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Sample records for highly luminescent lanthanide

  1. Luminescent Lanthanide Reporters for High-Sensitivity Novel Bioassays.

    Energy Technology Data Exchange (ETDEWEB)

    Anstey, Mitchell R.; Fruetel, Julia A.; Foster, Michael E.; Hayden, Carl C.; Buckley, Heather L.; Arnold, John

    2013-09-01

    Biological imaging and assay technologies rely on fluorescent organic dyes as reporters for a number of interesting targets and processes. However, limitations of organic dyes such as small Stokes shifts, spectral overlap of emission signals with native biological fluorescence background, and photobleaching have all inhibited the development of highly sensitive assays. To overcome the limitations of organic dyes for bioassays, we propose to develop lanthanide-based luminescent dyes and demonstrate them for molecular reporting applications. This relatively new family of dyes was selected for their attractive spectral and chemical properties. Luminescence is imparted by the lanthanide atom and allows for relatively simple chemical structures that can be tailored to the application. The photophysical properties offer unique features such as narrow and non-overlapping emission bands, long luminescent lifetimes, and long wavelength emission, which enable significant sensitivity improvements over organic dyes through spectral and temporal gating of the luminescent signal.Growth in this field has been hindered due to the necessary advanced synthetic chemistry techniques and access to experts in biological assay development. Our strategy for the development of a new lanthanide-based fluorescent reporter system is based on chelation of the lanthanide metal center using absorbing chromophores. Our first strategy involves "Click" chemistry to develop 3-fold symmetric chelators and the other involves use of a new class of tetrapyrrole ligands called corroles. This two-pronged approach is geared towards the optimization of chromophores to enhance light output.

  2. Luminescent macrocyclic lanthanide complexes

    Science.gov (United States)

    Raymond, Kenneth N [Berkeley, CA; Corneillie, Todd M [Campbell, CA; Xu, Jide [Berkeley, CA

    2012-05-08

    The present invention provides a novel class of macrocyclic compounds as well as complexes formed between a metal (e.g., lanthanide) ion and the compounds of the invention. Preferred complexes exhibit high stability as well as high quantum yields of lanthanide ion luminescence in aqueous media without the need for secondary activating agents. Preferred compounds incorporate hydroxy-isophthalamide moieties within their macrocyclic structure and are characterized by surprisingly low, non-specific binding to a variety of polypeptides such as antibodies and proteins as well as high kinetic stability. These characteristics distinguish them from known, open-structured ligands.

  3. New Opportunities for Lanthanide Luminescence

    Institute of Scientific and Technical Information of China (English)

    Jean-Claude G. Bünzli; Steve Comby; Anne-Sophie Chauvin; Caroline D. B. Vandevyver

    2007-01-01

    Trivalent lanthanide ions display fascinating optical properties. The discovery of the corresponding elements and their first industrial uses were intimately linked to their optical properties. This relationship has been kept alive until today when many high-technology applications of lanthanide-containing materials such as energy-saving lighting devices, displays, optical fibers and amplifiers, lasers, responsive luminescent stains for biomedical analyses and in cellulo sensing and imaging, heavily rely on the brilliant and pure-color emission of lanthanide ions. In this review we first outlined the basics of lanthanide luminescence with emphasis on f-f transitions, the sensitization mechanisms, and the assessment of the luminescence efficiency of lanthanide-containing emissive molecular edifices. Emphasis was then put on two fast developing aspects of lanthanide luminescence: materials for telecommunications and light emitting diodes, and biomedical imaging and sensing. Recent advances in NIR-emitting materials for plastic amplifiers and waveguides were described, together with the main solutions brought by researchers to minimize non-radiative deactivation of excited states. The demonstration in 1999 that erbium tris(8-hydroxyquinolinate) displayed a bright green emission suitable for organic light emitting diodes (OLEDs) was followed by realizing that in OLEDs, 25% of the excitation energy leads to singlet states and 75% to triplet states. Since lanthanide ions are good triplet quenchers, they now also play a key role in the development of these lighting devices. Luminescence analyses of biological molecules are among the most sensitive analytical techniques known. The long lifetime of the lanthanide excited states allows time-resolved spectroscopy to be used, suppressing the sample autofluorescence and reaching very low detection limits. Not only visible lanthanide sensors are now ubiquitously provided in medical diagnosis and in cell imaging, but the

  4. 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.

  5. 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.

  6. Luminescent lanthanide chelates and methods of use

    Science.gov (United States)

    Selvin, Paul R.; Hearst, John

    1997-01-01

    The invention provides lanthanide chelates capable of intense luminescence. The celates comprise a lanthanide chelator covalently joined to a coumarin-like or quinolone-like sensitizer. Exemplary sensitzers include 2- or 4-quinolones, 2- or 4-coumarins, or derivatives thereof e.g. carbostyril 124 (7-amino-4-methyl-2-quinolone), coumarin 120 (7-amino-4-methyl-2-coumarin), coumarin 124 (7-amino-4-(trifluoromethyl)-2-coumarin), aminomethyltrimethylpsoralen, etc. The chelates form high affinity complexes with lanthanides, such as terbium or europium, through chelator groups, such as DTPA. The chelates may be coupled to a wide variety of compounds to create specific labels, probes, diagnostic and/or therapeutic reagents, etc. The chelates find particular use in resonance energy transfer between chelate-lanthanide complexes and another luminescent agent, often a fluorescent non-metal based resonance energy acceptor. The methods provide useful information about the structure, conformation, relative location and/or interactions of macromolecules.

  7. Lanthanide-based luminescence biolabelling.

    Science.gov (United States)

    Sy, Mohamadou; Nonat, Aline; Hildebrandt, Niko; Charbonnière, Loïc J

    2016-04-14

    Luminescent lanthanide complexes display unrivalled spectroscopic properties, which place them in a special category in the luminescent toolbox. Their long-lived line-like emission spectra are the cornerstones of numerous analytical applications ranging from ultrasensitive homogeneous fluoroimmunoassays to the study of molecular interactions in living cells with multiplexed microscopy. However, achieving such minor miracles is a result of years of synthetic efforts and spectroscopic studies to understand and gather all the necessary requirements for the labels to be efficient. This feature article intends to survey these criteria and to discuss some of the most important examples reported in the literature, before explaining in detail some of the applications of luminescent lanthanide labels to bioanalysis and luminescence microscopy. Finally, the emphasis will be put on some recent applications that hold great potential for future biosensing.

  8. 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...

  9. Highly luminescent lanthanide complexes with novel bis-β-diketone ligand: synthesis, characterization and photoluminescent properties.

    Science.gov (United States)

    Li, Hong-Feng; Li, Guang-Ming; Chen, Peng; Sun, Wen-Bin; Yan, Peng-Fei

    2012-11-01

    A biphenyl-linked bis-β-diketone ligand, 3,3'-bis(3-phenyl-3-oxopropanol)biphenyl (BPB) has been prepared for the syntheses of a series of dinuclear lanthanide complexes. The ligand bears two benzoyl β-diketonate sites linked by a 3,3'-biphenyl spacer. Reaction of the doubly negatively charged bis-bidenate ligand with lanthanide ions forms triple-stranded dinuclear complexes Ln(2)(BPB)(3) (Ln=Nd (1), Sm (2), Eu (3), Yb (4) and Gd (5)). Electrospray mass spectrometry is used to identify the formation of the triple-stranded dinuclear complexes 1-5, which have been further characterized by various spectroscopic techniques. The complexes display strong visible and NIR luminescence upon excitation at ligands bands around 360 nm, depending on the choice of the lanthanides, and the emission quantum yields and luminescence lifetimes of 2-3 have been determined. It shows that the biphenyl-linked ligand BPB is a more efficient sensitizer than the monodiketone ligand DBM (dibenzoylmethane), through the comparisons of Ln(2)(BPB)(3) and Ln(DBM)(3) on their photoluminescent properties.

  10. Highly luminescent lanthanide complexes with novel bis-β-diketone ligand: Synthesis, characterization and photoluminescent properties

    Science.gov (United States)

    Li, Hong-Feng; Li, Guang-Ming; Chen, Peng; Sun, Wen-Bin; Yan, Peng-Fei

    2012-11-01

    A biphenyl-linked bis-β-diketone ligand, 3,3'-bis(3-phenyl-3-oxopropanol)biphenyl (BPB) has been prepared for the syntheses of a series of dinuclear lanthanide complexes. The ligand bears two benzoyl β-diketonate sites linked by a 3,3'-biphenyl spacer. Reaction of the doubly negatively charged bis-bidenate ligand with lanthanide ions forms triple-stranded dinuclear complexes Ln2(BPB)3 (Ln = Nd (1), Sm (2), Eu (3), Yb (4) and Gd (5)). Electrospray mass spectrometry is used to identify the formation of the triple-stranded dinuclear complexes 1-5, which have been further characterized by various spectroscopic techniques. The complexes display strong visible and NIR luminescence upon excitation at ligands bands around 360 nm, depending on the choice of the lanthanides, and the emission quantum yields and luminescence lifetimes of 2-3 have been determined. It shows that the biphenyl-linked ligand BPB is a more efficient sensitizer than the monodiketone ligand DBM (dibenzoylmethane), through the comparisons of Ln2(BPB)3 and Ln(DBM)3 on their photoluminescent properties.

  11. Highly luminescent bis-diketone lanthanide complexes with triple-stranded dinuclear structure.

    Science.gov (United States)

    Li, Hong-Feng; Yan, Peng-Fei; Chen, Peng; Wang, Yan; Xu, Hui; Li, Guang-Ming

    2012-01-21

    A new bis-β-diketone, 3,3'-bis(4,4,4-trifluoro-1,3-dioxobutyl)biphenyl (BTB), has been designed and prepared for the synthesis of a series of dinuclear lanthanide complexes [Ln(2)(BTB)(3)(C(2)H(5)OH)(2)(H(2)O)(2)] [Ln = Eu (1), Gd (2)], [Ln(2)(BTB)(3)(DME)(2)] [Ln = Nd (3), Yb (4); DME = ethylene glycol dimethyl ether] and [Eu(2)(BTB)(3)(L)(2)] [L = 2,2-bipydine (5); 1,10-phenanthroline (6); 4,7-diphenyl-1,10-phenanthroline (7)]. Complexes 1-7 have been characterized by various spectroscopic techniques and their photophysical properties are investigated. X-ray crystallographical analysis reveals that complexes 1, 3 and 4 adopt triple-stranded dinuclear structures which are formed by three bis-bidentate ligands with two lanthanide ions. The complexes 1 and 3-7 display strong visible red or NIR luminescence upon irradiation at ligand band around 372 nm, depending on the choice of the lanthanide. The solid-state photoluminescence quantum yields and the lifetimes of Eu(3+) complexes are determined and described.

  12. LANTHANIDE ENHANCE LUMINESCENCE (LEL) WITH ONE AND TWO PHOTON EXCITATION OF QUANTUM DYES LANTHANIDE (III) - MACROCYCLES

    Science.gov (United States)

    Title: Lanthanide Enhance Luminescence (LEL) with one and two photon excitation of Quantum Dyes? Lanthanide(III)-Macrocycles Principal Author:Robert C. Leif, Newport InstrumentsSecondary Authors:Margie C. Becker, Phoenix Flow Systems Al Bromm, Virginia Commonw...

  13. LANTHANIDE ENHANCE LUMINESCENCE (LEL) WITH ONE AND TWO PHOTON EXCITATION OF QUANTUM DYES LANTHANIDE (III) - MACROCYCLES

    Science.gov (United States)

    Title: Lanthanide Enhance Luminescence (LEL) with one and two photon excitation of Quantum Dyes? Lanthanide(III)-Macrocycles Principal Author:Robert C. Leif, Newport InstrumentsSecondary Authors:Margie C. Becker, Phoenix Flow Systems Al Bromm, Virginia Commonw...

  14. Novel lanthanide hybrid functional materials for high performance luminescence application: The relationship between structures and photophysical behaviors

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Jun [Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Jia, Lei [Department of Physics and Chemistry, Henan Polytechnic University, Jiaozuo 454000 (China); Ma, Yufei; Liu, Xiao; Tian, Hao; Liu, Weisheng [Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Tang, Yu, E-mail: tangyu@lzu.edu.cn [Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China)

    2012-09-14

    Functional luminescent hybrid materials have emerged as fascinating and promising materials for their versatile applications. In this report, novel efficient luminescent lanthanide (Tb{sup 3+}, Eu{sup 3+}) hybrid materials with a new kind of amide-type {beta}-diketone ligands covalently bonded to the silica gels have been assembled through the sol-gel progresses. The hybrid materials have been characterized by the Fourier transform infrared (FTIR) spectra, UV-vis absorption spectra, powder X-ray diffraction (PXRD), scanning electron microscope (SEM), and thermal analyses. The relationship between structures and photophysical behaviors of these materials was discussed in detail. The materials assembled by the precursors containing aromatic end group (Si-L{sup 1}-Ln) exhibited longer luminescence lifetimes and higher quantum efficiencies, suggesting that the existence of a suitable conjugated system should allow a more efficient energy transfer. Under UV irradiation, the materials emitted either bright green light or red light with different intensity which may lead to potential functional applications in optical devices and electronic devices. Highlights: Black-Right-Pointing-Pointer A new kind of efficient luminescent lanthanide hybrid materials has been assembled. Black-Right-Pointing-Pointer The materials can efficiently emit green or red light under UVA irradiation. Black-Right-Pointing-Pointer The relationship between photophysical behaviors and structures was discussed. Black-Right-Pointing-Pointer A suitable conjugated system should allow a more efficient energy transfer.

