doros T; Hendrich, Michael P

    2015-01-01

    Electron paramagnetic resonance (EPR) spectroscopy has long been a primary method for characterization of paramagnetic centers in materials and biological complexes. Transition metals in biological complexes have valence d-orbitals that largely define the chemistry of the metal centers. EPR spectra are distinctive for metal type, oxidation state, protein environment, substrates, and inhibitors. The study of many metal centers in proteins, enzymes, and biomimetic complexes has led to the development of a systematic methodology for quantitative interpretation of EPR spectra from a wide array of metal containing complexes. The methodology is now contained in the computer program SpinCount. SpinCount allows simulation of EPR spectra from any sample containing multiple species composed of one or two metals in any spin state. The simulations are quantitative, thus allowing determination of all species concentrations in a sample directly from spectra. This chapter will focus on applications to transition metals in biological systems using EPR spectra from multiple microwave frequencies and modes. © 2015 Elsevier Inc. All rights reserved.

  6. Preconcentration of metallic elements by complexation with ammonium pyrrolidine dithiocarbamate (APDC) for atomic absorption analysis

    International Nuclear Information System (INIS)

    Santos Coelho, Ricardo dos; Dantas, Elizabeth S.K.

    1997-01-01

    Ammonium pyrrolidine dithiocarbamate (APDC) forms stable chelates with many metals being therefore, used in systems of preconcentration for determination of heavy metals in water. In this work, the metals were complexed with APDC and extracted with methyl isobutyl ketone (MIBK). The results showed that the studied metals (Co, Cu, Fe, Ni, Pb, Cr and Cd), in the range of 2 to 5 μg, in 100 ml of sample, were quantitatively extracted in only one stage using 10 ml of MIBK and 5 ml of 4% APDC. The pH must be between 4 and 5. The complexes stability was also studied. The proposed method can be applied to pre concentrate heavy metals in natural waters. (author). 4 refs., 1 fig., 3 tabs

  7. Selective transport of metal ions through cation exchange membrane in the presence of a complexing agent

    Energy Technology Data Exchange (ETDEWEB)

    Tingchia Huang; Jaukai Wang (National Cheng Kung Univ., Tainan (Taiwan, Province of China))

    1993-01-01

    Selective transport of metal ions through a cation exchange membrane was studied in stirred batch dialyzer for the systems Ni[sup 2+]-Cu[sup 2+] and Cu[sup 2+]-Fe[sup 3+]. Oxalic acid, malonic acid, citric acid, glycine, and ethylenediaminetetraacetic acid were employed as the complexing agents added in the feed solution in order to increase the permselectivity of metal ions. The experimental results show that the selective transport behavior of metal ions depends on the valence and the concentration of metal ions, the stoichiometric ratio of complexing agent to metal ions, and the pH value of the feed solution, but is independent of the concentration of counterion in the stripping phase. A theoretical approach was formulated on the basis of the Nernst-Planck equation and interface quasi-equilibrium. Theoretical solutions obtained from numerical calculation were in agreement with the experimental data.

  8. N-heterocyclic carbene metal complexes as bio-organometallic antimicrobial and anticancer drugs.

    Science.gov (United States)

    Patil, Siddappa A; Patil, Shivaputra A; Patil, Renukadevi; Keri, Rangappa S; Budagumpi, Srinivasa; Balakrishna, Geetha R; Tacke, Matthias

    2015-01-01

    Late transition metal complexes that bear N-heterocyclic carbene (NHC) ligands have seen a speedy growth in their use as both, metal-based drug candidates and potentially active homogeneous catalysts in a plethora of C-C and C-N bond forming reactions. This review article focuses on the recent developments and advances in preparation and characterization of NHC-metal complexes (metal: silver, gold, copper, palladium, nickel and ruthenium) and their biomedical applications. Their design, syntheses and characterization have been reviewed and correlated to their antimicrobial and anticancer efficacies. All these initial discoveries help validate the great potential of NHC-metal derivatives as a class of effective antimicrobial and anticancer agents.

  9. Alkali-crown ether complexes at metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Thontasen, Nicha; Deng, Zhitao; Rauschenbach, Stephan [Max Planck Institute for Solid State Research, Stuttgart (Germany); Levita, Giacomo [University of Trieste, Trieste (Italy); Malinowski, Nikola [Max Planck Institute for Solid State Research, Stuttgart (Germany); Bulgarian Academy of Sciences, Sofia (Bulgaria); Kern, Klaus [Max Planck Institute for Solid State Research, Stuttgart (Germany); EPFL, Lausanne (Switzerland)

    2010-07-01

    Crown ethers are polycyclic ethers which, in solution, selectively bind cations depending on the size of the ring cavity. The study of a single host-guest complex is highly desirable in order to reveal the characteristics of these specific interactions at the atomic scale. Such detailed investigation is possible at the surface where high resolution imaging tools like scanning tunneling microscopy (STM) can be applied. Here, electrospray ion beam deposition (ES-IBD) is employed for the deposition of Dibenzo-24-crown-8 (DB24C8)-H{sup +}, -Na{sup +} and -Cs{sup +} complexes on a solid surface in ultrahigh vacuum (UHV). Where other deposition techniques have not been successful, this deposition technique combines the advantages of solution based preparation of the complex ions with a highly clean and controlled deposition in UHV. Single molecular structures and the cation-binding of DB24C8 at the surface are studied in situ by STM and MALDI-MS (matrix assisted laser desorption ionization mass spectrometry). The internal structure of the complex, i.e. ring and cavity, is observable only when alkali cations are incorporated. The BD24C8-H{sup +} complex in contrast appears as a compact feature. This result is in good agreement with theoretical models based on density functional theory calculations.

  10. Catalytic hydrogenation using complexes of base metals with tridentate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Hanson, Susan K.; Zhang, Guoqi; Vasudevan, Kalyan V.

    2017-02-14

    Complexes of cobalt and nickel with tridentate ligand PNHP.sup.R are effective for hydrogenation of unsaturated compounds. Cobalt complex [(PNHP.sup.Cy)Co(CH.sub.2SiMe.sub.3)]BAr.sup.F.sub.4 (PNHP.sup.Cy=bis[2-(dicyclohexylphosphino)ethyl]amine, BAr.sup.F.sub.4=B(3,5-(CF.sub.3).sub.2C.sub.6H.sub.3).sub.4)) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions (25-60.degree. C., 1-4 atm H.sub.2). Nickel complex [(PNHP.sup.Cy)Ni(H)]BPh.sub.4 was used for hydrogenation of styrene and 1-octene under mild conditions. (PNP.sup.Cy)Ni(H) was used for hydrogenating alkenes.

  11. Catalytic hydrogenation using complexes of base metals with tridentate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Vasudevan, Kalyan V.; Zhang, Guoqi; Hanson, Susan K.

    2016-09-06

    Complexes of cobalt and nickel with tridentate ligand PNHP.sup.R are effective for hydrogenation of unsaturated compounds. Cobalt complex [(PNHP.sup.Cy)Co(CH.sub.2SiMe.sub.3)]BAr.sup.F.sub.4 (PNHP.sup.Cy=bis[2-(dicyclohexylphosphino)ethyl]amine, BAr.sup.F.sub.4=B(3,5-(CF.sub.3).sub.2C.sub.6H.sub.3).sub.4)) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions (25-60.degree. C., 1-4 atm H.sub.2). Nickel complex [(PNHP.sup.Cy)Ni(H)]BPh.sub.4 was used for hydrogenation of styrene and 1-octene under mild conditions. (PNP.sup.Cy)Ni(H) was used for hydrogenating alkenes.

  12. Light induced electron transfer reactions of metal complexes

    International Nuclear Information System (INIS)

    Sutin, N.; Creutz, C.

    1980-01-01

    Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed

  13. Electron transfer reactions of metal complexes in solution

    International Nuclear Information System (INIS)

    Sutin, N.

    1977-01-01

    A few representative electron-transfer reactions are selected and their kinetic parameters compared with the predictions of activated complex models. Since Taube has presented an elegant treatment of intramolecular electron-transfer reactions, emphasis is on bimolecular reactions. The latter electron-transfer reactions are more complicated to treat theoretically since the geometries of their activated complexes are not as well known as for the intramolecular case. In addition in biomolecular reactions, the work required to bring the two reactants together needs to be calculated. Since both reactants generally carry charges this presents a non-trivial problem at the ionic strengths usually used to study bimolecular electron transfer

  14. Plasmon-enhanced optically stimulated luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Guidelli, E. J.; Baffa, O. [Universidade de Sao Paulo, Faculdade de Filosofia, Ciencias e Letras de Ribeirao Preto, Departamento de Fisica, Av. Bandeirantes 3900, 14040-901 Ribeirao Preto, Sao Paulo (Brazil); Ramos, A. P., E-mail: ederguidelli@gmail.com [Universidade de Sao Paulo, Faculdade de Filosofia, Ciencias e Letras de Ribeirao Preto, Departamento de Quimica, Av. Bandeirantes 3900, 14040-901 Ribeirao Preto, Sao Paulo (Brazil)

    2015-10-15

    Full text: Optically Stimulated Luminescence dosimeters (OSLD) have been largely used for personal, medical, and industrial radiation dosimetry. Developing highly sensitive and small-sized radiation detectors and dosimeters is essential for improving spatial resolution and consequently diagnosis quality and treatment efficacy in the case of applications in radiodiagnosis and radiation therapy, for instance. Conventional methods to improve the OSLD sensitivity consist of doping and co-doping the host materials with atoms of other elements, thereby increasing the amount of trapping and/or luminescent centers. Our group is researching on the use of the plasmon properties of noble metal nanoparticles to increase OSL intensity. Upon incidence of a light beam with appropriate resonant wavelengths, the oscillation of the free electrons at the nanoparticle surface originates the Localized Surface Plasmons (LSP) and the consequent plasmon resonance band. The interaction between the LSP and the surrounding luminescent material leads to new optical properties largely employed for enhancing several luminescent processes. Here we will show our results regarding the use of LSP to increase OSLD sensitivity. The interaction between the traps/luminescent centers and the plasmons depends on the distance between them, on the plasmon resonance band intensity and position, as well as on the surrounding medium. Therefore, the plasmon-enhanced luminescence is a promising tool to develop more sensitive and miniaturized OSLD. (Author)

  15. Plasmon-enhanced optically stimulated luminescence

    International Nuclear Information System (INIS)

    Guidelli, E. J.; Baffa, O.; Ramos, A. P.