  15. Salicylamide-lanthanide complexes for use as luminescent markers

    Science.gov (United States)

    Raymond, Kenneth N.; Petoud, Stephane; Cohen, Seth; Xu, Jide

    2002-01-01

    The present invention provides luminescent lanthanide metal chelates comprising a metal ion of the lanthanide series and a complexing agent comprising at least one salicylamidyl moiety. Also provided are probes incorporating the salicylamidyl ligands of the invention and methods utilizing the ligands of the invention and probes comprising the ligands of the invention.

  16. Phthalamide-lanthanide complexes for use as luminescent markers

    Science.gov (United States)

    Raymond, Kenneth N.; Petoud, Stephane; Cohen, Seth; Xu, Jide

    2008-10-28

    The present invention provides luminescent lanthanide metal chelates comprising a metal ion of the lanthanide series and a complexing agent comprising at least one phthalamidyl moiety. Also provided are probes incorporating the phthalamidyl ligands of the invention and methods utilizing the ligands of the invention and probes comprising the ligands of the invention.

  17. Phthalamide lanthanide complexes for use as luminescent markers

    Science.gov (United States)

    Raymond, Kenneth N.; Petoud, Stephane; Cohen, Seth M.; Xu, Jide

    2003-01-01

    The present invention provides luminescent lanthanide metal chelates comprising a metal ion of the lanthanide series and a complexing agent comprising at least one phthalamidyl moiety. Also provided are probes incorporating the phthalamidyl ligands of the invention and methods utilizing the ligands of the invention and probes comprising the ligands of the invention.

  18. Lanthanide-doped luminescent nanomaterials. From fundamentals to bioapplications

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Xueyuan; Tu, Datao; Liu, Yongsheng [Chinese Academy of Sciences, Fuzhou (China). Fujian Inst. of Research on the Structure of Matter

    2014-07-01

    Covers the frontiers in chemistry, physics and bioapplications of lanthanide-doped luminescent nanomaterials. Presents new insights into the optical behaviors of lanthanide in nanomaterials. Systematically reviews in-vitro biodetection and bioimaging based on lanthanide-doped inorganic nanocrystals. Lanthanide-Doped Luminescent Nanomaterials reviews the latest advances in the development of lanthanide-doped luminescent inorganic nanoparticles for potential bioapplications. This book covers the chemical and physical fundamentals of these nanoparticles, such as the controlled synthesis methodology, surface modification chemistry, optical physics, and their promising applications in diverse bioassays, with an emphasis on heterogeneous and homogeneous in-vitro biodetection of tumor biomarkers. This book is intended for those readers who are interested in systematically understanding the materials design strategy, optical behavior of lanthanide ions, and practical bioapplications of lanthanide nanoparticles. It primarily focuses on the interdisciplinary frontiers in chemistry, physics and biological aspects of luminescent nanomaterials. All chapters were written by scientists active in this field and for a broad audience, providing both beginners and advanced researchers with comprehensive information on the subject.

  19. Lanthanide-doped luminescent nanomaterials from fundamentals to bioapplications

    CERN Document Server

    Chen, Xueyuan; Tu, Datao

    2014-01-01

    Lanthanide-Doped Luminescent Nanomaterials reviews the latest advances in the development of lanthanide-doped luminescent inorganic nanoparticles for potential bioapplications. This book covers the chemical and physical fundamentals of these nanoparticles, such as the controlled synthesis methodology, surface modification chemistry, optical physics, and their promising applications in diverse bioassays, with an emphasis on heterogeneous and homogeneous in-vitro biodetection of tumor biomarkers. This book is intended for those readers who are interested in systematically understanding the materials design strategy, optical behavior of lanthanide ions, and practical bioapplications of lanthanide nanoparticles. It primarily focuses on the interdisciplinary frontiers in chemistry, physics and biological aspects of luminescent nanomaterials. All chapters were written by scientists active in this field and for a broad audience, providing both beginners and advanced researchers with comprehensive information on the ...

  20. Lanthanide-Doped KLu2F7 Nanoparticles with High Upconversion Luminescence Performance: A Comparative Study by Judd-Ofelt Analysis and Energy Transfer Mechanistic Investigation

    Science.gov (United States)

    Xu, Dekang; Li, Anming; Yao, Lu; Lin, Hao; Yang, Shenghong; Zhang, Yueli

    2017-02-01

    The development, design and the performance evaluation of rare-earth doped host materials is important for further optical investigation and industrial applications. Herein, we successfully fabricate KLu2F7 upconversion nanoparticles (UCNPs) through hydrothermal synthesis by controlling the fluorine-to-lanthanide-ion molar ratio. The structural and morphological results show that the samples are orthorhombic-phase hexagonal-prisms UCNPs, with average side length of 80 nm and average thickness of 110 nm. The reaction time dependent crystal growth experiment suggests that the phase transformation is a thermo-dynamical process and the increasing F-/Ln3+ ratio favors the formation of the thermo-dynamical stable phase - orthorhombic KLu2F7 structure. The upconversion luminescence (UCL) spectra display that the orthorhombic KLu2F7:Yb/Er UCNPs present stronger UCL as much as 280-fold than their cubic counterparts. The UCNPS also display better UCL performance compared with the popular hexagonal-phase NaREF4 (RE = Y, Gd). Our mechanistic investigation, including Judd-Ofelt analysis and time decay behaviors, suggests that the lanthanide tetrad clusters structure at sublattice level accounts for the saturated luminescence and highly efficient UCL in KLu2F7:Yb/Er UCNPs. Our research demonstrates that the orthorhombic KLu2F7 is a promising host material for UCL and can find potential applications in lasing, photovoltaics and biolabeling techniques.

  1. Ga(3+)/Ln(3+) Metallacrowns: A Promising Family of Highly Luminescent Lanthanide Complexes That Covers Visible and Near-Infrared Domains.

    Science.gov (United States)

    Chow, Chun Y; Eliseeva, Svetlana V; Trivedi, Evan R; Nguyen, Tu N; Kampf, Jeff W; Petoud, Stéphane; Pecoraro, Vincent L

    2016-04-20

    visible (Sm, Eu, Tb, Dy, Tm). All Ln-1 complexes possess very high quantum yield values with respect to other literature compounds, indicating a good sensitization efficiency of the [12-MCGa(III)shi-4] scaffold. Especially, as of today, the Yb-1 complex exhibits the highest NIR quantum yield reported for a lanthanide(III) complex containing C-H bonds with a value of 5.88(2)% in the solid state. This work is a significant step forward toward versatile, easily prepared luminescent lanthanide(III) complexes suitable for a variety of applications including highly in demand biological imaging, especially in the NIR domain.

  2. Lanthanide NIR luminescence for telecommunications, bioanalyses and solar energy conversion

    Institute of Scientific and Technical Information of China (English)

    Jean-Claude; G.; Bünzli; V.

    2010-01-01

    Present-day advanced technologies heavily rely on the exciting magnetic and spectroscopic properties of lanthanide ions. In particular, their ability to generate well-characterized and intense near-infrared (NIR) luminescence is exploited in any modern fiber-optic telecommunication network. In this feature article, we first summarize the whereabouts underlying the design of highly luminescent NIR molecular edifices and materials. We then focus on describing the main trends in three applications related to this spectral range: telecommunications, biosciences, and solar energy conversion. In telecommunications, efforts concentrate presently on getting easily processable polymer-based waveguide amplifiers. Upconversion nanophosphors emitting in the visible after NIR excitation are now ubiquitous in many bioanalyses while their application to bio-imaging is still in its early stages; however, highly sensitive NIR-NIR systems start to be at hand for both in vitro and in vivo imaging, as well as dual probes combining magnetic resonance and optical imaging. Finally, both silicon-based and dye-sensitized solar cells benefit from the downconversion and upconversion capabilities of lanthanide ions to harvest UV and NIR solar light and to boost the overall quantum efficiency of these next-generation devices.

  3. A Ratiometric Luminescent Thermometer Co-doped with Lanthanide and Transition Metals.

    Science.gov (United States)

    Li, Zhiqiang; Hou, Zhaohui; Ha, Denghui; Li, Huanrong

    2015-12-01

    Herein, we report the fabrication of a sensitive ratiometric and colorimetric luminescent thermometer with a wide operating-temperature range, from cryogenic temperatures up to high temperatures, through the combination of lanthanide and transition metal complexes. Benefiting from the transition metal complex as a self-reference, the lanthanide content in the mixed-coordination complex, Eu0.05(Mebip-mim bromine)0.15Zn0.95(Mebip-mim bromine)1.9, was lowered to 5%.

  4. From antenna to assay: lessons learned in lanthanide luminescence.

    Science.gov (United States)

    Moore, Evan G; Samuel, Amanda P S; Raymond, Kenneth N

    2009-04-21

    Ligand-sensitized, luminescent lanthanide(III) complexes are of considerable importance because their unique photophysical properties (microsecond to millisecond lifetimes, characteristic and narrow emission bands, and large Stokes shifts) make them well suited as labels in fluorescence-based bioassays. The long-lived emission of lanthanide(III) cations can be temporally resolved from scattered light and background fluorescence to vastly enhance measurement sensitivity. One challenge in this field is the design of sensitizing ligands that provide highly emissive complexes with sufficient stability and aqueous solubility for practical applications. In this Account, we give an overview of some of the general properties of the trivalent lanthanides and follow with a summary of advances made in our laboratory in the development of highly luminescent Tb(III) and Eu(III) complexes for applications in biotechnology. A focus of our research has been the optimization of these compounds as potential commercial agents for use in homogeneous time-resolved fluorescence (HTRF) technology. Our approach involves developing high-stability octadentate Tb(III) and Eu(III) complexes that rely on all-oxygen donor atoms and using multichromophore chelates to increase molar absorptivity; earlier examples utilized a single pendant chromophore (that is, a single "antenna"). Ligands based on 2-hydroxyisophthalamide (IAM) provide exceptionally emissive Tb(III) complexes with quantum yield values up to approximately 60% that are stable at the nanomolar concentrations required for commercial assays. Through synthetic modification of the IAM chromophore and time-dependent density functional theory (TD-DFT) calculations, we have developed a method to predict absorption and emission properties of these chromophores as a tool to guide ligand design. Additionally, we have investigated chiral IAM ligands that yield Tb(III) complexes possessing both high quantum yield values and strong circularly

  5. Nanoscale luminescent lanthanide-based metal–organic frameworks: properties, synthesis, and applications

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Dongqin; Song, Yonghai; Wang, Li, E-mail: lwanggroup@aliyun.com [Jiangxi Normal University, Key Laboratory of Functional Small Organic Molecule, Ministry of Education, Key Laboratory of Chemical Biology, Jiangxi Province, College of Chemistry and Chemical Engineering (China)

    2015-07-15

    Nanoscale luminescent lanthanide-based metal–organic frameworks (NLLn-MOFs) possess superior optical and physical properties such as higher luminescent lifetime, quantum yield, high stability, high surface area, high agent loading, and intrinsic biodegradability, and therefore are regarded as a novel generation of luminescent material compared with bulk lanthanide-based metal–organic frameworks (Ln-MOFs). Traditional luminescent Ln-MOFs have been well studied; however, NLLn-MOFs taking the advantages of nanomaterials have attracted extensive investigations for applications in optical imaging in living cells, light-harvesting, and sensing. In this review, we provide a survey of the latest progresses made in developing NLLn-MOFs, which contains the fundamental optical features, synthesis, and their potential applications. Finally, the future prospects and challenges of the rapidly growing field are summarized.

  6. A new luminescent lanthanide supramolecular network possessing free Lewis base sites for highly selective and sensitive Cu(2+) sensing.

    Science.gov (United States)

    Chu, Tianshu; Hu, Yunsong; Wu, Jinlun; Zeng, Chenghui; Yang, Yangyi; Ng, Seik Weng

    2016-06-08

    A series of new lanthanide complexes, formulated as [Ln2(DCSAL)3(H2O)11]·3DCSAL·4H2O [Ln = Eu (1), Gd (2) and Tb (3); DCSAL = 3,5-dichlorosalicylate], have been synthesized and characterized by single crystal X-ray analysis. They are dinuclear clusters and form a 3D supramolecular network viaπ-π stacking and halogen bonding interactions. 3 exhibits strong Tb characteristic emission, whose quantum yield is as high as 38%. Due to binding with Cu(2+) ions via its Lewis acid-base interactions, 3 displayed a high selectivity and sensitivity for Cu(2+) detection based on Tb(3+) emission quenching. The possible quenching mechanism was further proved to be a static quenching mechanism by Stern-Volmer plots and UV-vis spectrum. More importantly, the binding constant between 3 and Cu(2+) is also calculated by the Benesi-Hildebrand method, which is helpful for quantitative analysis.

  7. Luminescent 1-hydroxy-2-pyridinone chelates of lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Raymond, Kenneth N.; Xu, Jide; Moore, Evan G.; Werner, Eric J.

    2017-01-31

    The present invention provides luminescent complexes between a lanthanide ion and an organic ligand which contains 1,2-hydroxypyridinone units. The complexes of the invention are stable in aqueous solutions and are useful as molecular probes, for example in medical diagnostics and bioanalytical assay systems. The invention also provides methods of using the complexes of the invention.

  8. Luminescent 1-hydroxy-2-pyridinone chelates of lanthanides

    Science.gov (United States)

    Raymond, Kenneth N.; Xu, Jide; Moore, Evan G.; Werner, Eric J.

    2013-10-15

    The present invention provides luminescent complexes between a lanthanide ion and an organic ligand which contains 1,2-hydroxypyridinone units. The complexes of the invention are stable in aqueous solutions and are useful as molecular probes, for example in medical diagnostics and bioanalytical assay systems. The invention also provides methods of using the complexes of the invention.

  9. Luminescence properties of lanthanide and ytterbium lanthanide titanate thin films grown by atomic layer deposition

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, Per-Anders, E-mail: p.a.hansen@kjemi.uio.no; Fjellvåg, Helmer; Nilsen, Ola [Department of Chemistry, Centre for Materials Science and Nanotechnology, University of Oslo, Sem Sælandsvei 26, 0371 Oslo (Norway); Finstad, Terje G. [Department of Physics, Centre for Materials Science and Nanotechnology, University of Oslo, Sem Sælandsvei 24, 0371 Oslo (Norway)

    2016-01-15

    Lanthanide based luminescent materials are highly suitable as down conversion materials in combination with a UV-absorbing host material. The authors have used TiO{sub 2} as the UV-absorbing host material and investigated the energy transfer between TiO{sub 2} and 11 different lanthanide ions, Ln{sup 3+} (Ln = La, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb) in thin films grown by atomic layer deposition. They have also investigated the possibility to improve the overall energy transfer from TiO{sub 2} to Yb{sup 3+} with a second Ln{sup 3+}, in order to enhance down conversion. The films were grown at a substrate temperature of 300 °C, using the Ln(thd){sub 3}/O{sub 3} (thd = 2,2,6,6-tetramethyl-3,5-heptanedione) and TiCl{sub 4}/H{sub 2}O precursor pairs. The focus of the work is to explore the energy transfer from TiO{sub 2} to Ln{sup 3+} ions, and the energy transfer between Ln{sup 3+} and Yb{sup 3+} ions, which could lead to efficient down conversion. The samples have been characterized by x-ray diffraction, x-ray fluorescence, spectroscopic ellipsometry, and photoluminescence. All films were amorphous as deposited, and the samples have been annealed at 600, 800, and 1000 °C in order to investigate the correlation between the crystallinity and luminescence. The lanthanum titanium oxide samples showed a weak and broad emission centered at 540 nm, which was absent in all the other samples, indicating energy transfer from TiO{sub 2} to Ln{sup 3+} in all other lanthanide samples. In the amorphous phase, all samples, apart from La, Tb, and Tm, showed a typical f-f emission when excited by a 325 nm HeCd laser. None of the samples showed any luminescence after annealing at 1000 °C due to the formation of Ln{sub 2}Ti{sub 2}O{sub 7}. Samples containing Nd, Sm, and Eu show a change in emission spectrum when annealed at 800 °C compared to the as-deposited samples, indicating that the smaller lanthanides crystallize in a different manner than the larger

  10. An ionic liquid based synthesis method for uniform luminescent lanthanide fluoride nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Nunez, Nuria O; Ocana, Manuel [Instituto de Ciencia de Materiales de Sevilla, CSIC, Americo Vespucio 49, 41092, Isla de la Cartuja, Sevilla (Spain)

    2007-11-14

    We describe a facile procedure for the synthesis of uniform lanthanide fluoride nanophosphors by homogeneous precipitation in ethylene glycol solutions containing lanthanide precursors and an ionic liquid (1-butyl, 2-methylimidazolium tetrafluoroborate). It is shown that the use of this ionic liquid as a fluoride source, an appropriate choice of the solvent and the lanthanide precursor, and the adjustment of reaction temperature, are essential to obtain uniform nanoparticles. This method is applied to the preparation of pure YF{sub 3}, EuF{sub 3} and TbF{sub 3} nanoparticles as well as of Eu-doped YF{sub 3} and Tb-doped YF{sub 3}. In most cases, highly uniform nanoparticles were obtained, the size of which could be tuned in the nanometer range by adjusting the nature and concentration of the starting lanthanide precursor. The luminescent properties of the synthesized materials are also evaluated.

  11. Luminescent lanthanide cryptates: from the bench to the bedside.

    Science.gov (United States)

    Zwier, Jurriaan M; Bazin, Hervé; Lamarque, Laurent; Mathis, Gérard

    2014-02-17

    The design and application of luminescent lanthanide cryptates for sensing biological interactions is highlighted through the review of the work performed in our laboratory and with academic collaborations. The path from the initial applications probing biochemical interaction in vitro to "state-of-the-art" cellular assays toward clinical applications using homogeneous time-resolved fluorescence technology is described. An overview of the luminescent lanthanide macrocyclic compounds developed at Cisbio in the recent past is given with an emphasis on specific constraints required by specific applications. Recent assays for drug-discovery and diagnostic purposes using both antibody-based and suicide-enzyme-based technology are illustrated. New perspectives in the field of molecular medicine and time-resolved microscopy are discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-07-10

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

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

    Science.gov (United States)

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

    2013-11-01

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

  14. White-Light-Emitting Lanthanide Metallogels with Tunable Luminescence and Reversible Stimuli-Responsive Properties.

    Science.gov (United States)

    Chen, Pangkuan; Li, Qiaochu; Grindy, Scott; Holten-Andersen, Niels

    2015-09-16

    We have developed model light-emitting metallogels functionalized with lanthanide metal-ligand coordination complexes via a terpyridyl-end-capped four-arm poly(ethylene glycol) polymer. The optical properties of these highly luminescent polymer networks are readily modulated over a wide spectrum, including white-light emission, simply by tuning of the lanthanide metal ion stoichiometry. Furthermore, the dynamic nature of the Ln-N coordination bonding leads to a broad variety of reversible stimuli-responsive properties (mechano-, vapo-, thermo-, and chemochromism) of both sol-gel systems and solid thin films. The versatile functional performance combined with the ease of assembly suggests that this lanthanide coordination polymer design approach offers a robust pathway for future engineering of multi-stimuli-responsive polymer materials.

  15. From Antenna to Assay: Lessons Learned in Lanthanide Luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Moore, Evan; Samuel, Amanda; Raymond, Kenneth

    2008-09-25

    Ligand-sensitized luminescent lanthanide(III) complexes are of considerable current interest due to their unique photophysical properties (micro- to millisecond lifetimes, characteristic and narrow emission bands, and large Stokes shifts), which make them well suited to serve as labels in fluorescence-based bioassays. The long-lived Ln(III) emission can be temporally resolved from scattered light and background fluorescence, resulting in vastly enhanced measurement sensitivity. One of the challenges in this field is the design of sensitizing ligands that provide highly emissive Ln(III) complexes that also possess sufficient stability and aqueous solubility required for practical applications. In this account we give an overview of some of the general properties of the trivalent lanthanides and follow with a summary of advances made in our laboratory in the development of highly luminescent Tb(III) and Eu(III) complexes for applications in biotechnology. A focus of our research has been the optimization of these compounds as potential commercial agents for use in Homogeneous Time Resolved Fluorescence (HTRF) technology, the requirements and current use of which will be briefly discussed. Our approach involves developing high-stability octadentate Tb(III) and Eu(III) complexes that rely on all-oxygen donor atoms as well as using multi-chromophore chelates to increase molar absorptivity compared to earlier examples that utilize a single pendant antenna chromophore. We have found that ligands based on 2-hydroxyisophthalamide (IAM) provide exceptionally emissive Tb(III) complexes with quantum yield values up to ca. 60%. Solution thermodynamic studies have indicated that these complexes are stable at the nanomolar concentrations required for commercial assays. Through synthetic modification of the IAM-chromophore, in conjunction with time-dependent density functional theory (TD-DFT) calculations, we have developed a method to predict absorption and emission properties of

  16. Lanthanide-doped luminescent nano-bioprobes: from fundamentals to biodetection.

    Science.gov (United States)

    Liu, Yongsheng; Tu, Datao; Zhu, Haomiao; Ma, En; Chen, Xueyuan

    2013-02-21

    Trivalent lanthanide (Ln(3+))-doped luminescent inorganic nanoparticles (NPs), characterized by long-lived luminescence, large Stokes and/or anti-Stokes shifts, narrow emission bands and high photochemical stability, are considered to be promising candidates as luminescent bioprobes in biomedicine and biotechnology. In this feature article, we provide a brief overview of the most recent advances in Ln(3+)-doped luminescent inorganic NPs as sensors, which covers from their chemical and physical fundamentals to biodetection, such as controlled synthesis methodology, surface modification chemistry, optical physics, and their promising applications in diverse bioassays, with an emphasis on heterogeneous and homogeneous in vitro biodetection. Finally, some of the most important emerging trends and future efforts toward this active research field are also proposed.

  17. Recent Advance of Biological Molecular Imaging Based on Lanthanide-Doped Upconversion-Luminescent Nanomaterials

    Directory of Open Access Journals (Sweden)

    Yuanzeng Min

    2014-02-01

    Full Text Available Lanthanide-doped upconversion-luminescent nanoparticles (UCNPs, which can be excited by near-infrared (NIR laser irradiation to emit multiplex light, have been proven to be very useful for in vitro and in vivo molecular imaging studies. In comparison with the conventionally used down-conversion fluorescence imaging strategies, the NIR light excited luminescence of UCNPs displays high photostability, low cytotoxicity, little background auto-fluorescence, which allows for deep tissue penetration, making them attractive as contrast agents for biomedical imaging applications. In this review, we will mainly focus on the latest development of a new type of lanthanide-doped UCNP material and its main applications for in vitro and in vivo molecular imaging and we will also discuss the challenges and future perspectives.

  18. Dual Emissive-Reflective Display Materials with Large Emission Switching Using Highly Luminescent Lanthanide(III) Complex and Electrochromic Material

    Science.gov (United States)

    Kanazawa, Kenji; Nakamura, Kazuki; Kobayashi, Norihisa

    2013-05-01

    Electroswitching of emission and coloration was achieved by a combination of a luminescent Eu(III) complex and an electrochromic molecule of diheptyl viologen (HV2+), in order to utilize them as novel display devices with dual emissive-reflective modes. The coloration was associated with the HV2+ electrochromism. Emission control was also achieved by the HV2+ electrochromism via intermolecular energy transfer from the excited state of the Eu(III) ion to the HV+. In order to improve ON-OFF contrast in emission, the emission quantum yield of Eu(III) complex were considerably improved using low vibrational phosphine oxide ligands, resulting in the large control of emission switching.

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

    Science.gov (United States)

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

    2001-05-01

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

  20. Highly Efficient Visible-to-NIR Luminescence of Lanthanide(III) Complexes with Zwitterionic Ligands Bearing Charge-Transfer Character: Beyond Triplet Sensitization.

    Science.gov (United States)

    Pan, Mei; Du, Bin-Bin; Zhu, Yi-Xuan; Yue, Mei-Qin; Wei, Zhang-Wen; Su, Cheng-Yong

    2016-02-12

    Two zwitterionic-type ligands featuring π-π* and intraligand charge-transfer (ILCT) excited states, namely 1,1'-(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)dipyridinium-4-olate (TMPBPO) and 1-dodecylpyridin-4(1 H)-one (DOPO), have been prepared and applied to the assembly of lanthanide coordination complexes in an effort to understand the ligand-direction effect on the structure of the Ln complexes and the ligand sensitization effect on the luminescence of the Ln complexes. Due to the wide-band triplet states plus additional ILCT excitation states extending into lower energy levels, broadly and strongly sensitized photoluminescence of f→f transitions from various Ln(3+) ions were observed to cover the visible to near-infrared (NIR) regions. Among which, the Pr, Sm, Dy, and Tm complexes simultaneously display both strong visible and NIR emissions. Based on the isostructural feature of the Ln complexes, color tuning and single-component white light was achieved by preparation of solid solutions of the ternary systems Gd-Eu-Tb (for TMPBPO) and La-Eu-Tb and La-Dy-Sm (for DOPO). Moreover, the visible and NIR luminescence lifetimes of the Ln complexes with the TMPBPO ligand were investigated from 77 to 298 K, revealing a strong temperature dependence of the Tm(3+) ((3) H4 ) and Yb(3+) ((2) F5/2 ) decay dynamics, which has not been explored before for their coordination complexes.