    2015-10-01

    Full text: Optically Stimulated Luminescence dosimeters (OSLD) have been largely used for personal, medical, and industrial radiation dosimetry. Developing highly sensitive and small-sized radiation detectors and dosimeters is essential for improving spatial resolution and consequently diagnosis quality and treatment efficacy in the case of applications in radiodiagnosis and radiation therapy, for instance. Conventional methods to improve the OSLD sensitivity consist of doping and co-doping the host materials with atoms of other elements, thereby increasing the amount of trapping and/or luminescent centers. Our group is researching on the use of the plasmon properties of noble metal nanoparticles to increase OSL intensity. Upon incidence of a light beam with appropriate resonant wavelengths, the oscillation of the free electrons at the nanoparticle surface originates the Localized Surface Plasmons (LSP) and the consequent plasmon resonance band. The interaction between the LSP and the surrounding luminescent material leads to new optical properties largely employed for enhancing several luminescent processes. Here we will show our results regarding the use of LSP to increase OSLD sensitivity. The interaction between the traps/luminescent centers and the plasmons depends on the distance between them, on the plasmon resonance band intensity and position, as well as on the surrounding medium. Therefore, the plasmon-enhanced luminescence is a promising tool to develop more sensitive and miniaturized OSLD. (Author)

  16. Confirmation of molecular formulas of metallic complexes through X-ray fluorescence quantitative analysis

    International Nuclear Information System (INIS)

    Filgueiras, C.A.L.; Marques, E.V.; Machado, R.M.

    1984-01-01

    X-ray fluorescence spectrophotometry was employed to determined the metal content in a series of five transition element complexes (Mn, Ti, Zn, V). The results confirmed the molecular formulas of these complexes, already proposed on the basis of elemental microanalysis, solution condutimetry and other analytical methods. (C.L.B.) [pt

  17. BIOASSAY STUDIES OF METAL(II) COMPLEXES OF 2,2'-(ETHANE ...

    African Journals Online (AJOL)

    Preferred Customer

    diyldiimino)diacetic acid (EDDA) were prepared and characterized. Coordination complexes of the EDDA ... corresponding amines with alkyl halide to bear diammines of the same class with different substituents. ... Bioassay studies of metal(II) complexes of 2,2'-(ethane-1,2-diyldiimino)diacetic acid. Bull. Chem. Soc. Ethiop.

  18. Hydrogen storage material and process using graphite additive with metal-doped complex hydrides

    Science.gov (United States)

    Zidan, Ragaiy [Aiken, SC; Ritter, James A [Lexington, SC; Ebner, Armin D [Lexington, SC; Wang, Jun [Columbia, SC; Holland, Charles E [Cayce, SC

    2008-06-10

    A hydrogen storage material having improved hydrogen absorbtion and desorption kinetics is provided by adding graphite to a complex hydride such as a metal-doped alanate, i.e., NaAlH.sub.4. The incorporation of graphite into the complex hydride significantly enhances the rate of hydrogen absorbtion and desorption and lowers the desorption temperature needed to release stored hydrogen.

  19. Synthesis and Spectral Characterization of Antifungal Sensitive Schiff Base Transition Metal Complexes

    Science.gov (United States)

    Sakthivel, A.; Rajasekaran, K.

    2007-01-01

    New N2O2 donor type Schiff base has been designed and synthesized by condensing acetoacetanilido-4-aminoantipyrine with 2-aminobenzoic acid in ethanol. Solid metal complexes of the Schiff base with Cu(II), Ni(II), Co(II), Mn(II), Zn(II), VO(IV), Hg(II) and Cd(II) metal ions were synthesized and characterized by elemental analyses, magnetic susceptibility, molar conduction, fast atom bombardment (FAB) mass, IR, UV-Vis, and 1H NMR spectral studies. The data show that the complexes have the composition of ML type. The UV-Vis. and magnetic susceptibility data of the complexes suggest a square-planar geometry around the central metal ion except VO(IV) complex which has square-pyramidal geometry. The in vitro antifungal activities of the compounds were tested against fungi such as Aspergillus niger, Aspergillus flavus, Rhizopus stolonifer, Candida albicans, Rhizoctonia bataicola and Trichoderma harizanum. All the metal complexes showed stronger antifungal activities than the free ligand. The minimum inhibitory concentrations (MIC) of the metal complexes were found in the range of 10~31 µg/ml. PMID:24015086

  20. Humic substances in natural waters and their complexation with trace metals and radionuclides: a review

    International Nuclear Information System (INIS)

    Boggs, S. Jr.; Livermore, D.; Seitz, M.G.

    1985-07-01

    Dissolved humic substances (humic and fulvic acids) occur in surface waters and groundwaters in concentrations ranging from less than 1 mg(C)/L to more than 100 mg(C)/L. Humic substances are strong complexing agents for many trace metals in the environment and are also capable of forming stable soluble complexes or chelates with radionuclides. Concentrations of humic materials as low as 1 mg(C)/L can produce a detectable increase in the mobility of some actinide elements by forming soluble complexes that inhibit sorption of the radionuclides onto rock materials. The stability of trace metal- or radionuclide-organic complexes is commonly measured by an empirically determined conditional stability constant (K'), which is based on the ratio of complexed metal (radionuclide) in solution to the product concentration of uncomplexed metal and humic complexant. Larger values of stability constants indicate greater complex stability. The stability of radionuclide-organic complexes is affected both by concentration variables and envionmental factors. In general, complexing is favored by increased of radionuclide, increased pH, and decreased ionic strength. Actinide elements are generally most soluble in their higher oxidation states. Radionuclides can also form stable, insoluble complexes with humic materials that tend to reduce radionuclide mobility. These insoluble complexes may be radionuclide-humate colloids that subsequently precipitate from solution, or complexes of radionuclides and humic substances that sorb to clay minerals or other soil particulates strongly enough to immobilize the radionuclides. Colloid formation appears to be favored by increased radionuclide concentration and lowered pH; however, the conditions that favor formation of insoluble complexes that sorb to particulates are still poorly understood. 129 refs., 25 figs., 19 tabs

  1. A comprehensive in vitro biological investigation of metal complexes ...

    African Journals Online (AJOL)

    Md. Mahabob Ullah Mazumder

    ... Journal of Medicine journal homepage: http://www.elsevier.com/locate/ajme .... two new complexes containing Fe (III) and Mo(VI) of two tridentate ONO donor · sets ligands. Der Chem Sin. .... Pharmaceuticals (Basel). 2014;7(4):453–463. 13.

  2. Synthesis of first row transition metal carboxylate complexes by ring ...

    Indian Academy of Sciences (India)

    tion of pyromellitic dianhydride with methanol and ring opening of pyromellitic dianhydride takes place. The corresponding carboxylate complex formed dur- ing the process can be crystallised by adding biden- tate nitrogen donor ligands such as 1,10-phenanthroline or 2,2 - bipyridine.20 From the reaction with 1,10-.

  3. Stability constant of the trisglycinto metal complexes | Na'aliya ...

    African Journals Online (AJOL)

    The stability constants of iron, manganese, cobalt, and nickel complexes of glycine have been determined in aqueous solution by potentiometric titration with standard sodium hydroxide solution. The values of the stepwise stability constants were obtained by ORIGIN '50' program. The overall stability constants of the ...

  4. Quantification of trace metals in water using complexation and filter concentration.

    Science.gov (United States)

    Dolgin, Bella; Bulatov, Valery; Japarov, Julia; Elish, Eyal; Edri, Elad; Schechter, Israel

    2010-06-15

    Various metals undergo complexation with organic reagents, resulting in colored products. In practice, their molar absorptivities allow for quantification in the ppm range. However, a proper pre-concentration of the colored complex on paper filter lowers the quantification limit to the low ppb range. In this study, several pre-concentration techniques have been examined and compared: filtering the already complexed mixture, complexation on filter, and dipping of dye-covered filter in solution. The best quantification has been based on the ratio of filter reflectance at a certain wavelength to that at zero metal concentration. The studied complex formations (Ni ions with TAN and Cd ions with PAN) involve production of nanoparticle suspensions, which are associated with complicated kinetics. The kinetics of the complexation of Ni ions with TAN has been investigated and optimum timing could be found. Kinetic optimization in regard to some interferences has also been suggested.

  5. Selective Decontamination Effect of Metal Ions in Soil Using Supercritical CO2 and TBP Complex

    International Nuclear Information System (INIS)

    Park, Jihye; Park, Kwangheon; Jung, Wonyoung

    2014-01-01

    Decontamination of soil pollution is difficult because the type of contamination largely depends on the characteristics of the pollutant and the area. Also, existing soil decontamination methods generate large quantities of secondary waste and additional process costs. For this reason, new decontamination methods are always under active investigation. A method involving the use of supercritical carbon dioxide with excellent permeability in place of chemical solvents is currently being studied. Unlike other heavy metals in fission products, uranium is used as fuel, and must be handled carefully. Therefore, in this paper, we studied a supercritical carbon dioxide method for decontaminating heavy metal ions in soil using tri-n-butyl phosphate(TBP), which is well known as a ligand for the extraction of metal ions of actinium. We investigated the decontamination effect of heavy metal ions in the soil using TBP-HNO 3 Complex and supercritical carbon dioxide. The study results showed that when heavy metals in soil are extracted using supercritical carbon dioxide, the extraction efficiency is different according to the type of pollutant metal ions in the soil. When TBP-HNO 3 Complex is used with an extractant, uranium extraction is very effective, but lithium, strontium, and cesium extraction is not effective. Therefore, in the case of a mixture of uranium and other metals such as lithium, strontium, cesium, and so on in soil contaminated by fission product leaks from nuclear power plants, we can selectively decontaminate uranium with supercritical carbon dioxide and TBP-HNO 3 Complex

  6. Lutetium-177 complexation of DOTA and DTPA in the presence of competing metals

    International Nuclear Information System (INIS)

    Watanabe, Satoshi; Ishioka, Noriko S.; Hashimoto, Kazuyuki

    2013-01-01

    177 Lu complexation of DOTA and DTPA is investigated by the addition of Ca(II), Fe(II) and Zn(II). The 177 Lu complexation yield of DTPA was higher than that of DOTA in the presence of Ca(II), Fe(II) and Zn(II). Therefore, it was found that the 177 Lu complexation of DTPA was more advantageous compared with DOTA in the presence of competing metals, Ca, Fe and Zn. (author)

  7. Synthesis of complex plutonium oxides with alkaline-earth metals

    International Nuclear Information System (INIS)

    Suzuki, Yasufumi; Nakajima, Kunihisa; Iwai, Takashi; Ohmichi, Toshihiko; Yamawaki, Michio.