  1. New cross-linking quinoline- and quinolone-based luminescent lanthanide probes for sensitive labeling

    Science.gov (United States)

    Pillai, Shyamala; Wirpsza, Laura; Kozlov, Maxim; Marras, Salvatore A. E.; Krasnoperov, Lev N.; Mustaev, Arkady

    2012-03-01

    New luminescent lanthanide chelates containing thiol-, amine-, and click-reactive groups in antenna-fluorophore moieties were synthesized. The chelates include diethylenetriaminepentaacetic acid (DTPA) coupled to two types of chromophores: 7-amino-4-trifluoromethyl-2(1H) quinolinone, and 7-amino-4-trifluoromethyl-2-alkoxyquinoline. The synthesized compounds were characterized using NMR, light absorption, steady-state and time-resolved fluorescent spectroscopy. Some of the compounds displayed high brightness with Tb3+, Eu3+, and Dy3+. Obtained reactive lanthanide chelates can be easily attached to biological molecules. The probes demonstrated high performance in molecular beaconbased DNA hybridization assays (sub-pico molar detection limit), in bacterial proteome labeling, and in live cell imaging.

  2. Pyrolytic synthesis and luminescence of porous lanthanide Eu-MOF.

    Science.gov (United States)

    Jin, Guangya; Liu, Zhijian; Sun, Hongfa; Tian, Zhiyong

    2016-02-01

    A lanthanide metal coordination polymer [Eu2(BDC)3(DMSO)(H2O)] was synthesized by the reaction of europium oxide with benzene-1,3-dicarboxylic acid (H2BDC) in a mixed solution of dimethyl sulfoxide (DMSO) and water under hydrothermal conditions. The crystal structure of Eu2(BDC)3(DMSO)(H2O) was characterized by X-ray diffraction (XRD). Thermo-gravimetric analysis of Eu2(BDC)3(DMSO)(H2O) indicated that coordinated DMSO and H2O molecules could be removed to create Eu2(BDC)3(DMSO)(H2O)-py with permanent microporosity, which was also verified by powder XRD (PXRD) and elemental analysis. Both Eu2(BDC)3(DMSO)(H2O) and Eu2(BDC)3(DMSO)(H2O)-py showed mainly Eu-based luminescence and had characteristic emissions in the range 550-700 nm.

  3. A luminescent mixed-lanthanide-organic framework sensor for decoding different volatile organic molecules.

    Science.gov (United States)

    Zhan, Chao; Ou, Sha; Zou, Chao; Zhao, Min; Wu, Chuan-De

    2014-07-01

    A flexible tripodal polyaromatic acid (4,4',4″-(((2,4,6-trimethylbenzene-1,3,5-triyl)-tris(methylene))-tris(oxy))tribenzoic acid, H3TCM) was used to adapt the coordination sites of lanthanide ions for the construction of microporous lanthanide-organic frameworks (LOFs) [LnTCM(H2O)2]·3DMF·H2O (Ln-TCM; Ln = La, Eu, and/or Tb). In these LOFs, the emission band of TCM matches well with the excitation energy of lanthanide ions (Eu(3+) and Tb(3+)) which results in high-efficient resonance energy transfer from TCM to lanthanide ions. Moreover, the mixed EuxTb1-x-TCM has tunable pores to adapt different induced-fit-type host-guest interactions which can modulate both the energy transfer efficiency from TCM to Ln(3+) ions and the energy allocation between Eu(3+) and Tb(3+) ions in the luminescence spectra. We demonstrate that the Eu(x)Tb(1-x)-TCM sensor has the capability of decoding different volatile organic molecules (VOMs) with a clearly differentiable and unique emission intensity ratio of (5)D0 → (7)F2 (Eu(3+), 614 nm) to (5)D4 → (7)F5 (Tb(3+), 545 nm) transitions for every different VOM. Compared with the traditional absolute emission intensity method, such a self-referencing emission intensity strategy has generated self-calibrating, highly differentiable, and very stable luminescent signals for decoding different VOMs from the unique Eu(x)Tb(1-x)-TCM platform, which has great potential for practical applications.

  4. Sol-Gel Electrolytes Incorporated by Lanthanide Luminescent Materials and Their Photophysical Properties

    Science.gov (United States)

    Yu, Chufang; Zhang, Zhengyang; Fu, Meizhen; Gao, Jinwei; Zheng, Yuhui

    2017-10-01

    A group of silica gel electrolytes with lanthanide luminescent hybrid materials were assembled and investigated. Photophysical studies showed that terbium and europium hybrids displayed characteristic green and red emissions within the electrolytes. The influence of different concentration of the lanthanide hybrids on the electrochemical behavior of a gelled electrolyte valve-regulated lead-acid battery were studied through cyclic voltammograms, electrochemical impedance spectroscopy, water holding experiments and mobility tests. The morphology and particle size were analyzed by scanning electron microscopy. The results proved that lanthanide (Tb3+/Eu3+) luminescent materials are effective additives which will significantly improve the electrochemical properties of lead-acid batteries.

  5. Synthesis and luminescence properties of lanthanide complexes with a new tripodal ligands featuring salicylamide arms.

    Science.gov (United States)

    Song, Xue-Qin; Dong, Wen-Kui; Zhang, Yu-Jie; Liu, Wei-Sheng

    2010-01-01

    A series of luminescent lanthanide complexes with a new tripodal ligand featuring salicylamide arms, 2,2',2''-nitrilotris(2-furfurylaminoformylphenoxy)triethylamine (L), were synthesized and characterized by elemental analysis, IR and molar conductivity measurements. Photophysical properties of the complexes were studied by means of UV-vis absorption and steady-state luminescence spectroscopy. Excited-state luminescence lifetimes and quantum yield of the complexes were determined. Luminescence studies demonstrated that the tripodal ligand featuring salicylamide arms exhibits a good antennae effect with respect to the Tb(III) and Dy(III) ion due to efficient intersystem crossing and ligand to metal energy transfer. From a more general perspective, this work offers interesting perspectives for the development of efficient luminescent stains and enlarges the arsenal for developing novel luminescent lanthanide complexes of salicylamide derivatives.

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

    Science.gov (United States)

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

    2016-06-01

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

  7. Establishing the Structural Integrity of Core-Shell Nanoparticles against Elemental Migration using Luminescent Lanthanide Probes.

    Science.gov (United States)

    Chen, Bing; Peng, Dengfeng; Chen, Xian; Qiao, Xvsheng; Fan, Xianping; Wang, Feng

    2015-10-19

    Core-shell structured nanoparticles are increasingly used to host luminescent lanthanide ions but the structural integrity of these nanoparticles still lacks sufficient understanding. Herein, we present a new approach to detect the diffusion of dopant ions in core-shell nanostructures using luminescent lanthanide probes whose emission profile and luminescence lifetime are sensitive to the chemical environment. We show that dopant ions in solution-synthesized core-shell nanoparticles are firmly confined in the designed locations. However, annealing at certain temperatures (greater than circa 350 °C) promotes diffusion of the dopant ions and leads to degradation of the integrity of the nanoparticles. These insights into core-shell nanostructures should enhance our ability to understand and use lanthanide-doped luminescent nanoparticles.

  8. Temperature-dependent luminescence properties of lanthanide(III) β-diketonate complex-doped LAPONITE®.

    Science.gov (United States)

    Xu, Qianqian; Li, Zhiqiang; Wang, Yige; Li, Huanrong

    2016-03-01

    In this work, by doping the lanthanide(III)-hexafluoroacetylacetone complex into LAPONITE®, we obtained a lanthanide-based organic-inorganic hybrid material. The resulting hybrid materials were fully characterized with elementary analysis, scanning electron microscopy (SEM) and powder X-ray diffraction (PXRD) techniques. The Ln(3+) and HFA loadings were experimentally determined to be roughly 0.3 per u.c. and 0.72 per u.c. by analyzing the supernatant (titration against EDTA) and elemental analysis, respectively. XRD patterns suggest that at least partial complexes are intercalated within the interlayers of the LAPONITE®. The in situ formation of luminescent Ln(3+) complexes is confirmed by the luminescence data. Furthermore, the emission intensity ratio of the (5)D4→(7)F5 transition (Tb(3+)) to the (5)D0→(7)F2 transition (Eu(3+)) of the hybrid material containing both Eu(3+) and Tb(3+) can be linearly related to temperature in the range from 197 K to 287 K (temperature sensitivity: 1.107% per K), which will be an appealing alternative for in situ and real time detection of temperature in many special areas. This strategy presents new opportunities for the development of highly sensitive and stable thermo sensors.

  9. Rapid homogeneous immunoassay for cardiac troponin I using switchable lanthanide luminescence.

    Science.gov (United States)

    Päkkilä, Henna; Malmi, Eeva; Lahtinen, Satu; Soukka, Tero

    2014-12-15

    Homogeneous assays are advantageous because of their simplicity and rapid kinetics but typically their performance is severely compromised compared to heterogeneous assay formats. Here, we report a homogeneous immunoassay utilizing switchable lanthanide luminescence for detection and site-specifically labeled recombinant antibody fragments as binders to improve the assay performance. Switchable lanthanide luminescence enabled elimination of assay background due to division of the luminescent lanthanide chelate into two non-luminescent label moieties. Simultaneous biomolecular recognition of model analyte cardiac troponin I by two antibody fragments brought the label moieties together and resulted in self-assembly of luminescent mixed chelate complex. The assay was very rapid as maximal signal-to-background ratios were achieved already after 6 min of incubation. Additionally, the limit of detection was 0.38 ng/mL (16 pM), which was comparable to the limit of detection for the heterogeneous reference assay based on the same binders (0.26 ng/mL or 11 pM). This is the first study to apply switchable lanthanide luminescence in immunoassays and demonstrates the versatile potential of the technology for rapid and sensitive homogeneous assays.

  10. Bifunctional composite microspheres of silica/lanthanide-polyoxometalates/Au: Study on luminescence and catalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun, E-mail: junwang924@mail.ccnu.edu.cn; Fan, Shaohua; Zhao, Weiqian; Lu, Xuelian; Li, Wuke

    2013-12-02

    In this paper, the synthesis and properties of composite silica microspheres grafted with gold nanoparticles and lanthanide-polyoxometalates are described. This synthesis employs polyethyleneimine as the crosslink polymer to immobilize the Au nanoparticles and lanthanide-polyoxometalates on silica spheres, which results in the formation of bifunctional composite microspheres of silica/lanthanide-polyoxometalates/Au. The composite material was found to be catalytically active in the oxidation of styrene, and benzaldehyde and styrene oxide were the main products. Catalyzed oxidation of styrene demonstrates the size-dependent activity of catalysts and the smaller catalyst shows the higher selectivity. Moreover, the composite particles show bright red luminescence under UV light, which could be seen by naked eyes. The luminescence properties of composite material and the effect of Au nanoparticles on the luminescence of Eu ion were investigated, and energy could be more effectively transferred from ligand to lanthanide ion when Au nanoparticles were grafted on silica spheres. The integration of luminescent components and Au particles makes it possible to label catalyst and monitor the catalyzed reactions. - Highlights: • The bifunctional composite microspheres were fabricated. • Both polyoxometalates and Au nanoparticles could be grafted on silica spheres. • The composite particles exhibit the excellent luminescence and catalytic activity. • The Au nanoparticles affect the luminescence properties of Eu{sup 3+} ions.

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

    Science.gov (United States)

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

    2006-03-20

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

  12. Quantifying the formation of chiral luminescent lanthanide assemblies in an aqueous medium through chiroptical spectroscopy and generation of luminescent hydrogels.

    Science.gov (United States)

    Bradberry, Samuel J; Savyasachi, Aramballi Jayant; Peacock, Robert D; Gunnlaugsson, Thorfinnur

    2015-01-01

    Herein we present the synthesis and the photophysical evaluation of water-soluble chiral ligands (2·(R,R) and 2·(S,S)) and their application in the formation of lanthanide directed self-assembled structures. These pyridine-2,6-dicarboxylic amide based ligands, possessing two naphthalene moieties as sensitising antennae, that can be used to populate the excited state of lanthanide ions, were structurally modified using 3-propanesultone and caesium carbonate, allowing for the incorporation of a water-solubilising sulfonate motif. We show, using microwave synthesis, that Eu(III) forms chiral complexes in 1 : 3 (M : L) stoichiometries (Eu·[2·(R,R)]3 and Eu·[2·(S,S)]3) with these ligands, and that the red Eu(III)-centred emission arising from these complexes has quantum yields (Φtot) of 12% in water. Both circular dichroism (CD) and circular polarised luminescence (CPL) analysis show that the complexes are chiral; giving rise to characteristic CD and CPL signatures for both the Λ and the Δ complexes, which both possess characteristic luminescence dissymmetry factors (g(lum)), describing the structure in solution. The self-assembly process was also monitored in situ by observing the changes in the ligand absorption and fluorescence emission, as well as in the Eu(III) luminescence. The change, fitted using non-linear regression analysis, demonstrated high binding affinity for Eu(III) which in part can be assigned to being driven by additional hydrophobic effects. Moreover, using CD spectroscopy, the changes in the chiroptical properties of both (2·(R,R) and 2·(S,S)) were monitored in real time. Fitting the changes in the CD spectra allowed for the step-wise binding constants to be determined for these assemblies; these matched well with those determined from both the ground and the excited state changes. Both the ligands and the Eu(III) complexes were then used in the formation of hydrogels; the Eu(III)-metallogels were luminescent to the naked-eye.