    1995-03-01

    Complex plutonium(IV) oxides with strontium and barium, SuPuO 3 and BaPuO 3 , were synthesized and their crystal structure was analyzed. Compacted mixture of plutonium dioxide powder and the carbonate of strontium or barium was heated in a stream of argon gas using a cell with a small orifice. The products obtained were found to be composed of a nearly single phase showing the structure of orthorhombic slightly distorted from cubic. (author)

  8. On complexing of trivalent iron alcoholates. On transition metal alkoxyaluminates

    International Nuclear Information System (INIS)

    Rogova, T.V.; Turova, N.Ya.; Kozlova, N.I.

    1986-01-01

    When studying solubility in system Y(OR) 3 -Fe(OR) 3 -ROH (where R=i-Pr), the existence in solution of two complexes YF 2 (OR) 9 and YFe 3 (OR) 12 is ascertained, the range of X-ray amorphous glass formation being located between the two compositions. Preparative, IR- and mass-spectrometric studies of the glasses testify to the absence of bimetal alcoholates of Fe and Y of a definite composition in solid and gaseous phases

  9. Poly-functional description of metal complexation by natural organic matter: theory and practice

    International Nuclear Information System (INIS)

    Buffle, J.; Filella, M.; Altmann, R.S.

    1995-01-01

    The Differential Equilibrium Function (DEF) approach to metal complexation interpretation and prediction is compared to other models or approaches. The basic features of DEF are summarized, both from the experimental and theoretical points of view. The relation of DEF with key environmental concepts or parameters, in particular minor vs major complexing sites, the buffering intensity of natural organic matter (NOM), and their poly functional vs polyelectrolyte properties, is discussed. The relation between DEF and Freundlich isotherm is described quantitatively. The practical applications of DEF are discussed for (i) interpretation of metal complexation by NOM, and (ii) prediction of metal complexation by NOM. It is shown that DEF (i.e. sound extrapolation is possible with care). DEF cans be readily incorporated in metal species distribution codes (e.g. MINEQL). DEF is not equivalent to a molecular complexation model which describes complexation at each individual site; DEF gives a rigorous representation of complexation by NOM as a whole chemical system. (authors). 23 refs., 6 figs

  10. Wastewater treatment from heavy metal ions using nanoactivated complexes of natural zeolite and diatomite

    Directory of Open Access Journals (Sweden)

    Malkin Polad

    2018-04-01

    Full Text Available Despite the wide practical use of sorption methods and complexones in treatment of industrial wastewater, some problems are still to be solved in this field. These are the most significant: insufficient sorption capacity of materials, lack of reliable methods for regenerating sorbents and resource-saving ecology friendly treatment technologies with the use of sorbents as well as methods of utilization of heavy metals from waste by complex formation. An important factor affecting the behavior of heavy metals in the soil is the medium acidity. With a neutral and slightly alkaline reaction of the medium, hardly soluble compounds are formed: hydroxides, sulphides, phosphates, carbonates, and oxalates of heavy metals. When acidity increases the reverse process runs in the soil: hardly soluble compounds become more mobile, while mobility of many heavy metals increases. However, the effect of soil acidity on mobility of heavy metals is ambiguous. Although mobility of many heavy metals decreases with increasing pH of the medium (for example, Fe, Mn, Zn, Co, etc., there are a number of metals whose mobility increases with soil neutralization. These include molybdenum and chromium, which are able to form soluble salts in a weak ly acidic and alkaline medium. In addition, heavy metals such as mercury and cadmium are able to maintain mobility in an alkaline medium through formation of complex compounds with organic matter in soils. Heavy metals interact with a solid phase of the soil by mechanisms of specific and nonspecific adsorption. In this article, a technique of wastewater treatment from heavy metal ions using nanoactivated complexes of natural zeolite and diatomite is proposed. This technique can reduce significant costs in preparation of raw materials and subsequent chemical modification of them. Technological solutions aimed at disposal and recycling of industrial wastewater have been proposed. These solutions make it possible to obtain the water

  11. The role of cerium variable charge state in the luminescence and scintillation mechanism in complex oxide scintillators: the effect of air annealing

    Czech Academy of Sciences Publication Activity Database

    Nikl, Martin; Babin, Vladimir; Mareš, Jiří A.; Kamada, K.; Kurosawa, S.; Yoshikawa, A.; Touš, J.; Houžvička, J.; Blažek, K.

    2016-01-01

    Roč. 169, Jan (2016), s. 539-543 ISSN 0022-2313. [International Conference on Luminescence and Optical Spectroscopy of Condensed Matter /17./. Wroclaw, 13.07.2014-18.07.2014] R&D Projects: GA ČR GA13-09876S; GA TA ČR TA04010135 Institutional support: RVO:68378271 Keywords : scintillator * aluminum garnets * perovskites * air annealing Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.686, year: 2016

  12. Luminescent beam stop

    Energy Technology Data Exchange (ETDEWEB)

    Bryant, Diane; Morton, Simon A.

    2017-10-25

    This disclosure provides systems, methods, and apparatus related to beam stops. In one aspect, a device comprises a luminescent material, a beam stop plate, and an optical fiber. The luminescent material is a parallelepiped having a first side and a second side that are squares and having a third side that is a rectangle or a square. The first side and the second side are perpendicular to the third side. The beam stop plate is attached to the first side of the luminescent material. The optical fiber has a first end and a second end, with the first end of the optical fiber attached to the third side of the luminescent material.

  13. Luminescence detection of shellfish

    International Nuclear Information System (INIS)

    Sanderson, D.C.W.; Carmichael, L.A.; Spencer, J.Q.; Naylor, J.D.

    1996-01-01

    The Scottish Universities Research and Reactor Centre (SURRC) has been active in the development and application of luminescence techniques in the detection of irradiated foods, in support of UK legislation. Thermoluminescence (TL), photostimulated luminescence (PSL) and photo-transfer luminescence (PTTL) are radiation-specific phenomena which arise due to energy stored by trapped charge carriers following irradiation. The energy released following stimulation is accompanied by detectable luminescence. The TL method involves preparation of pure silicate extracts from the sample and subsequent TL analysis, whereas PSL uses stimulation by electromagnetic radiation (visible, or near visible wavelengths) thus avoiding heating the sample. (author)

  14. Molecular Speciation of Trace Metal Organic Complexes in the Pacific Ocean

    Science.gov (United States)

    Repeta, D.; Boiteau, R. M.; Bundy, R. M.; Babcock-Adams, L.

    2017-12-01

    Microbial production across approximately one third of the surface ocean is limited by extraordinarily low (picomolar) concentrations of dissolved iron, essentially all of which is complexed to strong organic ligands of unknown composition. Other biologically important trace metals (cobalt, copper, zinc, nickel) are also complexed to strong organic ligands, which again have not been extensively characterized. Nevertheless, organic ligands exert a strong influence on metal bioavailability and toxicity. For example, amendment experiments using commercially available siderophores, organic compounds synthesized by microbes to facilitate iron uptake, show these ligands can both facilitate or impede iron uptake depending on the siderophore composition and available uptake pathways. Over the past few years we have developed analytical techniques using high pressure liquid chromatography interfaced with inductively coupled plasma and electrospray ionization mass spectrometry to identify and quantify trace metal organic complexes in laboratory cultures of marine microbes and in seawater. We found siderophores to be widely distributed in the ocean, particularly in regions characterized by low iron concentrations. We also find chemically distinct complexes of copper, zinc, colbalt and nickel that we have yet to fully characterize. We will discuss some of our recent work on trace metal organic speciation in seawater and laboratory cultures, and outline future efforts to better understand the microbial cycling of trace metal organic complexes in the sea.

  15. Spectroscopic characterization of metal complexes of novel Schiff base. Synthesis, thermal and biological activity studies

    Science.gov (United States)

    Omar, M. M.; Mohamed, Gehad G.; Ibrahim, Amr A.

    2009-07-01

    Novel Schiff base (HL) ligand is prepared via condensation of 4-aminoantipyrine and 2-aminobenzoic acid. The ligand is characterized based on elemental analysis, mass, IR and 1H NMR spectra. Metal complexes are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance and thermal analyses (TGA, DrTGA and DTA). The molar conductance data reveal that all the metal chelates are non-electrolytes. IR spectra show that HL is coordinated to the metal ions in a uninegatively tridentate manner with NNO donor sites of the azomethine N, amino N and deprotonated caroxylic-O. From the magnetic and solid reflectance spectra, it is found that the geometrical structures of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, ΔH*, ΔS* and ΔG* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia Coli, Pseudomonas aeruginosa, Staphylococcus Pyogones and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent Shciff base ligand against one or more bacterial species.

  16. Metal complexes in cancer therapy – an update from drug design perspective

    Directory of Open Access Journals (Sweden)

    Ndagi U

    2017-03-01

    Full Text Available Umar Ndagi, Ndumiso Mhlongo, Mahmoud E Soliman Molecular Modelling and Drug Design Research Group, School of Health Sciences, University of KwaZulu-Natal, Westville, Durban, South Africa Abstract: In the past, metal-based compounds were widely used in the treatment of disease conditions, but the lack of clear distinction between the therapeutic and toxic doses was a major challenge. With the discovery of cisplatin by Barnett Rosenberg in 1960, a milestone in the history of metal-based compounds used in the treatment of cancers was witnessed. This forms the foundation for the modern era of the metal-based anticancer drugs. Platinum drugs, such as cisplatin, carboplatin and oxaliplatin, are the mainstay of the metal-based compounds in the treatment of cancer, but the delay in the therapeutic accomplishment of other metal-based compounds hampered the progress of research in this field. Recently, however, there has been an upsurge of activities relying on the structural information, aimed at improving and developing other forms of metal-based compounds and nonclassical platinum complexes whose mechanism of action is distinct from known drugs such as cisplatin. In line with this, many more metal-based compounds have been synthesized by redesigning the existing chemical structure through ligand substitution or building the entire new compound with enhanced safety and cytotoxic profile. However, because of increased emphasis on the clinical relevance of metal-based complexes, a few of these drugs are currently on clinical trial and many more are awaiting ethical approval to join the trial. In this review, we seek to give an overview of previous reviews on the cytotoxic effect of metal-based complexes while focusing more on newly designed metal-based complexes and their cytotoxic effect on the cancer cell lines, as well as on new approach to metal-based drug design and molecular target in cancer therapy. We are optimistic that the concept of selective

  17. Luminescent amine sensor based on europium(III) chelate.

    Science.gov (United States)

    Petrochenkova, Nataliya V; Mirochnik, Anatolii G; Emelina, Tatyana B; Sergeev, Alexander A; Leonov, Andrei A; Voznesenskii, Sergey S

    2018-07-05

    The effect of methylamine vapor on luminescence of Eu(III) tris-benzoylacetonate (I) immobilized in thin-layer chromatography plates has been investigated. It has been revealed that interaction of I with analyte vapor results in increase of the intensity of Eu(III) luminescence. The mechanism of the effect of methylamine vapors on intensification of the Eu(III) luminescence has been suggested using the data of IR spectroscopy and quantum chemistry calculations. The mechanism of luminescence sensitization consists in bonding of an analyte molecule with a water molecule into the coordination sphere of Eu(III). As a result, the bond of a water molecule with the luminescence centre weakens, rigid structural fragment including europium ion, water and methylamine molecules forms. The presence of such fragment must naturally promote decrease of influence of OH-vibrations on luminescence of the complex I. Copyright © 2018 Elsevier B.V. All rights reserved.

  18. The preparation and use of metal salen complexes derived from cyclobutane diamine

    Science.gov (United States)

    Patil, Smita

    The helix is an important chiral motif in nature, there is increasing development in field of helical transition metal complexes and related supramolecular structures. Hence, the goals of this work are to apply the principles of helicity in order to produce metal complexes with predictable molecular shapes and to study their properties as asymmetric catalysts. Computational studies suggest that the (1R,2 R)-cyclobutyldiamine unit can produce highly twisted salen complexes with a large energy barrier between the M and P helical forms. To test this prediction, the tartrate salt of (1R,2R)-cyclobutyldiamine was synthesized and condensed with a series of saliclaldehydes to produce novel salen ligands. The salicylaldehydes chosen have extended phenanthryl or benz[a]anthryl sidearms to encourage formation of helical coordination complexes. These ligands were metallated with zinc, iron and manganese salts to produce salen metal complexes which were characterized by NMR analysis, high-resolution mass spectrometry, and IR spectroscopy. A second ligand type, neutral bis(pyridine-imine) has also been synthesized from (1R,2R)-cyclobutyldiamine and quinolylaldehydes. The synthesis of bis(pyridine-imine) ligands was conducted using greener method, solvent assisted grinding. These ligands, in-situ with nickel metal salts, showed good catalytic activity for asymmetric Diels-Alder reactions. The third ligand type studied was chiral acid-functionalized Schiff-base ligands. These were synthesized by the condensation of 3-formyl-5-methyl salicylic acid and (1R,2R)-cyclobutyldiamine. With this type of ligand, there is possibility of producing both mono and dinuclear metal complexes. In our studies, we were only able to synthesize mononuclear complexs. These were tested as catalysts for asymmetric direct Mannich-type reaction, but were found to be ineffective.

  19. Interaction of natural complexing agents with soil bound heavy metals -geochemical and environmental technical aspects

    International Nuclear Information System (INIS)

    Fischer, K.

    1994-01-01

    The sanitation of heavy metal polluted soils requires the application of an adequate technology, which should be consistent in its ecological aims and methodology. Therefore a research programme has been developed at the 'Institute of Ecological Chemistry' of the 'GSF-Research Center', Neuherberg, which has its starting point in the study of influences of natural organic complexing agents on the chemical activity and dynamic of heavy metals in soils. The groundlaying idea is to elevate the concentration of complexing agents in the soil solution by additional application and possible stimulation of their microbial production to such an extent, that heavy metals will be enhanced solubilized, mobilized and removed together with the seepage water. Batch experiments in order to extract heavy metals from typical soil components (bentonite, peat) by amino acids demonstrate, that removal rates up to 95% can be obtained. (orig.) [de

  20. A molecular mechanics (MM3(96)) force field for metal-amide complexes

    International Nuclear Information System (INIS)

    Hay, B.P.; Clement, O.; Sandrone, G.; Dixon, D.A.

    1998-01-01

    A molecular mechanics (MM3(96)) force field is reported for modeling metal complexes of amides in which the amide is coordinated through oxygen. This model uses a points-on-a-sphere approach which involves the parameterization of the Msingle bondO stretch, the Msingle bondO double-bond C bend, and the Msingle bondO double-bond Csingle bondX (X = C, H, N) torsion interactions. Relationships between force field parameters and metal ion properties (charge, ionic radius, and electronegativity) are presented that allow the application of this model to a wide range of metal ions. The model satisfactorily reproduces the structures of over fifty amide complexes with the alkaline earths, transition metals, lanthanides, and actinides

  1. Selective transport and incorporation of highly charged metal and metal complex ions in self-assembled polyelectrolyte multilayer membranes

    International Nuclear Information System (INIS)

    Toutianoush, Ali; Tieke, Bernd

    2002-01-01

    The transport of aqueous salts containing mono-, di- and trivalent metal and tetravalent metal complex ions across ultrathin polyvinylammonium/polyvinylsulphate (PVA/PVS) membranes is described. The membranes were prepared by electrostatic layer-by-layer (LBL) assembly of the two polyelectrolytes. Using spectroscopic measurements and permeability studies, it is demonstrated that the transport of copper(II) chloride, lanthanum(III) chloride, barium chloride and potassium hexacyanoferrate(II) is accompanied by the permanent incorporation of the metal and metal complex ions in the membrane. Upon the uptake of copper, lanthanum and hexacyanoferrate ions, the membranes become cross-linked so that the permeation rates of other salts not taken up by the membrane, e.g. sodium chloride, potassium chloride and magnesium chloride, are decreased. The uptake of barium ions leads to a decrease of the cross-linking density of the membrane so that the permeation rate of NaCl is increased. Possible mechanisms for the ion uptake are discussed

  2. Metal distributions in complexes with Chlorella vulgaris in seawater and wastewater

    Energy Technology Data Exchange (ETDEWEB)

    Pascucci, P.R.; Kowalak, A.D.

    1999-10-01

    Divalent cadmium (Cd), copper (Cu), iron (Fe), nickel (Ni), lead (Pb), and zinc (Zn) simultaneous complexes with an algal biomass Chlorella vulgaris were studied for bioremediation purposes in various aqueous media: distilled-deionized water (DDIW), seawater, nuclear-reactor pool water, and process wastewater. Reactions were monitored using various dry masses of algae at constant temperature and constant metal concentrations for reaction times ranging from 0 to 150 minutes. Complexes occurred within 30 minutes and reached a steady state after 80 to 120 minutes. Distribution constants (K{prime}{sub d}) were calculated for the complexes and relative orders of K{prime}{sub d} were reported. The K{prime}{sub d} are used to evaluate relative efficiency of metal remediation from waters. Lead, Cu, and Ni complexes had the greatest K{prime}{sub d} values and those metals were most efficiently removed from these waters. Zinc and Fe formed the most labile complexes. The order of K{prime}{sub d} values for complexes in DDIW was Pb > Cu > Cd > Zn, then Cu > Cd > Zn in seawater, Cd > Cu > Zn in reactor pool water, and Ni > Cd > Cu > Zn > Fe in wastewater. C. vulgaris biomass may potentially be used as an alternative to traditional water treatment methods for simultaneous extraction of metals from seawater, process wastewater, or drinking water.

  3. Synthesis, Characterization and Biological Evaluation of Transition Metal Complexes Derived from N, S Bidentate Ligands

    Directory of Open Access Journals (Sweden)

    Enis Nadia Md Yusof

    2015-05-01

    Full Text Available Two bidentate NS ligands were synthesized by the condensation reaction of S-2-methylbenzyldithiocarbazate (S2MBDTC with 2-methoxybenzaldehyde (2MB and 3-methoxybenzaldehyde (3MB. The ligands were reacted separately with acetates of Cu(II, Ni(II and Zn(II yielding 1:2 (metal:ligand complexes. The metal complexes formed were expected to have a general formula of [M(NS2] where M = Cu2+, Ni2+, and Zn2+. These compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and various spectroscopic techniques. The magnetic susceptibility measurements and spectral results supported the predicted coordination geometry in which the Schiff bases behaved as bidentate NS donor ligands coordinating via the azomethine nitrogen and thiolate sulfur. The molecular structures of the isomeric S2M2MBH (1 and S2M3MBH (2 were established by X-ray crystallography to have very similar l-shaped structures. The Schiff bases and their metal complexes were evaluated for their biological activities against estrogen receptor-positive (MCF-7 and estrogen receptor-negative (MDA-MB-231 breast cancer cell lines. Only the Cu(II complexes showed marked cytotoxicity against the cancer cell lines. Both Schiff bases and other metal complexes were found to be inactive. In concordance with the cytotoxicity studies, the DNA binding studies indicated that Cu(II complexes have a strong DNA binding affinity.

  4. Synthesis, structure, DNA/BSA binding and antibacterial studies of NNO tridentate Schiff base metal complexes

    Science.gov (United States)

    Sakthi, Marimuthu; Ramu, Andy

    2017-12-01

    A new salicylaldehyde derived 2,4-diiodo-6-((2-phenylaminoethylimino)methyl)phenol Schiff base(L) and its transition metal complexes of the type MLCl where, M = Cu(II), Ni(II), Co(II), Mn(II) and Zn(II) have been synthesized. The coordination mode of Schiff base holding NNO donor atoms with metal ions was well investigated by elemental analysis, ESI-mass as well as IR, UV-vis, CV and NMR spectral studies. The binding efficiency and mode of these complexes with biological macromolecules viz., herring sperm DNA (HS- DNA) and bovine serum albumin (BSA) have been explored through various spectroscopic techniques. The characteristic changes in absorption, emission and, circular dichroism spectra of the complexes with DNA indicate the noticeable interaction between them. From the all spectral information complexes could interact with DNA via non-intercalation mode of binding. The hyperchromisim in absorption band and hypochromisim in emission intensity of BSA with different complex concentrations shown significant information, and the binding affinity value has been predicted from Stern-Volmer plots. Further, all the complexes could cleave the circular plasmid pUC19 DNA efficiently by using an activator H2O2. The ligand and all metal(II) complexes showed good antibacterial activities. The molecular docking studies of the complexes with DNA were performed in order to make a comparison and conclusion with spectral technic results.

  5. Sub-ppb level detection of uranium using ligand sensitized luminescence

    International Nuclear Information System (INIS)

    Kumar, Satendra; Maji, S.; Joseph, M.; Sankaran, K.