  13. f-state luminescence of lanthanide and actinide ions in solution

    Energy Technology Data Exchange (ETDEWEB)

    Beitz, J.V.

    1993-09-01

    Detailed studies of the luminescence of aquated Am{sup 3+} are presented in the context of prior lanthanide and actinide ion work. The luminescing state of aquated Am{sup 3+} is confirmed to be {sup 5}D{sub l} based on observed emission and excitation spectra. The luminescence lifetime of Am{sup 3+} in H{sub 2}O solution is (22 {plus_minus} 3) ns and (155 {plus_minus} 4) ns in D{sub 2}O solution at 295 K. Judd-Ofelt transition intensity theory qualitatively describes the observed Am{sup 3+} relative integrated fluorescence intensities. Recent luminescence studies on complexed trivalent f-element ions in solution are reviewed as to the similarities and differences between lanthanide ion 4f state and actinide ion 5f state properties.

  14. Hybrid silica luminescent materials based on lanthanide-containing lyotropic liquid crystal with polarized emission

    Energy Technology Data Exchange (ETDEWEB)

    Selivanova, N.M., E-mail: natsel@mail.ru [Kazan National Research Technological University, 68 Karl Marx Str., Kazan 420015 (Russian Federation); Vandyukov, A.E.; Gubaidullin, A.T. [A.E. Arbuzov Institute of Organic and Physical Chemistry of the Kazan Scientific Center of the Russian Academy of Sciences, 8 Acad. Arbuzov Str., Kazan 420088 (Russian Federation); Galyametdinov, Y.G. [Kazan National Research Technological University, 68 Karl Marx Str., Kazan 420015 (Russian Federation)

    2014-11-14

    This paper represents the template method for synthesis of hybrid silica films based on Ln-containing lyotropic liquid crystal and characterized by efficient luminescence. Luminescence films were prepared in situ by the sol–gel processes. Lyotropic liquid crystal (LLC) mesophases C{sub 12}H{sub 25}O(CH{sub 2}CH{sub 2}O){sub 10}H/Ln(NO{sub 3}){sub 3}·6H{sub 2}O/H{sub 2}O containing Ln (III) ions (Dy, Tb, Eu) were used as template. Polarized optical microscopy, X-ray powder diffraction, and FT-IR-spectroscopy were used for characterization of liquid crystal mesophases and hybrid films. The morphology of composite films was studied by the atomic force microscopy method (AFM). The optical properties of the resulting materials were evaluated. It was found that hybrid silica films demonstrate significant increase of their lifetime in comparison with an LLC system. New effects of linearly polarized emission revealed for Ln-containing hybrid silica films. Polarization in lanthanide-containing hybrid composites indicates that silica precursor causes orientation of emitting ions. - Highlights: • We suggest a new simple approach for creating luminescence hybrid silica films. • Ln-containing hybrid silica films demonstrate yellow, green and red emissions. • Tb(III)-containing hybrid film have a high lifetime. • We report effects of linearly polarized emission in hybrid film.

  15. 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.

  16. Time-resolved luminescent biosensing based on inorganic lanthanide-doped nanoprobes.

    Science.gov (United States)

    Zheng, Wei; Tu, Datao; Huang, Ping; Zhou, Shanyong; Chen, Zhuo; Chen, Xueyuan

    2015-03-11

    Time-resolved (TR) photoluminescence (PL) biosensing has been widely adopted in many research and medical institutions. However, commercial molecular TRPL bioprobes like lanthanide (Ln(3+))-chelates suffer from poor photochemical stability and long-term toxicity. Inorganic Ln(3+)-doped nanocrystals (NCs), owing to their superior physicochemical properties over Ln(3+)-chelates, are regarded as a new generation of luminescent nanoprobes for TRPL biosensing. The long-lived PL of Ln(3+)-doped NCs combined with the TRPL technique is able to completely suppress the interference of the short-lived background, resulting in a background-free signal and therefore a remarkable sensitivity for biosensing. In this feature article, we summarize the latest advancements in inorganic Ln(3+)-doped NCs as TRPL nano-bioprobes from their fundamental optical properties to their potential applications for ultrasensitive biodetection and high-resolution bioimaging. Future efforts towards the commercialization of these nanoprobes are also proposed.

  17. Luminescent lanthanide nanomaterials: an emerging tool for theranostic applications.

    Science.gov (United States)

    Ranjan, Shashi; Jayakumar, Muthu Kumara Gnanasammandhan; Zhang, Yong

    2015-05-01

    Lanthanide materials have been gaining popularity for use in various theranostic applications, primarily due to their unique optical properties such as narrow emission bands, multiple emission wavelengths, emission tunability, long fluorescence lifetime and large Stokes shift. Apart from these, some lanthanide materials also exhibit magnetic and light-up conversion properties. Such nanomaterials have been used for a wide range of applications ranging from detection of biomarkers, in vitro and in vivo imaging to therapeutic applications. Recently, combined modalities of lanthanide nanomaterials for simultaneous detection/imaging and delivery of therapeutic agents (termed 'theranostics') have been explored. The various advantages and disadvantages of using lanthanide nanomaterials as theranostic agents and potential areas for future development have been discussed in this review.

  18. A Lanthanide MOF Thin-Film Fixed with Co3 O4 Nano-Anchors as a Highly Efficient Luminescent Sensor for Nitrofuran Antibiotics.

    Science.gov (United States)

    Zhang, Feng; Yao, Hua; Chu, Tianshu; Zhang, Gaowei; Wang, Yi; Yang, Yangyi

    2017-08-01

    Nitrofurans are a group of widely used veterinary antibiotics, which have been banned due to antibiotics pollution. Development of a rapid and effective method for the detection of nitrofuran antibiotics (NFAs) is an important challenge. Herein, we designed a chemical sensor based on a thin-film composed of the lanthanide metal-organic framework (Ln-MOF) {[Eu2 (BCA)3 (H2 O)(DMF)3 ]⋅0.5DMF⋅H2 O}n (Eu-BCA, in which BCA is 2,2'-biquinoline-4,4'-dicarboxylate) coated on a cost-effective stainless steel wire mesh (SSWM) by Co3 O4 nano-anchor fixation method. The MOF coatings were well adhered to the SSWM, resulting in a three-dimensional porous, flexible, and processable sensor. The structure of the as-prepared MOF thin-film was confirmed by powder X-ray diffraction (PXRD), and the surface morphology was examined by scanning electron microscopy (SEM). Significantly, the Eu-BCA thin-film was highly selective and sensitive to NFAs, and yet remained unaffected by other common antibiotics that may be present. The limits of detection for nitrofurantoin (NFT) and nitrofurazone (NFZ) are 0.21 and 0.16 μm, respectively. NFAs were also successfully detected in water from the Pearl River in Guangzhou, and from bovine serum samples. Hence, the reported Ln-MOF thin-film is a promising sensor for the detection of NFAs, thereby helping to protect human beings from all manner of hazards that arise from the abuse of antibiotics in livestock breeding. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Preparation of core-shell NaGdF4 nanoparticles doped with luminescent lanthanide ions to be used as upconversion-based probes.

    Science.gov (United States)

    Wang, Feng; Deng, Renren; Liu, Xiaogang

    2014-07-01

    Sodium gadolinium fluoride (NaGdF4) is an ideal host material for the incorporation of luminescent lanthanide ions because of its high photochemical stability, low vibrational energy and its ability to mediate energy exchanges between the lanthanide dopants. This protocol describes the detailed experimental procedure for synthesizing core-shell NaGdF4 nanoparticles that incorporate lanthanide ions into different layers for efficiently converting a single-wavelength, near-IR excitation into a tunable visible emission. These nanoparticles can then be used as luminescent probes in biological samples, in 3D displays, in solar energy conversion and in photodynamic therapy. The NaGdF4 nanoparticles are grown through co-precipitation in a binary solvent mixture of oleic acid and 1-octadecene. Doping by lanthanides with controlled compositions and concentrations can be achieved concomitantly with particle growth. The lanthanide-doped NaGdF4 nanoparticles then serve as seed crystals for subsequent epitaxial growth of shell layers comprising different lanthanide dopants. The entire procedure for the preparation and isolation of the core-shell nanoparticles comprising two epitaxial shell layers requires ∼15 h for completion.

  20. 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.

  1. Synthesis and luminescence properties of lanthanide complexes with a new tripodal ligand featuring N-thenylsalicylamide arms.

    Science.gov (United States)

    Song, Xue-Qin; Zheng, Qing-Fang; Wang, Li; Liu, Wei-Sheng

    2012-01-01

    To explore the relationship between the structure of the ligands and the luminescent properties of the lanthanide complexes, luminescent lanthanide complexes of a new tripodal ligand, featuring N-thenylsalicylamide arms, were synthesized and characterized by elemental analysis, IR and TGA measurements. Photophysical properties of the complexes were studied by means of UV - visible absorption and steady-state luminescence spectroscopy. The results of UV - vis spectra indicate that metal binding does not disturb the electronic structure of the ligand. Excited-state luminescence lifetimes and quantum yields of the complexes were determined. The photoluminescence analysis suggested that there is an efficient ligand - Ln(III) energy transfer for the Tb(III) complex, and the ligand is an efficient 'antenna' for Tb(III). From a more general perspective, the results demonstrated the potential application of the lanthanide complex as luminescent materials in material chemistry. Copyright © 2012 John Wiley & Sons, Ltd.

  2. Water-Soluble 2-Hydroxyisophthalamides for Sensitization of Lanthanide Luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Samuel, Amanda P. S.; Moore, Evan G.; Melchior, Marco; Xu, Jide; Raymond, Kenneth N.

    2008-02-20

    A series of octadentate ligands featuring the 2-hydroxyisophthalamide (IAM) antenna chromophore (to sensitize Tb(III) and Eu(III) luminescence) has been prepared and characterized. The length of the alkyl amine scaffold that links the four IAM moieties has been varied in order to investigate the effect of the ligand backbone on the stability and photophysical properties of the Ln(III) complexes. The amine backbones utilized in this study are N,N,N{prime},N{prime}-tetrakis-(2-aminoethyl)-ethane-1,2-diamine [H(2,2)-], N,N,N{prime},N{prime}-tetrakis-(2-aminoethyl)-propane-1,3-diamine [H(3,2)-] and N,N,N{prime},N{prime}-tetrakis-(2-aminoethyl)-butane-1,4-diamine [H(4,2)-]. These ligands also incorporate methoxyethylene [MOE] groups on each of the IAM chromophores to increase their water solubility. The aqueous ligand protonation constants and Tb(III) and Eu(III) formation constants were determined from solution thermodynamic studies. The resulting values indicate that at physiological pH, the Eu(III) and Tb(III) complexes of H(2,2)-IAM-MOE and H(4,2)-IAM-MOE are sufficiently stable to prevent dissociation at nanomolar concentrations. The photophysical measurements for the Tb(III) complexes gave overall quantum yield values of 0.56, 0.39, and 0.52 respectively for the complexes with H(2,2)-IAM-MOE, H(3,2)-IAM-MOE and H(4,2)-IAM-MOE, while the corresponding Eu(III) complexes displayed significantly weaker luminescence, with quantum yield values of 0.0014, 0.0015, and 0.0058, respectively. Analysis of the steady state Eu(III) emission spectra provides insight into the solution symmetries of the complexes. The combined solubility, stability and photophysical performance of the Tb(III) complexes in particular make them well suited to serve as the luminescent reporter group in high sensitivity time-resolved fluoroimmunoassays.

  3. Water-Soluble 2-Hydroxyisophthalamides for Sensitization of Lanthanide Luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Samuel, Amanda P. S.; Moore, Evan G.; Melchior, Marco; Xu, Jide; Raymond, Kenneth N.