    2015-01-01

    Uranyl ion (UO 2 2+ ) is known to exhibit weak luminescence in aqueous medium due to poor molar absorptivity and low quantum yield. In order to enhance the luminescence of uranyl ion in aqueous medium, luminescence enhancing reagents such as H 3 PO 4 , H 2 SO 4 , HClO 4 have been widely used. Like lanthanides, uranyl luminescence can also be sensitized by using some organic ligands. Pyridine 2,6-dicarboxylic acid (PDA) has shown enhancement of luminescence of uranyl in aqueous medium. Enhancement in intensity is due to sensitization of uranyl luminescence by PDA. In order to see the effect of non-aqueous medium, in this work, luminescence of uranyl-PDA complex has been studied in acetonitrile medium. More than one order luminescence enhancement has been observed compared to UO 2 2+ - PDA complex in aqueous medium. The lifetime of uranyl luminescence of the complex in acetonitrile medium is 90 μs which is very high compared to 10 μs in aqueous medium, suggesting that the luminescence enhancement is a result of reduction in non-radiative decay channels in acetonitrile medium. The large enhancement of uranyl luminescence of uranyl-PDA complex in acetonitrile medium can be used for ultra-trace level detection of uranium. Linearity in the luminescence intensity has been observed over the uranium concentration range of 5 to 80 ppb and the detection limit calculated using the criterion of 3 σ is ~ 0.2 ppb. (author)

  6. High-performance liquid chromatography of metal complexes of pheophytins a and b

    International Nuclear Information System (INIS)

    Brykina, G.D.; Lazareva, E.E.; Uvarova, M.I.; Shpigun, O.A.

    1997-01-01

    Cu(2), Zn(2), Pb(2), Hg(2), and Ce(4) complexes of phenophytins a and b were synthesized. The chromatographic retention parameters of pheophytins a and b, chlorophylls a and b, and the above complexes were determined under conditions of normal-phase and reversed-phase high-performance liquid chromatography (HPLC). The adsorption of metal pheophytinates in the hexane-n-butanol (96:4)-Silasorb 600 and acetonitrile-ethanol-acetic acid (40:40:16)-Nucleosil C 18 systems was studied by HPLC. Factors that affect the chromatographic and adsorption characteristics of compounds (structural differences between pheophytinates of the a and b series, the nature of the central metal atom, and the nature of the mobile and stationary phases) are discussed. It is demonstrated that pheophytins a and b their metal complexes can be identified and quantiatively determined by HPLC in the concentration range (0.6-44.0)[10 -6 M

  7. Structural and Spectral Properties of Curcumin and Metal- Curcumin Complex Derived from Turmeric (Curcuma longa)

    Science.gov (United States)

    Bich, Vu Thi; Thuy, Nguyen Thi; Binh, Nguyen Thanh; Huong, Nguyen Thi Mai; Yen, Pham Nguyen Dong; Luong, Tran Thanh

    Structural and spectral properties of curcumin and metal- curcumin complex derived from turmeric (Curcuma longa) were studied by SEM and vibrational (FTIR and Raman) techniques. By comparison between curcumin commercial, fresh turmeric and a yellow powder obtained via extraction and purification of turmeric, we have found that this insoluble powder in water is curcumin. The yellow compound could complex with certain ion metal and this metal-curcumin coloring complex is water soluble and capable of producing varying hues of the same colors and having antimicrobial, cytotoxicity activities for use in foodstuffs and pharmacy. The result also demonstrates that Micro-Raman spec-troscopy is a valuable non-destructive tool and fast for investigation of a natural plant even when occurring in low concentrations.

  8. New trends in the optical and electronic applications of polymers containing transition-metal complexes.

    Science.gov (United States)

    Liu, Shu-Juan; Chen, Yang; Xu, Wen-Juan; Zhao, Qiang; Huang, Wei

    2012-04-13

    Polymers containing transition-metal complexes exhibit excellent optical and electronic properties, which are different from those of polymers with a pure organic skeleton and combine the advantages of both polymers and metal complexes. Hence, research about this class of polymers has attracted more and more interest in recent years. Up to now, a number of novel polymers containing transition-metal complexes have been exploited, and significant advances in their optical and electronic applications have been achieved. In this article, we summarize some new research trends in the applications of this important class of optoelectronic polymers, such as chemo/biosensors, electronic memory devices and photovoltaic devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Kinetic studies of the solvent extraction of metal complexes

    International Nuclear Information System (INIS)

    Mirza, M.Y.; Nwabue, F.I.; Okafo, E.N.

    1981-01-01

    The rate of forward extraction of Zr(IV) from 2M sulphuric acid into 1-phenyl-3-methyl-4-benzoyl-pyrazole-5-one (HPsub (z)) dissolved in chloroform and backward extraction of the tetrakis-chelate, Zr(Pz) 4 have been measured under various conditions. The rate of forward reaction is proportional to [Zr 4+ ], [HPsub(z)] 2 and [H + ] -2 , while that of back extraction to [Zr(Pz) 4 ]sub(org), [HPsub(z)] -2 sub(org) and [H + ] 2 . The rate determining step in the forward extraction is established to be the formation of the second complex between the dissociated form of HPz, Pz - and the Zr(H 2 O) 2 SO 4 Pz + species in the aqueous phase while it is the reverse in the backward extraction. The velocity constants for both rate controlling steps have been determined and the extraction constant agrees with the value obtained from the equilibrium data. (author)

  10. Paramagnetic metal complexes as potential relaxation agents for NMR imaging

    International Nuclear Information System (INIS)

    Coroiu, Ilioara; Demco, D. E.; Darabont, Al.; Bogdan, M.

    1997-01-01

    The development of nuclear magnetic resonance (NMR) imaging technique as a clinical diagnostic modality has prompted the need for a new class of pharmaceuticals. These drugs must be administered to a patient in order to enhance the image contrast between the normal and diseased tissue and/or indicate the status of organ function or blood flow. Paramagnetic compounds are presently undergoing extensive evaluation as contrast agents in magnetic resonance imaging (MRI). These agents increase contrast in MRI by differentially localizing in tissue where they increase the relaxation rates of nearby water protons. The longitudinal R 1 and transverse R 2 relaxivities were measured as a function of molar concentrations for some new paramagnetic complexes like the following: dysprosium, erbium and gadolinium citrates, gadolinium methylene diphosphonate, dysprosium and gadolinium iminodiacetate, manganese para-aminobenzoate and copper nicotinate. The available theoretical approaches for quantitative understanding are presented. (authors)

  11. 'Pincer' dicarbene complexes of some early transition metals and uranium.

    Science.gov (United States)

    Pugh, David; Wright, Joseph A; Freeman, Sandra; Danopoulos, Andreas A

    2006-02-14

    The complexes [(C-N-C)MX(n)(thf)(m)] with the 'pincer' 2,6-bis(imidazolylidene)pyridine, (C-N-C) = 2,6-bis(arylimidazol-2-ylidene)pyridine, aryl = 2,6-Pr(i)2C6H3, M = V, X = Cl, n = 2, m = 1 1a; M = Cr, X = Cl, n = 2, m = 0, 2a, X = Br, 2b; M = Mn, X = Br, n = 2, m = 0, 3; M = Nb, X = Cl, n = 3, m = 0, 4; and M = U, X = Cl, n = 4, m = 0, 5, were synthesised by (a) substitution of labile tmed (1a), thf (2a, 3, 5) or dme (4) by free (C-N-C) or by (b) reaction of the bisimidazolium salt (CH-N-CH)Br2 with {Cr[N(SiMe3)2]2(thf)2} followed by amine elimination (2b). Attempted alkylation of 1a, 2, 3a and 4 with Grignard or alkyl lithiums gave intractable mixtures, and in one case [reaction of 1a with (mesityl)MgBr] resulted in exchange of Cl by Br (1b). Oxidation of 1a or [(C-N-C)VCl3] with 4-methylmorpholine N-oxide afforded the trans-V(C-N-C)(=O)Cl2, 6, which by reaction with AgBF4 in MeCN gave trans-[V(C-N-C)(=O)(MeCN)2][BF4]2, 7. Reaction of 1a with p-tolyl azide gave trans-V(C-N-C)(=N-p-tolyl)Cl2 8. The complex trans-Ti(C-N-C)(=NBu(t))Cl2, 9, was prepared by substitution of the pyridine ligands in Ti(NBu(t))Cl2(py)3 by C-N-C.

  12. Alkali Metal Variation and Twisting of the FeNNFe Core in Bridging Diiron Dinitrogen Complexes.

    Science.gov (United States)

    McWilliams, Sean F; Rodgers, Kenton R; Lukat-Rodgers, Gudrun; Mercado, Brandon Q; Grubel, Katarzyna; Holland, Patrick L

    2016-03-21

    Alkali metal cations can interact with Fe-N2 complexes, potentially enhancing back-bonding or influencing the geometry of the iron atom. These influences are relevant to large-scale N2 reduction by iron, such as in the FeMoco of nitrogenase and the alkali-promoted Haber-Bosch process. However, to our knowledge there have been no systematic studies of a large range of alkali metals regarding their influence on transition metal-dinitrogen complexes. In this work, we varied the alkali metal in [alkali cation]2[LFeNNFeL] complexes (L = bulky β-diketiminate ligand) through the size range from Na(+) to K(+), Rb(+), and Cs(+). The FeNNFe cores have similar Fe-N and N-N distances and N-N stretching frequencies despite the drastic change in alkali metal cation size. The two diketiminates twist relative to one another, with larger dihedral angles accommodating the larger cations. In order to explain why the twisting has so little influence on the core, we performed density functional theory calculations on a simplified LFeNNFeL model, which show that the two metals surprisingly do not compete for back-bonding to the same π* orbital of N2, even when the ligand planes are parallel. This diiron system can tolerate distortion of the ligand planes through compensating orbital energy changes, and thus, a range of ligand orientations can give very similar energies.

  13. Silica nanoparticles with a substrate switchable luminescence

    International Nuclear Information System (INIS)

    Bochkova, O D; Mustafina, A R; Fedorenko, S V; Konovalov, A I

    2011-01-01

    Silica nanoparticles with visible (Tb and Ru doped), near IR (Yb doped) and dual visible-near IR luminescence (Ru-Yb doped) were obtained by reverse w/o microemulsion procedure. Plenty of luminescent complexes (from 4900 to 10000) encapsulated into each nanoparticle ensures the intensive luminescence of nanoparticles and their applicability as biomarkers. The silica surface decoration by definite anchor groups is the required step for the gaining to these nanoparticles marking and sensing functions. Thus covalent and non-covalent surface modification of these nanoparticles was developed to provide the binding with biotargets and sensing of anions. The dicationic surfactant coating of negatively charged Tb(III)-TCAS doped silica nanoparticles was chosen as the basis for the anion responsible system. The reversible insertion of the quenching anions (namely phenol red) into the surfactant based layer at the surface of luminescent nanoparticles switches off the Tb-centered luminescence. In turn the reversible reestablishment of the luminescence results from the competitive insertion of the non-quenching anions into the surfactant layer at the silica/water interface. The hydrophobic anions exemplified by dodecylsulfates versus hydrophilic ones (hydrophosphates) are preferable in the competition with phenol red anions.

  14. Thermal quenching of luminescence processes in feldspars

    DEFF Research Database (Denmark)

    Poolton, N.R.J.; Bøtter-Jensen, L.; Duller, G.A.T.

    1995-01-01

    , which display very different behaviour. The first involves the internal transitions of common transition metal ions. The second is typical of centres not displaying excited states within the band gap that are likely to arise from direct recombination between the conduction band and the ground state......The technique of optically stimulated luminescence has important uses in the dose evaluation of irradiated feldspars. The luminescence process involves the eviction of electrons from donor traps, charge transfer through the conduction band, and recombination at acceptor sites; each...

  15. Solvent-induced controllable synthesis, single-crystal to single-crystal transformation and encapsulation of Alq3 for modulated luminescence in (4,8)-connected metal-organic frameworks.

    Science.gov (United States)

    Lan, Ya-Qian; Jiang, Hai-Long; Li, Shun-Li; Xu, Qiang

    2012-07-16

    In this work, for the first time, we have systematically demonstrated that solvent plays crucial roles in both controllable synthesis of metal-organic frameworks (MOFs) and their structural transformation process. With solvent as the only variable, five new MOFs with different structures have been constructed, in which one MOF undergoes solvent-induced single-crystal to single-crystal (SCSC) transformation that involves not only solvent exchange but also the cleavage and formation of coordination bonds. Particularly, a significant crystallographic change has been realized through an unprecedented three-step SCSC transformation process. Furthermore, we have demonstrated that the obtained MOF could be an excellent host for chromophores such as Alq3 for modulated luminescent properties.

  16. Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions

    KAUST Repository

    Kaur, Sukhmanpreet

    2017-07-04

    Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4 ± 0.05, 7 ± 0.05 and 9 ± 0.05) and three different temperatures (15 ± 0.5°C, 30 ± 0.5°C and 45 ± 0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

  17. Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions

    Science.gov (United States)

    Kaur, Sukhmanpreet; Kumar, Vijay; Chawla, Mohit; Cavallo, Luigi; Poater, Albert; Upadhyay, Niraj

    2017-07-01

    Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4±0.05, 7±0.05 and 9±0.05) and three different temperatures (15±0.5°C, 30±0.5°C and 45±0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

  18. Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions

    KAUST Repository

    Kaur, Sukhmanpreet; Kumar, Vijay; Chawla, Mohit; Cavallo, Luigi; Poater, Albert; Upadhyay, Niraj

    2017-01-01

    Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4 ± 0.05, 7 ± 0.05 and 9 ± 0.05) and three different temperatures (15 ± 0.5°C, 30 ± 0.5°C and 45 ± 0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

  19. Photoactivatable metal complexes: from theory to applications in biotechnology and medicine.

    Science.gov (United States)

    Smith, Nichola A; Sadler, Peter J

    2013-07-28

    This short review highlights some of the exciting new experimental and theoretical developments in the field of photoactivatable metal complexes and their applications in biotechnology and medicine. The examples chosen are based on some of the presentations at the Royal Society Discussion Meeting in June 2012, many of which are featured in more detail in other articles in this issue. This is a young field. Even the photochemistry of well-known systems such as metal-carbonyl complexes is still being elucidated. Striking are the recent developments in theory and computation (e.g. time-dependent density functional theory) and in ultrafast-pulsed radiation techniques which allow photochemical reactions to be followed and their mechanisms to be revealed on picosecond/nanosecond time scales. Not only do some metal complexes (e.g. those of Ru and Ir) possess favourable emission properties which allow functional imaging of cells and tissues (e.g. DNA interactions), but metal complexes can also provide spatially controlled photorelease of bioactive small molecules (e.g. CO and NO)--a novel strategy for site-directed therapy. This extends to cancer therapy, where metal-based precursors offer the prospect of generating excited-state drugs with new mechanisms of action that complement and augment those of current organic photosensitizers.

  20. Preparation and Characterization of Styrene Bearing Diethanolamine Side Group, Styrene Copolymer Systems, and Their Metal Complexes

    Directory of Open Access Journals (Sweden)

    Aslışah Açıkses

    2018-01-01

    Full Text Available The two copolymer systems of styrene bearing diethanol amine side group and styrene were prepared by free radical polymerization method at 60°C in presence of 1,4-dioxane as solvent and AIBN as initiator. Their metal complexes were prepared by reaction of the copolymer used as ligand P(DEAMSt-co-StL′′ and Ni(II and Co(II metal ions, which was carried out in presence of ethanol and NaOH at 65°C for 48 h in pH = 7.5. The structures of the copolymers used as ligand and metal complexes were identified by FT-IR, 1H-NMR spectra, and elemental analysis. The properties of the copolymers used as ligand and metal complexes were characterized by SEM-EDX, AAS, DSC, TGA, and DTA techniques. Then, the electrical properties of the copolymers and metal complexes were examined as a function of the temperature and frequency, and the activation energies (Ea were estimated with conductivity measurements.

  1. Electron density in non-ideal metal complexes. Pt. 1

    International Nuclear Information System (INIS)

    Varghese, J.N.; Maslen, E.N.

    1985-01-01

    The structure of copper sulphate pentahydrate was refined using an accurate set of X-ray data: Msub(r)=249.68, triclinic, Panti 1, a=6.1224(4), b=10.7223(4), c=5.9681(4) A, α=82.35(2), β=107.33(2), γ=102.60(4) 0 , V=364.02(3) A 3 , Z=2, Dsub(x)=2.278 Mg m -3 , Mo Kα, lambda=0.71069 A, μ=3.419 mm -1 , F(000)=254.0, T=298 K, R=0.039 for 7667 reflections. The structural parameters are compared with those obtained by neutron diffraction. The differences between X-ray and neutron positions are related to the hydrogen bonding in the structure. The dominant features in the residual density near the two crystallographically independent Cu atoms result from the redistribution of 3d electrons due to bonding. The density is anisotropic, as expected in view of the Jahn-Teller distortion in the structure. Marked differences in the d-electron distributions for the two Cu atoms correlate with small variations in molecular geometry. Second-nearest-neighbour effects, such as those arising from differently oriented ligating waters, are significant in this structure. Sharp features in the difference density close to the Cu nuclei are similar to those in other Cu 2+ complexes, indicating that the electron density in this region is more reliable than previously believed. (orig.)

  2. Density functional theory study on Herzberg-Teller contribution in Raman scattering from 4-aminothiophenol-metal complex and metal-4-aminothiophenol-metal junction

    Science.gov (United States)

    Liu, Shasha; Zhao, Xiuming; Li, Yuanzuo; Zhao, Xiaohong; Chen, Maodu

    2009-06-01

    Density functional theory (DFT) and time-dependent DFT calculations have been performed to investigate the Raman scattering spectra of metal-molecule complex and metal-molecule-metal junction architectures interconnected with 4-aminothiophenol (PATP) molecule. The simulated profiles of normal Raman scattering (NRS) spectra for the two complexes (Ag2-PATP and PATP-Au2) and the two junctions (Ag2-PATP-Au2 and Au2-PATP-Ag2) are similar to each other, but exhibit obviously different Raman intensities. Due to the lager static polarizabilities of the two junctions, which directly influence the ground state chemical enhancement in NRS spectra, the calculated normal Raman intensities of them are stronger than those of two complexes by the factor of 102. We calculate preresonance Raman scattering (RRS) spectra with incident light at 1064 nm, which is much lower than the S1 electronic transition energy of complexes and junctions. Ag2-PATP-Au2 and Au2-PATP-Ag2 junctions yield higher Raman intensities than those of Ag2-PATP and PATP-Au2 complexes, especially for b2 modes. This effect is mainly attributed to charge transfer (CT) between the metal gap and the PAPT molecule which results in the occurrence of CT resonance enhancement. The calculated pre-RRS spectra strongly depend on the electronic transition state produced by new structures. With excitation at 514.5 nm, the calculated pre-RRS spectra of two complexes and two junctions are stronger than those of with excitation at 1064 nm. A charge difference densities methodology has been used to visually describe chemical enhancement mechanism of RRS spectrum. This methodology aims at visualizing intermolecular CT which provides direct evidence of the Herzberg-Teller mechanism.

  3. Solventless acid-free synthesis of mesostructured titania: Nanovessels for metal complexes and metal nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Dag, Oe.; Celik, Oe.; Ozin, G.A. [Department of Chemistry, Bilkent University, 06533 Ankara (Turkey); Soten, I.; Polarz, S.; Coombs, N. [Materials Chemistry Research Group, Chemistry Department, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6 (Canada)

    2003-01-01

    A new and highly reproducible method to obtain mesostructured titania materials is introduced in this contribution. The mesostructured titania is obtained by employing self-assembled structures of non-ionic alkyl-poly(ethylene oxide) surfactants as templates. The materials are produced without additional solvents such as alcohols, or even water. Only the titanium(IV) ethoxide and the surfactant (C{sub 12}EO{sub 10}) are needed. Water, in the form of that attached to the surfactant and from the atmosphere, induces growth of titania nanoclusters in the synthesis sol. It is indicated that these nanoclusters interact with the surfactant EO-head groups to form a new titanotropic amphiphile. The new amphiphiles self-assemble into titanium nanocluster-surfactant hybrid lyotropic phases, which are transformed to the final mesostructured materials by further condensation of the titania network. The titania materials can be obtained also with noble-metal particles immobilized in the mesostructured framework. It is seen that when different metal salts are used as the metal precursors, different interactions with the titania walls are found. The materials are characterized by X-ray diffraction (XRD), polarization optical microscopy (POM), transmission electron microscopy (TEM), UV-vis spectroscopy, and micro-Raman analysis. (Abstract Copyright [2003], Wiley Periodicals, Inc.)