    2008-02-20

    A series of octadentate ligands featuring the 2-hydroxyisophthalamide (IAM) antenna chromophore (to sensitize Tb(III) and Eu(III) luminescence) has been prepared and characterized. The length of the alkyl amine scaffold that links the four IAM moieties has been varied in order to investigate the effect of the ligand backbone on the stability and photophysical properties of the Ln(III) complexes. The amine backbones utilized in this study are N,N,N{prime},N{prime}-tetrakis-(2-aminoethyl)-ethane-1,2-diamine [H(2,2)-], N,N,N{prime},N{prime}-tetrakis-(2-aminoethyl)-propane-1,3-diamine [H(3,2)-] and N,N,N{prime},N{prime}-tetrakis-(2-aminoethyl)-butane-1,4-diamine [H(4,2)-]. These ligands also incorporate methoxyethylene [MOE] groups on each of the IAM chromophores to increase their water solubility. The aqueous ligand protonation constants and Tb(III) and Eu(III) formation constants were determined from solution thermodynamic studies. The resulting values indicate that at physiological pH, the Eu(III) and Tb(III) complexes of H(2,2)-IAM-MOE and H(4,2)-IAM-MOE are sufficiently stable to prevent dissociation at nanomolar concentrations. The photophysical measurements for the Tb(III) complexes gave overall quantum yield values of 0.56, 0.39, and 0.52 respectively for the complexes with H(2,2)-IAM-MOE, H(3,2)-IAM-MOE and H(4,2)-IAM-MOE, while the corresponding Eu(III) complexes displayed significantly weaker luminescence, with quantum yield values of 0.0014, 0.0015, and 0.0058, respectively. Analysis of the steady state Eu(III) emission spectra provides insight into the solution symmetries of the complexes. The combined solubility, stability and photophysical performance of the Tb(III) complexes in particular make them well suited to serve as the luminescent reporter group in high sensitivity time-resolved fluoroimmunoassays.

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

    Energy Technology Data Exchange (ETDEWEB)

    Liu Mingjing [State Key Laboratory of Fine Chemicals, School of Chemistry, Dalian University of Technology, Dalian 116024 (China); Ye Zhiqiang, E-mail: zhiqiangye2001@yahoo.com.cn [State Key Laboratory of Fine Chemicals, School of Chemistry, Dalian University of Technology, Dalian 116024 (China); Xin Chenglong [State Key Laboratory of Fine Chemicals, School of Chemistry, Dalian University of Technology, Dalian 116024 (China); Yuan Jingli, E-mail: jingliyuan@yahoo.com.cn [State Key Laboratory of Fine Chemicals, School of Chemistry, Dalian University of Technology, Dalian 116024 (China)

    2013-01-25

    Highlights: Black-Right-Pointing-Pointer A lanthanide complex-based ratiometric luminescent pH sensor was developed. Black-Right-Pointing-Pointer The sensor can luminously respond to pH in weakly acidic to neutral media. Black-Right-Pointing-Pointer The sensor can be used for monitoring pH with time-resolved luminescence mode. Black-Right-Pointing-Pointer The sensor can be also used for monitoring pH with absorbance mode. Black-Right-Pointing-Pointer 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 Prime -hydroxy-2,2 Prime :6 Prime ,2 Prime Prime -terpyridine-6,6 Prime Prime -diyl) bis(methylenenitrilo) tetrakis(acetic acid) (HTTA), was designed and synthesized for developing time-resolved luminescence pH sensors based on its Eu{sup 3+} and Tb{sup 3+} complexes. The luminescence characterization results reveal that the luminescence intensity of HTTA-Eu{sup 3+} is strongly dependent on the pH values in weakly acidic to neutral media (pK{sub a} = 5.8, pH 4.8-7.5), while that of HTTA-Tb{sup 3+} is pH-independent. This unique luminescence response allows the mixture of HTTA-Eu{sup 3+} and HTTA-Tb{sup 3+} (the HTTA-Eu{sup 3+}/Tb{sup 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{sup 3+} emission at 540 nm to its Eu{sup 3+} emission at 610 nm, I{sub 540nm}/I{sub 610nm}, as a signal. Moreover, the UV absorption spectrum changes of the HTTA-Eu{sup 3+}/Tb{sup 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{sub 290nm

  5. Spectroscopic studies on the lanthanide sensitized luminescence and chemiluminescence properties of fluoroquinolone with different structure

    Science.gov (United States)

    Sun, Chunyan; Ping, Hong; Zhang, Minwei; Li, Hongkun; Guan, Fengrui

    2011-11-01

    Lanthanide sensitized luminescence and chemiluminescence (CL) are of great importance because of the unique spectral properties, such as long lifetime, large Stokes shifts, and narrow emission bands characteristic to lanthanide ions (Ln 3+). With the fluoroquinolone (FQ) compounds including enoxacin (ENX), norfloxacin (NFLX), lomefloxacin (LMFX), fleroxacin (FLRX), ofloxacin (OFLX), rufloxacin (RFX), gatifloxacin (GFLX) and sparfloxacin (SPFX), the luminescence and CL properties of Tb 3+-FQ and Eu 3+-FQ complexes have been investigated in this contribution. Ce 4+-SO 32- in acidic conditions was taken as the CL system and sensitized CL intensities of Tb 3+-FQ and Eu 3+-FQ complexes were determined by flow-injection analysis. The luminescence and CL spectra of Tb 3+-FQ complexes show characteristic peaks of Tb 3+ at 490 nm, 545 nm, 585 nm and 620 nm. Complexes of Tb 3+-ENX, Tb 3+-NFLX, Tb 3+-LMFX and Tb 3+-FLRX display relatively strong emission intensity compared with Tb 3+-OFLX, Tb 3+-RFX, Tb 3+-GFLX and Tb 3+-SPFX. Quite weak peaks with unique characters of Eu 3+ at 590 nm and 617 nm appear in the luminescence and CL spectra of Eu 3+-ENX, but no notable sensitized luminescence and CL of Eu 3+ could be observed when Eu 3+ is added into other FQ. The distinct differences on emission intensity of Tb 3+-FQ and Eu 3+-FQ might originate from the different energy gap between the triplet levels of FQ and the excited levels of the Ln 3+. The different sensitized luminescence and CL signals among Tb 3+-FQ complexes could be attributed to different optical properties and substituents of these FQ compounds. The detailed mechanism involved in the luminescence and CL properties of Tb 3+-FQ and Eu 3+-FQ complexes has been investigated by analyzing the luminescence and CL spectra, quantum yields, and theoretical calculation results.

  6. Syntheses, structures and tunable luminescence of lanthanide metal-organic frameworks based on azole-containing carboxylic acid ligand

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Dian; Rao, Xingtang; Yu, Jiancan; Cui, Yuanjing, E-mail: cuiyj@zju.edu.cn; Yang, Yu; Qian, Guodong, E-mail: gdqian@zju.edu.cn

    2015-10-15

    Design and synthesis of a series of isostructural lanthanide metal-organic frameworks (LnMOFs) serving as phosphors by coordinate the H{sub 2}TIPA (5-(1H-tetrazol-5-yl)isophthalic acid) ligands and lanthanide ions is reported. The color of the luminescence can be tuned by adjusting the relative concentration of the lanthanide ions in the host framework GdTIPA, and near-pure-white light emission can be achieved. - Graphical abstract: Lanthanide metal-organic frameworks (LnMOFs) with tunable luminescence were synthesized using an azole-containing carboxylic acid as ligand. - Highlights: • A series of isostructural LnMOFs serving as phosphor is reported. • We model the GdTIPA: Tb{sup 3+}, Eu{sup 3+} which can tune color and emit white light. • The scheme and mechanism of luminescent LnMOFs are also presented and discussed.

  7. Multicolour optical coding from a series of luminescent lanthanide complexes with a unique antenna.

    Science.gov (United States)

    Wartenberg, Nicolas; Raccurt, Olivier; Bourgeat-Lami, Elodie; Imbert, Daniel; Mazzanti, Marinella

    2013-03-04

    The bis-tetrazolate-pyridine ligand H(2)pytz sensitises efficiently the visible and/or near-IR luminescence emission of ten lanthanide cations (Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb). The Ln(III) complexes present sizeable quantum yields in both domains with a single excitation source. The wide range of possible colour combinations in water, organic solvents and the solid state makes the complexes very attractive for labelling and encoding.

  8. Calix[4]arene-triacids as receptors for lanthanides; synthesis and luminescence of neutral Eu3+ and Tb3+ complexes

    NARCIS (Netherlands)

    Rudkevich, Dmitry M.; Verboom, Willem; Tol, van der Erik B.; Staveren, van Catharina J.; Kaspersen, Frans M.; Verhoeven, Jan W.; Reinhoudt, David N.

    1995-01-01

    Calix[4]arene triacids (3a–d) have been prepared that are able to form neutral complexes with lanthanides. Complexes of 3a–d with Eu3+ and Tb3+ have been studied with respect to their luminescent properties in a protic solvent (methanol). In all cases it was found that the luminescent lifetime of th

  9. Lanthanide ion and tetrathiafulvalene-based ligand as a "magic" couple toward luminescence, single molecule magnets, and magnetostructural correlations.

    Science.gov (United States)

    Pointillart, Fabrice; le Guennic, Boris; Cador, Olivier; Maury, Olivier; Ouahab, Lahcène

    2015-11-17

    The synthesis of molecules featuring different properties is a perpetual challenge for the chemists' community. The coexistence and even more the synergy of those properties open new perspectives in the field of molecular devices and molecular electronics. In that sense, coordination chemistry contributed to the development of new functional molecules through, for instance, single-molecule magnets (SMMs) and light emitting molecules with potential applications in high capacity data storage and OLEDs, respectively. The appealing combination of both electronic properties into one single object may offer the possibility to have magnetized luminescent entities at nanometric scale. To that end, lanthanides seem to be one of the key ingredients since their peculiar electronic structures endow them with specific magnetic and luminescence properties. Indeed, lanthanides cover a wide range of emission wavelengths, from infrared to UV, which add up to a large variety of magnetic behaviors, from the fully isotropic spin (e.g., Gd(III)) to highly anisotropic magnetic moments (e.g., Dy(III)). In lanthanide complexes, ligands play a fundamental role because on one hand they govern the orientation of the magnetic moment of anisotropic lanthanides and on the other hand they can sensitize efficiently the luminescence. The design of appropriate organic ligands to elaborate such chemical objects with the desired property appears to be essential but remains a perpetual challenge. In this Account, we describe the design of lanthanide-based complexes that emit light, behave as SMMs, or combine both properties. We have paid peculiar attention to the design of ligands based on the tetrathiafulvalene (TTF) moiety. TTF and its derivatives are well-known chemical entities, stable at different oxidation states, and employed mainly in the synthesis of molecular conductors and superconductors. In addition to their redox properties, TTF-based derivatives act as organic chromophores for the

  10. Diverse lanthanide coordination polymers tuned by the flexibility of ligands and the lanthanide contraction effect: syntheses, structures and luminescence.

    Science.gov (United States)

    Zhou, Xiaoyan; Guo, Yanling; Shi, Zhaohua; Song, Xueqin; Tang, Xiaoliang; Hu, Xiong; Zhu, Zhentong; Li, Pengxuan; Liu, Weisheng

    2012-02-14

    Two new flexible exo-bidentate ligands were designed and synthesized, incorporating different backbone chain lengths bearing two salicylamide arms, namely 2,2'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(N-benzylbenzamide) (L(I)) and 2,2'-(2,2'-(ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(oxy)bis(N-benzylbenzamide) (L(II)). These two structurally related ligands are used as building blocks for constructing diverse lanthanide polymers with luminescent properties. Among two series of lanthanide nitrate complexes which have been characterized by elemental analysis, TGA analysis, X-ray powder diffraction, and IR spectroscopy, ten new coordination polymers have been determined using X-ray diffraction analysis. All the coordination polymers exhibit the same metal-to-ligand molar ratio of 2 : 3. L(I), as a bridging ligand, reacts with lanthanide nitrates forming two different types of 2D coordination complexes: herringbone framework {[Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)](∞) (Ln = La (1), and Pr (2), m = 1, 2)} as type I,; and honeycomb framework {[Ln(2)(NO(3))(6)(L(I))(3)·nCH(3)OH](∞) (Ln = Nd (3), Eu (4), Tb (5), and Er (6), n = 0 or 3)} as type II, which change according to the decrease in radius of the lanthanide. For L(II), two distinct structure types of 1D ladder-like coordination complexes were formed with decreasing lanthanide radii: [Ln(2)(NO(3))(6)(L(II))(3)·2C(4)H(8)O(2)](∞) (Ln = La (7), Pr (8), Nd (9)) as type III, [Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)·nCH(3)OH](∞) (Ln = Eu (10), Tb (11), and Er (12), m, n = 2 or 0) as type IV. The progressive structural variation from the 2D supramolecular framework to 1D ladder-like frameworks is attributed to the varying chain length of the backbone group in the flexible ligands. The photophysical properties of trivalent Sm, Eu, Tb, and Dy complexes at room temperature were also investigated in detail.

  11. Extending the lanthanide-terephthalate system: Isolation of an unprecedented Tb(III)-based coordination polymer with high potential porosity and luminescence properties

    Science.gov (United States)

    Le Natur, François; Calvez, Guillaume; Freslon, Stéphane; Daiguebonne, Carole; Bernot, Kevin; Guillou, Olivier

    2015-04-01

    A novel coordination polymer with chemical formula {[Tb(bdc)1.5(H2O)]ṡ(DMF)(H2O)}∞ (1) has been synthesized by reaction between 1,4-benzene-dicarboxylic acid (H2bdc) and di-cationic hexanuclear entity [Tb6O(OH)8(NO3)6(H2O)12]2+ in an ethylene glycol (EG)/N,N-dimethylformamide (DMF) mixture. This compound has been obtained as single crystals by slow evaporation in air at room temperature. If the hexanuclear entity is destroyed during the reaction, the coordination polymer that is obtained is original and presents promising potential micro-porosity and luminescent properties. It crystallizes in the monoclinic system, space group C12/c1 (No. 15) with the cell parameters a = 23.7540(1) Å, b = 10.5390(4) Å, c = 19.7580(3) Å, β = 125.8100(1)° and Z = 8.

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

    Science.gov (United States)

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

    2015-02-25

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

  13. Understanding the interaction between trivalent lanthanide ions and stereoregular polymethacrylates through luminescence, binding isotherms, NMR, and interaction with cetylpyridinium chloride.

    Science.gov (United States)

    Kogej, Ksenija; Fonseca, Sofia M; Rovisco, José; Azenha, M Emília; Ramos, M Luísa; Seixas de Melo, J Sérgio; Burrows, Hugh D

    2013-11-26

    Complexation of isotactic, syndiotactic, and atactic poly(methacrylic acid), PMA, with trivalent lanthanide ions has been studied in water at a degree of neutralization 0.5. Metal ion binding is shown by quenching of cerium(III) fluorescence, enhancement of Tb(III) luminescence, and lanthanide-induced line broadening in the PMA (1)H NMR spectra. Comparison with lanthanide-acetate complexation suggests carboxylate binds in a bidentate fashion, while Ce(III) luminescence quenching suggests an ≈3:1 carboxylate:metal ion stoichiometry, corresponding to charge neutralization. The presence of both free and bound Ce(III) cations in PMA solutions is confirmed from luminescence decays. Studies of Tb(3+) luminescence lifetime in H2O and D2O solutions show complexation is accompanied by loss of 5-6 water molecules, indicating that each bidentate carboxylate replaces two coordinated water molecules. The behavior depends on pH and polyelectrolyte stereoregularity, and stronger binding is observed with isotactic polyelectrolyte. Binding of cetylpyridinium chloride, CPC, in these systems is studied by luminescence, NMR, and potentiometry. NMR and Tb(3+) luminescence lifetime studies show the strongest binding with the isotactic polymer. Binding of surfactant to poly(methacrylate) in the presence of lanthanides is noncooperative, i.e., it binds to the free sites; binding isotherms in the presence of lanthanides are shifted to higher free surfactant concentrations, compared with sodium ions, have lower slopes and show a clear two-step binding mechanism. While CPC readily replaces the Na(+) ions of poly(methacrylate) and binds very strongly (low critical association concentrations), exchange is much more difficult with the strongly bound trivalent lanthanide ions. Effects of tacticity are seen, with surfactant interacting most strongly with isotactic chains in the initial stages of binding, while in the final stages of binding the interaction is strongest with atactic poly(methacrylate).

  14. Syntheses, structures and luminescent properties of lanthanide coordination polymers assembled from imidazophenanthroline derivative and oxalate ligands

    Science.gov (United States)

    Zhao, Hui; Sun, Xiao-Xia; Hu, Huai-Ming; An, Ran; Yang, Meng-Lin; Xue, Ganglin

    2017-01-01

    Nine new lanthanide coordination polymers, namely, [Ln(Hsfpip)(ox)0.5(H2O)]n·2n(H2O) ((Ln=Eu (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), Y(7)), [Ln(H2sfpip)(ox)(H2O)4]n·2n(H2O) (Ln=Nd (8) Sm (9)), [H2ox=oxalic acid, H3sfpip=2-(2,4-disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline] have been synthesized under hydrothermal conditions and characterized by IR spectra, elemental analysis, powder X-ray diffraction and single crystal X-ray diffraction. When sodium oxalate is added, the reactions of lanthanide ions with H3sfpip resulted in two types of structures. Compounds 1-7 are obtained at pH 5.0 and exhibit 3D tfz-d networks with ox2- anions as linkers to bridge the adjacent layers. Compounds 8-9 are obtained at pH 2.0, and display a 1D chain which is further extended to a 3D supramolecular framework through intermolecular hydrogen bonds and π-π interactions. The structural variation from compounds 1-7 to 8-9 can attribute to the pH effect on construction of lanthanide coordination polymers. Moreover, the thermal stabilities and luminescence properties of 1-9 were also investigated.

  15. Structural, magnetic and luminescent properties of lanthanide complexes with N-salicylideneglycine.

    Science.gov (United States)

    Vančo, Ján; Trávníček, Zdeněk; Kozák, Ondřej; Boča, Roman

    2015-04-28

    A series of anionic heavy lanthanide complexes, involving the N-salicylideneglycinato(2-) Schiff base ligand (salgly) and having the general formula K[Ln(salgly)₂(H₂O)₂]∙H₂O (1-6), where Ln stands for Gd, Tb, Dy, Ho, Er and Tm, was prepared using the one-pot template synthesis. The complexes were thoroughly characterized by elemental and Thermogravimetric/Differential Thermal Analyses (TG/DTA), Fourier Transform Infrared Spectroscopy (FT-IR), and photoluminescence spectroscopies, electrospray-ionization mass spectrometry, and their magnetic properties were studied by temperature-dependent dc magnetic measurements using the superconducting quantum interference device (SQUID). The X-ray structure of the terbium(III) complex (2), representing the unique structure between the lanthanide complexes of N-salicylideneamino acids, was determined. The results of spectral and structural studies revealed the isostructural nature of the prepared complexes, in which the lanthanide ion is octacoordinated by two O,N,O-donor salgly ligands and two aqua ligands. The analysis of magnetic data confirmed that the complexes behave as paramagnets obeying the Curie law. The results of photoluminescence spectral studies of the complexes showed the different origin in their luminescent properties between the solid state and solution. An antenna effect of the Schiff base ligand was observed in a powder form of the complex only, while it acts as a fluorophore in a solution.

  16. 3D lanthanide metal-organic frameworks constructed from 2,6-naphthalenedicarboxylate ligand: synthesis, structure, luminescence and dye adsorption

    Science.gov (United States)

    Zhu, Yajing; Wang, Li; Chen, Xiaodong; Wang, Pengcheng; Fan, Yong; Zhang, Ping

    2017-07-01

    A series of novel isostructural 3D lanthanide metal-organic frameworks {[Ln2(NDC)3(H2O)4]·(DMF)4}n (Ln=Eu(1), Gd(2), Tb(3), Er(4), Yb(5), Dy(6), Y(7), Lu(8), H2NDC =2,6-Naphthalenedicarboxylic acid, DMF=N,N-dimethylformamide) with a rhombic channel along the b axis and high thermal stabilities, have been successfully synthesized under solvothermal conditions. The network can be described as 2, 4, 5-connected net with Schäfli symbol of (42.62.82)2(42.63.85)2(6). Luminescent studies illustrate that 1, 2, 7 and 8 exhibit strong luminescent emitting of the corresponding Ln(III) centers in the visible range, while 5 shows near-infrared range (NIR) luminescence. Further studies of 1 and 2A (activated product of 2) show that 1 displays good stability in different solvents and excellent fluorescence sensing for organic solvent small molecules and 2A ([Gd2(NDC)3(H2O)4]n) exhibits good adsorption capacity for organic dyes in water, especially for crystal violet.

  17. An integrated closed-tube 2-plex PCR amplification and hybridization assay with switchable lanthanide luminescence based spatial detection.

    Science.gov (United States)

    Lahdenperä, Susanne; Spangar, Anni; Lempainen, Anna-Maija; Joki, Laura; Soukka, Tero

    2015-06-21

    Switchable lanthanide luminescence is a binary probe technology that inherently enables a high signal modulation in separation-free detection of DNA targets. A luminescent lanthanide complex is formed only when the two probes hybridize adjacently to their target DNA. We have now further adapted this technology for the first time in the integration of a 2-plex polymerase chain reaction (PCR) amplification and hybridization-based solid-phase detection of the amplification products of the Staphylococcus aureus gyrB gene and an internal amplification control (IAC). The assay was performed in a sealed polypropylene PCR chip containing a flat-bottom reaction chamber with two immobilized capture probe spots. The surface of the reaction chamber was functionalized with NHS-PEG-azide and alkyne-modified capture probes for each amplicon, labeled with a light harvesting antenna ligand, and covalently attached as spots to the azide-modified reaction chamber using a copper(i)-catalyzed azide-alkyne cycloaddition. Asymmetric duplex-PCR was then performed with no template, one template or both templates present and with a europium ion carrier chelate labeled probe for each amplicon in the reaction. After amplification europium fluorescence was measured by scanning the reaction chamber as a 10 × 10 raster with 0.6 mm resolution in time-resolved mode. With this assay we were able to co-amplify and detect the amplification products of the gyrB target from 100, 1000 and 10,000 copies of isolated S. aureus DNA together with the amplification products from the initial 5000 copies of the synthetic IAC template in the same sealed reaction chamber. The addition of 10,000 copies of isolated non-target Escherichia coli DNA in the same reaction with 5000 copies of the synthetic IAC template did not interfere with the amplification or detection of the IAC. The dynamic range of the assay for the synthetic S. aureus gyrB target was three orders of magnitude and the limit of detection of 8 p

  18. 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.

  19. Visible-near-infrared luminescent lanthanide ternary complexes based on beta-diketonate using visible-light excitation.

    Science.gov (United States)

    Sun, Lining; Qiu, Yannan; Liu, Tao; Feng, Jing; Deng, Wei; Shi, Liyi

    2015-11-01

    We used the synthesized dinaphthylmethane (Hdnm) ligand whose absorption extends to the visible-light wavelength, to prepare a family of ternary lanthanide complexes, named as [Ln(dnm)3 phen] (Ln = Sm, Nd, Yb, Er, Tm, Pr). The properties of these complexes were investigated by Fourier transform infrared (FT-IR) spectroscopy, diffuse reflectance (DR) spectroscopy, thermogravimetric analyses, and excitation and emission spectroscopy. Generally, excitation with visible light is much more advantageous than UV excitation. Importantly, upon excitation with visible light (401-460 nm), the complexes show characteristic visible (Sm(3+)) as well as near-infrared (Sm(3+), Nd(3+), Yb(3+), Er(3+), Tm(3+), Pr(3+)) luminescence of the corresponding lanthanide ions, attributed to the energy transfer from the ligands to the lanthanide ions, an antenna effect. Now, using these near-infrared luminescent lanthanide complexes, the luminescent spectral region from 800 to 1650 nm, can be covered completely, which is of particular interest for biomedical imaging applications, laser systems, and optical amplification applications.

  20. Coordinatively Unsaturated Lanthanide(III) Helicates: Luminescence Sensors for Adenosine Monophosphate in Aqueous Media.

    Science.gov (United States)

    Sahoo, Jashobanta; Arunachalam, Rajendran; Subramanian, Palani S; Suresh, Eringathodi; Valkonen, Arto; Rissanen, Kari; Albrecht, Markus

    2016-08-08

    Coordinatively unsaturated double-stranded helicates [(H2 L)2 Eu2 (NO3 )2 (H2 O)4 ](NO3 )4 , [(H2 L)2 Tb2 (H2 O)6 ](NO3 )6 , and [(H2 L)2 Tb2 (H2 O)6 ]Cl6 (H2 L=butanedioicacid-1,4-bis[2-(2-pyridinylmethylene)hydrazide]) are easily obtained by self-assembly from the ligand and the corresponding lanthanide(III) salts. The complexes are characterized by X-ray crystallography showing the helical arrangement of the ligands. Co-ligands at the metal ions can be easily substituted by appropriate anions. A specific luminescence response of AMP in presence of ADP, ATP, and other anions is observed. Specificity is assigned to the perfect size match of AMP to bridge the two metal centers and to replace quenching co-ligands in the coordination sphere.

  1. Reversible Luminescence Modulation upon an Electric Field on a Full Solid-State Device Based on Lanthanide Dimers.

    Science.gov (United States)

    Yi, Xiaohui; Shang, Jie; Pan, Liang; Tan, Hongwei; Chen, Bin; Liu, Gang; Huang, Gang; Bernot, Kevin; Guillou, Olivier; Li, Run-Wei

    2016-06-22

    Switching luminescence of lanthanide-based molecules through an external electric field is considered as a promising approach toward novel functional molecule-based devices. Classic routes use casted films and liquid electrolyte as media for redox reactions. Such protocol, even if efficient, is relatively hard to turn into an effective solid-state device. In this work, we explicitly synthesize lanthanide-based dimers whose luminescent behavior is affected by the presence of Cu(2+) ions. Excellent evaporability of the dimers and utilization of Cu(2+)-based solid-state electrolyte makes it possible to reproduce solution behavior at the solid state. Reversible modulation of Cu(2+) ions transport can be achieved by an electric field in a solid-state device, where lanthanide-related luminescence is driven by an electric field. These findings provide a proof-of-concept alternative approach for electrically driven modulation of solid-state luminescence and show promising potential for information storage media in the future.