  4. Synthesis and antimalarial activity of metal complexes of cross-bridged tetraazamacrocyclic ligands.

    Science.gov (United States)

    Hubin, Timothy J; Amoyaw, Prince N-A; Roewe, Kimberly D; Simpson, Natalie C; Maples, Randall D; Carder Freeman, TaRynn N; Cain, Amy N; Le, Justin G; Archibald, Stephen J; Khan, Shabana I; Tekwani, Babu L; Khan, M O Faruk

    2014-07-01

    Using transition metals such as manganese(II), iron(II), cobalt(II), nickel(II), copper(II), and zinc(II), several new metal complexes of cross-bridged tetraazamacrocyclic chelators namely, cyclen- and cyclam-analogs with benzyl groups, were synthesized and screened for in vitro antimalarial activity against chloroquine-resistant (W2) and chloroquine-sensitive (D6) strains of Plasmodium falciparum. The metal-free chelators tested showed little or no antimalarial activity. All the metal complexes of the dibenzyl cross-bridged cyclam ligand exhibited potent antimalarial activity. The Mn(2+) complex of this ligand was the most potent with IC50s of 0.127 and 0.157μM against the chloroquine-sensitive (D6) and chloroquine-resistant (W2) P. falciparum strains, respectively. In general, the dibenzyl hydrophobic ligands showed better anti-malarial activity compared to the activity of monobenzyl ligands, potentially because of their higher lipophilicity and thus better cell penetration ability. The higher antimalarial activity displayed by the manganese complex for the cyclam ligand in comparison to that of the cyclen, correlates with the larger pocket of cyclam compared to that of cyclen which produces a more stable complex with the Mn(2+). Few of the Cu(2+) and Fe(2+) complexes also showed improvement in activity but Ni(2+), Co(2+) and Zn(2+) complexes did not show any improvement in activity upon the metal-free ligands for anti-malarial development. Published by Elsevier Ltd.

  5. New Nanomaterials and Luminescent Optical Sensors for Detection of Hydrogen Peroxide

    Directory of Open Access Journals (Sweden)

    Natalia A. Burmistrova

    2015-10-01

    Full Text Available Accurate methods that can continuously detect low concentrations of hydrogen peroxide (H2O2 have a huge application potential in biological, pharmaceutical, clinical and environmental analysis. Luminescent probes and nanomaterials are used for fabrication of sensors for H2O2 that can be applied for these purposes. In contrast to previous reviews focusing on the chemical design of molecular probes for H2O2, this mini-review highlights the latest luminescent nanoparticular materials and new luminescent optical sensors for H2O2 in terms of the nanomaterial composition and luminescent receptor used in the sensors. The nanomaterial section is subdivided into schemes based on gold nanoparticles, polymeric nanoparticles with embedded enzymes, probes showing aggregation-induced emission enhancement, quantum dots, lanthanide-based nanoparticles and carbon based nanomaterials, respectively. Moreover, the sensors are ordered according to the type of luminescent receptor used within the sensor membranes. Among them are lanthanide complexes, metal-ligand complexes, oxidic nanoparticles and organic dyes. Further, the optical sensors are confined to those that are capable to monitor the concentration of H2O2 in a sample over time or are reusable. Optical sensors responding to gaseous H2O2 are not covered. All nanomaterials and sensors are characterized with respect to the analytical reaction towards H2O2, limit of detection (LOD, analytical range, electrolyte, pH and response time/incubation time. Applications to real samples are given. Finally, we assess the suitability of the nanomaterials to be used in membrane-based sensors and discuss future trends and perspectives of these sensors in biomedical research.

  6. Magnetic interactions as a stabilizing factor of semiquinone species of lawsone by metal complexation

    International Nuclear Information System (INIS)

    Valle-Bourrouet, Grettel; Ugalde-Saldivar, Victor M.; Gomez, Martin; Ortiz-Frade, Luis A.; Gonzalez, Ignacio; Frontana, Carlos

    2010-01-01

    Changes in electrochemical reactivity for lawsone anions (lawsone, 2-hydroxy-1,4-naphthoquinone, HLw) being coordinated to a series of metallic ions in dimethylsulfoxide solution were evaluated. Upon performing cyclic voltammetry experiments for metal complexes of this quinone with pyridine (Py) - structural formula M(II)(Lw - ) 2 (Py) 2 ; M: Co(II), Ni(II), Zn(II) - it was found that the reduction of coordinated Lw - units occurs during the first and second electron uptake in the analyzed compounds. The stability of the electrogenerated intermediates for each complex depends on the d electron configuration in each metal center and is determined by magnetic interactions with the available spins considering an octahedral conformation for all the compounds. This was evidenced by in situ spectroelectrochemical-ESR measurements in the Zn(II) complex in which due to the lack of magnetic interaction owing to its electron configuration, the structure of the coordinated anion radical species was determined. Successive reduction of the associated Lw - units leads to partial dissociation of the complex, determined by the identification of free radical dianion structures in solution. These results show some insights on how metal-lawsone complexation can modify the solution reactivity and stability of the electrogenerated radical species.

  7. Magnetic interactions as a stabilizing factor of semiquinone species of lawsone by metal complexation

    Energy Technology Data Exchange (ETDEWEB)

    Valle-Bourrouet, Grettel [Universidad de Costa Rica, Escuela de Quimica, San Jose (Costa Rica); Ugalde-Saldivar, Victor M. [Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Ciudad Universitaria, C.P. 04510, Mexico, D.F. (Mexico); Gomez, Martin [Departamento de Sistemas Biologicos, Universidad Autonoma Metropolitana-Xochimilco, C.P. 04960, Mexico, D.F. (Mexico); Ortiz-Frade, Luis A. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Parque Tecnologico Queretaro, Sanfandila, 76703, Pedro Escobedo, Queretaro (Mexico); Gonzalez, Ignacio [Universidad Autonoma Metropolitana - Iztapalapa, Departamento de Quimica, Area de Electroquimica, Apartado postal 55-534, 09340, Mexico, D.F. (Mexico); Frontana, Carlos, E-mail: ultrabuho@yahoo.com.m [Departamento de Quimica, Centro de Investigacion y Estudios Avanzados, Av. Instituto Politecnico Nacional No. 2508 Col. San Pedro Zacatenco, C.P. 07360, Mexico, D.F. (Mexico)

    2010-12-01

    Changes in electrochemical reactivity for lawsone anions (lawsone, 2-hydroxy-1,4-naphthoquinone, HLw) being coordinated to a series of metallic ions in dimethylsulfoxide solution were evaluated. Upon performing cyclic voltammetry experiments for metal complexes of this quinone with pyridine (Py) - structural formula M(II)(Lw{sup -}){sub 2}(Py){sub 2}; M: Co(II), Ni(II), Zn(II) - it was found that the reduction of coordinated Lw{sup -} units occurs during the first and second electron uptake in the analyzed compounds. The stability of the electrogenerated intermediates for each complex depends on the d electron configuration in each metal center and is determined by magnetic interactions with the available spins considering an octahedral conformation for all the compounds. This was evidenced by in situ spectroelectrochemical-ESR measurements in the Zn(II) complex in which due to the lack of magnetic interaction owing to its electron configuration, the structure of the coordinated anion radical species was determined. Successive reduction of the associated Lw{sup -} units leads to partial dissociation of the complex, determined by the identification of free radical dianion structures in solution. These results show some insights on how metal-lawsone complexation can modify the solution reactivity and stability of the electrogenerated radical species.

  8. [Ultraviolet-visible spectrometry analysis of insoluble xanthate heavy metal complexes].

    Science.gov (United States)

    Qiu, Bo; Liu, Jin-Feng; Liu, Yao-Chi; Yang, Zhao-Guang; Li, Hai-Pu

    2014-11-01

    A ultraviolet-visible spectrometry method of determining insoluble xanthate heavy metal complexes in flotation wastewater was the first time to be put forward. In this work, the changes of ultraviolet-visible spectra of xanthate solution after the addition of various heavy metal ions were investigated firstly. It was found that Pb2+ and Cu2+ can form insoluble complexes with xanthate, while Fe2+, Zn2+ and Mn2+ have little effect on the ultraviolet absorption of xanthate solution. Then the removal efficiencies of filter membrane with different pore sizes were compared, and the 0.22 μm membrane was found to be effective to separate copper xanthate or lead xanthate from the filtrate. Furthermore, the results of the study on the reaction of sodium sulfide and insoluble xanthate heavy metal complexes showed that S(2-) can release the xanthate ion quantitatively from insoluble complexes to solution. Based on the above research, it was concluded that the amount of insoluble xanthate heavy metal complexes in water samples can be obtained through the increase of free xanthate in the filtrate after the addition of sodium sulfide. Finally, the feasibility of this method was verified by the application to the analysis of flotation wastewater from three ore-dressing plants in the Thirty-six Coves in Chenzhou.

  9. Antimicrobial and thermal properties of metal complexes of grafted fabrics with acrylic acid by gamma irradiation

    International Nuclear Information System (INIS)

    Hassan, M.S.; Attia, R.M.; Zohdy, M.H.; Khalil, E.M.

    2009-01-01

    Cotton, cotton/ ET blend and PET fabrics were treated against microbial effect by radiation -induced grafting of acrylic acid followed by metal complexation with some divalent transition metal ions like Co (l l), Ni(l l) and Cu(l l).The microbial resistance was evaluated by testing the mechanical properties of the treated fabrics after burring for one and two weeks in a moist soil reach with microorganisms. Also, the structural damage of the fabrics caused by biodegradation was examined by scanning electron microscope (SEM). Moreover, the effect of this treatment on the thermal decomposition behaviour was investigated by thermogravimetric analysis (TGA). On the basis of microbial studies, it was found that the metal complexation of the grafted fabrics with acrylic acid enhanced the microbial resistance of the fabrics and the microbial resistance could be arranged according to the complexed metal ions as follows: copper> nickel> cobalt. Also, the thermal stability of different fabrics could be arranged as follow: grafted fabrics complexes with Cu (l l) grafted fabrics complexes with Co (l l)

  10. Antimicrobial and Thermal Properties of Metal Complexes of Grafted Fabrics with Acrylic Acid by Gamma Irradiation

    International Nuclear Information System (INIS)

    Hassan, M.S.; Attia, R.M.; Zohdy, M.H.

    2008-01-01

    Cotton, cotton/PET blend and PET fabrics were treated against microbial effect by radiation - induced grafting of acrylic acid followed by metal complexation with some divalent transition metal ions Co (II), Ni (II) and Cu (II). The microbial resistance was evaluated by testing the mechanical properties of the treated fabrics after burring for one and two weeks in a moist soil reach with microorganisms. Also, the growth of microorganisms was examined by scanning electron microscope (SEM). Moreover, the effect of this treatment on the thermal decomposition behavior was investigated by thermogravimetric analysis (TGA). On the basis of microbial studies, it was found that the metal complexation of the grafted fabrics with acrylic acid enhanced the antimicrobial resistance of the fabrics and the antimicrobial resistance could be arranged according to the metal ions as follows: copper> nickel> cobalt. Also, the thermal stability of different fabrics could be arranged as follow: grafted fabrics complexed with Cu (II) > grafted fabrics complexed with Ni (II) > grafted fabrics complexed with Co (II)

  11. Synthesis, structural modelling and luminescence of a novel erbium(III) complex with 2,4-nonanedione and 2,2‧-bipyridine ligands for chitosan matrices doping

    Science.gov (United States)

    Martín-Ramos, P.; Chamorro-Posada, P.; Ramos Silva, M.; Pereira da Silva, P. S.; Martín, I. R.; Lahoz, F.; Lavín, V.; Martín-Gil, J.

    2015-03-01

    We report the synthesis, the Sparkle/PM7 semi-empirical quantum model for the ground state geometry and the absorption/luminescent properties of the Er3+ ternary complex [Er(nd)3(bipy)] (where Hnd is 2,4-nonanedione and bipy is 2,2‧-bipyridine). The solid-state electronic absorption spectra and the photoluminescent spectra show long-wavelength 4f-4f transitions which provide a potential use of the compound as a NIR-emitting material for the doping of polymer-based matrices for waveguides or for bio-analytical applications. The dispersion of the novel complex in a biocompatible chitosan film has been assessed.

  12. Device and method for luminescence enhancement by resonant energy transfer from an absorptive thin film

    Science.gov (United States)

    Akselrod, Gleb M.; Bawendi, Moungi G.; Bulovic, Vladimir; Tischler, Jonathan R.; Tisdale, William A.; Walker, Brian J.

    2017-12-12

    Disclosed are a device and a method for the design and fabrication of the device for enhancing the brightness of luminescent molecules, nanostructures, and thin films. The device includes a mirror, a dielectric medium or spacer, an absorptive layer, and a luminescent layer. The absorptive layer is a continuous thin film of a strongly absorbing organic or inorganic material. The luminescent layer may be a continuous luminescent thin film or an arrangement of isolated luminescent species, e.g., organic or metal-organic dye molecules, semiconductor quantum dots, or other semiconductor nanostructures, supported on top of the absorptive layer.

  13. A multifunctional chemical sensor based on a three-dimensional lanthanide metal-organic framework

    Energy Technology Data Exchange (ETDEWEB)

    Du, Pei-Yao [College of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071 (China); Liao, Sheng-Yun [Department of Applied Chemistry, Tianjin University of Technology, Tianjin 300384 (China); Gu, Wen, E-mail: guwen68@nankai.edu.cn [College of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071 (China); Liu, Xin, E-mail: liuxin64@nankai.edu.cn [College of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071 (China)

    2016-12-15

    A 3D lanthanide MOF with formula [Sm{sub 2}(abtc){sub 1.5}(H{sub 2}O){sub 3}(DMA)]·H{sub 2}O·DMA (1) has been successfully synthesized via solvothermal method. Luminescence studies reveal that 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. In addition, 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules, which suggests that 1 is also a promising luminescent probe for high selective sensing of ethanol. - Highlights: • A three-dimensional lanthanide metal-organic framework has been synthesized. • Complex 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. • Complex 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules.

  14. A multifunctional chemical sensor based on a three-dimensional lanthanide metal-organic framework

    International Nuclear Information System (INIS)

    Du, Pei-Yao; Liao, Sheng-Yun; Gu, Wen; Liu, Xin

    2016-01-01

    A 3D lanthanide MOF with formula [Sm 2 (abtc) 1.5 (H 2 O) 3 (DMA)]·H 2 O·DMA (1) has been successfully synthesized via solvothermal method. Luminescence studies reveal that 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. In addition, 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules, which suggests that 1 is also a promising luminescent probe for high selective sensing of ethanol. - Highlights: • A three-dimensional lanthanide metal-organic framework has been synthesized. • Complex 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. • Complex 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules.

  15. Preparation and properties of chitosan-metal complex: Some factors influencing the adsorption capacity for dyes in aqueous solution.

    Science.gov (United States)

    Rashid, Sadia; Shen, Chensi; Yang, Jing; Liu, Jianshe; Li, Jing

    2018-04-01

    Chitosan-metal complexes have been widely studied in wastewater treatment, but there are still various factors in complex preparation which are collectively responsible for improving the adsorption capacity need to be further studied. Thus, this study investigates the factors affecting the adsorption ability of chitosan-metal complex adsorbents, including various kinds of metal centers, different metal salts and crosslinking degree. The results show that the chitosan-Fe(III) complex prepared by sulfate salts exhibited the best adsorption efficiency (100%) for various dyes in very short time duration (10min), and its maximum adsorption capacity achieved 349.22mg/g. The anion of the metal salt which was used in preparation played an important role to enhance the adsorption ability of chitosan-metal complex. SO 4 2- ions not only had the effect of crosslinking through electrostatic interaction with amine group of chitosan polymer, but also could facilitate the chelation of metal ions with chitosan polymer during the synthesis process. Additionally, the pH sensitivity and the sensitivity of ionic environment for chitosan-metal complex were analyzed. We hope that these factors affecting the adsorption of the chitosan-metal complex can help not only in optimizing its use but also in designing new chitosan-metal based complexes. Copyright © 2017. Published by Elsevier B.V.

  16. Spatial structure of transition metal complexes in solution determined by EXAFS spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Erenburg, S.B. E-mail: simon@che.nsk.su; Bausk, N.V.; Zemskova, S.M.; Mazalov, L.N

    2000-06-21

    CdK EXAFS, ZnK and CuK EXAFS and XANES spectra were measured for solutions of cadmium, zinc and copper dialkyldithiocarbamates in organic solvents with varying donating abilities: tributylphosphine, methylene chloride, benzene, dibutylsulfide, pyridine, dimethylsulfoxide and for some model compounds. The parameters of the local surroundings of the Cd, Zn and Cu atoms for complex forms in solutions were determined using EXAFS spectroscopy. Spatial structure models of the complex forms in a metal chelate - nonaqueous solvent system are suggested.

  17. Spatial structure of transition metal complexes in solution determined by EXAFS spectroscopy

    International Nuclear Information System (INIS)

    Erenburg, S.B.; Bausk, N.V.; Zemskova, S.M.; Mazalov, L.N.

    2000-01-01

    CdK EXAFS, ZnK and CuK EXAFS and XANES spectra were measured for solutions of cadmium, zinc and copper dialkyldithiocarbamates in organic solvents with varying donating abilities: tributylphosphine, methylene chloride, benzene, dibutylsulfide, pyridine, dimethylsulfoxide and for some model compounds. The parameters of the local surroundings of the Cd, Zn and Cu atoms for complex forms in solutions were determined using EXAFS spectroscopy. Spatial structure models of the complex forms in a metal chelate - nonaqueous solvent system are suggested

  18. Investigation of complexing ability of ionites with various groups to some heavy and transition metal ions

    Directory of Open Access Journals (Sweden)

    Yedil Yergozhin

    2013-05-01

    Full Text Available The physico-chemical and complexing properties of the sorbent based on chloromethylated styrene and divinylbenzene copolymer with nicotinamide groups and copolymers based on metacryloilaminobenzene acids with 2-methyl-5-vinylpyridineisomers are studied. By potentiometric titration method the constant of polyelectrolytes functional groups ionization, the composition and strength of the resulting complexes with ions of some heavy and transition metals are determined.

  19. Supramolecular assembly of group 11 phosphorescent metal complexes for chemosensors of alcohol derivatives

    Science.gov (United States)

    Lintang, H. O.; Ghazalli, N. F.; Yuliati, L.

    2018-04-01

    We report on systematic study on vapochromic sensing of ethanol by using phosphorescent trinuclear metal pyrazolate complexes with supramolecular assembly of weak intermolecular metal-metal interactions using 4-(3,5-dimethoxybenzyl)-3,5-dimethyl pyrazole ligand (1) and group 11 metal ions (Cu(I), Ag(I), Au(I)). Upon excitation at 284, the resulting complexes showed emission bands with a peak centered at 616, 473 and 612 nm for 2(Cu), 2(Ag) and 2(Au), respectively. Chemosensor 2(Cu) showed positive response to ethanol vapors in 5 mins by blue-shifting its emission band from 616 to 555 nm and emitting bright orange to green. Otherwise 2(Au) gave shifting from its emission band centered at 612 to 587 nm with Δλ of 25 nm (41%) and color changes from red-orange to light green-orange while 2(Ag) showed quenching in its original emission intensity at 473 nm in 40% with color changes from dark green to less emissive. These results demonstrate that sensing capability of chemosensor 2(Cu) with suitable molecular design of ligand and metal ion in the complex is due to the formation of a weak intermolecular hydrogen bonding interaction of O atom at the methoxy of the benzyl ring with the OH of the vapors at the outside of the molecules.

  20. Molybdenum/alkali metal/ethylene glycol complexes useful as epoxidation catalysts

    International Nuclear Information System (INIS)

    Marquis, E.T.; Sanderson, J.R.; Keating, K.P.

    1987-01-01

    This patent describes a clear, storage stable solution of a molybdenum/alkali metal/ethylene glycol complex in ethylene glycol made by the process comprising: reacting at an elevated temperature between about 25 0 and 150 0 C a solid ammonium molybdate or a hydrate thereof and a solid alkali metal molybdate or a hydrate thereof with ethylene glycol, such that the ratio of moles of ethylene glycol to total gram atoms of molybdenum in the molybdates ranges from about 7:10 to 10:1, and the ratio of gram atoms of molybdenum in the ammonium molybdate or hydrate thereof to gram atoms of molybdenum in the alkali metal molybdate is from about 1:1 to about 20:1 to thereby provide a reaction product composed of a solution of an alkali metal-containing complex of molybdenum, alkali metal and ethylene glycol and by-products, including water, in the ethylene glycol and subsequently stripping the solution at a reduced pressure to remove from about 5 to about 25% of the reaction product, as distillate, to thereby provide a storage stable solution of the complex in the ethylene glycol having a molybdenum content of about 6 wt. % to about 20 wt. %, a water concentration of about 0.1 wt. % to about 6 wt. % and an acid number of more than about 60