  2. Probing high energy levels of lanthanide ions - experiment and theory

    NARCIS (Netherlands)

    Peijzel, P.S.

    2004-01-01

    This thesis describes vacuum ultraviolet (VUV) spectroscopy of lanthanide ions. High-resolution emission and excitation spectra were recorded to investigate the VUV energy levels of lanthanide ions in fluoride and phosphate host lattices. A parameterized model for the calculation of the energy-level

  3. Acidic 1,3-propanediaminetetraacetato lanthanides with luminescent and catalytic ester hydrolysis properties

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Mao-Long; Shi, Yan-Ru; Yang, Yu-Chen; Zhou, Zhao-Hui, E-mail: zhzhou@xmu.edu.cn

    2014-11-15

    In acidic solution, a serials of water-soluble coordination polymers (CPs) were isolated as zonal 1D-CPs 1,3-propanediaminetetraacetato lanthanides [Ln(1,3-H{sub 3}pdta)(H{sub 2}O){sub 5}]{sub n}·2Cl{sub n}·3nH{sub 2}O [Ln=La, 1; Ce, 2; Pr, 3; Nd, 4; Sm, 5] (1,3-H{sub 4}pdta=1,3-propanediaminetetraacetic acid, C{sub 11}H{sub 18}N{sub 2}O{sub 8}) in high yields. When 1 eq. mol potassium hydroxide was added to the solutions of 1D-CPs, respectively, two 1D-CPs [Ln(1,3-H{sub 2}pdta)(H{sub 2}O){sub 3}]{sub n}·Cl{sub n}·2nH{sub 2}O [Ln=Sm, 6; Gd, 7] were isolated at room temperature and seven 2D-CPs [Ln(1,3-H{sub 2}pdta)(H{sub 2}O){sub 2}]{sub n}·Cl{sub n}·2nH{sub 2}O [Ln=La, 8; Ce, 9; Pr, 10; Nd, 11; Sm, 12; Eu, 13; Gd, 14] were isolated at 70 °C. When the crystals of 1–4 were hydrothermally heated at 180 °C with 1–2 eq. mol potassium hydroxide, four 3D-CPs [Ln(1,3-Hpdta)]{sub n}·nH{sub 2}O [Ln=La, 15; Ce, 16; Pr, 17; Nd, 18] were obtained. The two 2D-CPs [Ln(1,3-Hpdta)(H{sub 2}O)]{sub n}·4nH{sub 2}O (Sm, 19; Eu, 20) were isolated in similar reaction conditions. With the increments of pH value in the solution and reaction temperature, the structure becomes more complicated. 1–5 are soluble in water and 1 was traced by solution {sup 13}C({sup 1}H) NMR technique, the water-soluble lanthanides 1 and 5 show catalytic activity to ester hydrolysis reaction respectively, which indicate their important roles in the hydrolytic reaction. The europium complexes 13 and 20 show visible fluorescence at an excitation of 394 nm. The structure diversity is mainly caused by the variation of coordinated ligand in different pH values and lanthanide contraction effect. Acidic conditions are favorable for the isolations of lanthanide complexes in different structures and this may helpful to separate different lanthanides. The thermal stability investigations reveal that acidic condition is favorable to obtain the oxides at a lower temperature. - Graphical abstract: A series

  4. NIR persistent luminescence of lanthanide ion-doped rare-earth oxycarbonates: the effect of dopants.

    Science.gov (United States)

    Caratto, Valentina; Locardi, Federico; Costa, Giorgio Andrea; Masini, Roberto; Fasoli, Mauro; Panzeri, Laura; Martini, Marco; Bottinelli, Emanuela; Gianotti, Enrica; Miletto, Ivana

    2014-10-22

    A series of luminescent rare-earth ion-doped hexagonal II-type Gd oxycarbonate phosphors Gd2-xRExO2CO3 (RE = Eu(3+), Yb(3+), Dy(3+)) have been successfully synthesized by thermal decomposition of the corresponding mixed oxalates. The Yb(3+) doped Gd-oxycarbonate has evidenced a high persistent luminescence in the NIR region, that is independent from the temperature and makes this materials particular attractive as optical probes for bioimaging.

  5. Lanthanide doped ultrafine hybrid nanostructures: multicolour luminescence, upconversion based energy transfer and luminescent solar collector applications.

    Science.gov (United States)

    Singh, Priyam; Shahi, Praveen Kumar; Singh, Sunil Kumar; Singh, Akhilesh Kumar; Singh, Manish Kumar; Prakash, Rajiv; Rai, Shyam Bahadur

    2017-01-05

    We herein demonstrate novel inorganic-organic hybrid nanoparticles (HNPs) composed of inorganic NPs, NaY0.78Er0.02Yb0.2F4, and an organic β-diketonate complex, Eu(TTA)3Phen, for energy harvesting applications. Both the systems maintain their core integrity and remain entangled through weak interacting forces. HNPs incorporate the characteristic optical behaviour of both the systems i.e. they give an intense red emission under UV excitation, due to Eu(3+) in organic complexes, and efficient green upconversion emission of Er(3+) in inorganic NPs for NIR (980 nm) excitation. However, (i) an energy transfer from Er(3+) (inorganic NPs) to Eu(3+) (organic complex) under NIR excitation, and (ii) an increase in the decay time of (5)D0 → (7)F2 transition of Eu(3+) for HNPs as compared to the Eu(TTA)3Phen complex, under different excitation wavelengths, are added optical characteristics which point to an important role of the interface between both the systems. Herein, the ultra-small size (6-9 nm) and spherical shape of the inorganic NPs offer a large surface area, which improves the weak interaction force between both the systems. Furthermore, the HNPs dispersed in the PMMA polymer have been successfully utilized for luminescent solar collector (LSC) applications.

  6. Design of lanthanide fingers: compact lanthanide-binding metalloproteins.

    Science.gov (United States)

    am Ende, Christopher W; Meng, Hai Yun; Ye, Mao; Pandey, Anil K; Zondlo, Neal J

    2010-08-16

    Lanthanides have interesting chemical properties; these include luminescent, magnetic, and catalytic functions. Toward the development of proteins incorporating novel functions, we have designed a new lanthanide-binding motif, lanthanide fingers. These were designed based on the Zif268 zinc finger, which exhibits a beta beta alpha structural motif. Lanthanide fingers utilize an Asp(2)Glu(2) metal-coordination environment to bind lanthanides through a tetracarboxylate peptide ligand. The iterative design of a general lanthanide-binding peptide incorporated the following key elements: 1) residues with high alpha-helix and beta-sheet propensities in the respective secondary structures; 2) an optimized big box alpha-helix N-cap; 3) a Schellman alpha-helix C-cap motif; and 4) an optional D-Pro-Ser type II' beta-turn in the beta-hairpin. The peptides were characterized for lanthanide binding by circular dichroism (CD), NMR, and fluorescence spectroscopy. In all instances, stabilization of the peptide secondary structures resulted in an increase in metal affinity. The optimized protein design was a 25-residue peptide that was a general lanthanide-binding motif; this binds all lanthanides examined in a competitive aqueous environment, with a dissociation constant of 9.3 microM for binding Er(3+). CD spectra of the peptide-lanthanide complexes are similar to those of zinc fingers and other beta beta alpha proteins. Metal binding involves residues from the N-terminal beta-hairpin and the C terminal alpha-helical segments of the peptide. NMR data indicated that metal binding induced a global change in the peptide structure. The D-Pro-Ser type II' beta-turn motif could be replaced by Thr-Ile to generate genetically encodable lanthanide fingers. Replacement of the central Phe with Trp generated genetically encodable lanthanide fingers that exhibited terbium luminescence greater than that of an EF-hand peptide.

  7. Highly emitting near-infrared lanthanide "encapsulated sandwich" metallacrown complexes with excitation shifted toward lower energy.

    Science.gov (United States)

    Trivedi, Evan R; Eliseeva, Svetlana V; Jankolovits, Joseph; Olmstead, Marilyn M; Petoud, Stéphane; Pecoraro, Vincent L

    2014-01-29

    Near-infrared (NIR) luminescent lanthanide complexes hold great promise for practical applications, as their optical properties have several complementary advantages over organic fluorophores and semiconductor nanoparticles. The fundamental challenge for lanthanide luminescence is their sensitization through suitable chromophores. The use of the metallacrown (MC) motif is an innovative strategy to arrange several organic sensitizers at a well-controlled distance from a lanthanide cation. Herein we report a series of lanthanide “encapsulated sandwich” MC complexes of the form Ln3+ [12-MC(Zn(II),quinHA)-4]2[24-MC(Zn(II),quinHA)-8] (Ln3+ [Zn(II)MC(quinHA)]) in which the MC framework is formed by the self-assembly of Zn2+ ions and tetradentate chromophoric ligands based on quinaldichydroxamic acid (quinHA). A first-generation of luminescent MCs was presented previously but was limited due to excitation wavelengths in the UV. We report here that through the design of the chromophore of the MC assembly, we have significantly shifted the absorption wavelength toward lower energy (450 nm). In addition to this near-visible inter- and/or intraligand charge transfer absorption, Ln3+ [Zn(II)MC(quinHA)] exhibits remarkably high quantum yields, long luminescence lifetimes (CD3OD; Yb3+, QLn(L) = 2.88(2)%, τobs = 150.7(2) μs; Nd3+, QLn(L) = 1.35(1)%, τobs = 4.11(3) μs; Er3+, QLn(L) = 3.60(6)·10–2%, τobs = 11.40(3) μs), and excellent photostability. Quantum yields of Nd3+ and Er3+ MCs in the solid state and in deuterated solvents, upon excitation at low energy, are the highest values among NIR-emitting lanthanide complexes containing C–H bonds. The versatility of the MC strategy allows modifications in the excitation wavelength and absorptivity through the appropriate design of the ligand sensitizer, providing a highly efficient platform with tunable properties.

  8. Synthesis and luminescent properties of the novel poly(ethylene-co-acrylic acid) films based on surface modification with lanthanide (Eu3+, Tb3+) complexes

    Science.gov (United States)

    Wu, Yuewen; Chu, Yang; Yu, Zhenjiang; Hao, Haixia; Wu, Qingyao; Xie, Hongde

    2017-10-01

    Two kinds of novel fluorescent films have been successfully synthesized by surface modification on the poly(ethylene-co-acrylic acid) films using the lanthanide (Eu3+, Tb3+) complexes. The process consists of three steps: conversion of carboxylic acid groups on the surface of the poly(ethylene-co-acrylic acid) films to acid chloride groups, synthesis of the lanthanide complexes bearing amino groups, and amidation to form the modified films. To characterize the modified films, Fourier transform infrared, thermogravimetric analysis, static water contact angle measurements and photoluminescence tests have been employed. Fourier transform infrared verifies the successful preparation of the lanthanide complexes and the modified poly(ethylene-co-acrylic acid) films. These films can emit strong characteristic red and green light under UV light excitation. In addition, the films both have short lifetime (1.14 ms and 1.21 ms), high thermal stability (Td = 408 °C and 411 °C) and, compared with unmodified ones, increased hydrophilicity. All these results suggest that the modified films have potential application as luminescent materials under high temperature.

  9. Ratiometric near infrared luminescent thermometer based on lanthanide metal-organic frameworks

    Science.gov (United States)

    Yue, Dan; Zhang, Jun; Zhao, Dian; Lian, Xiusheng; Cui, Yuanjing; Yang, Yu; Qian, Guodong

    2016-09-01

    A near infrared luminescent MOFs thermometer (Nd0.676Yb0.324BTC) was prepared via a simple solvothermal method using Ln3+ (Ln=Nd, Yb) ions and 1, 3, 5-benznenetricarboxylic acid (H3BTC), and characterized by PXRD, TGA, ICP, and photoluminescence (PL) spectrum. These results indicate that the Nd0.676Yb0.324BTC displays high relative sensitivity and excellent repeatability in the physiological temperature range (288-323 K), and the maximum relative sensitivity is determined to be 1.187% K-1 at 323 K. These NIR luminescent MOFs may have potential applications in physiological temperature sensing.

  10. Luminescent hybrid materials based on zeolite L crystals and lanthanide complexes: host-guest assembly and ultraviolet-visible excitation.

    Science.gov (United States)

    Chen, Lei; Yan, Bing

    2014-10-15

    Several kinds of host-guest hybrid materials have been synthesized employing a ship in a bottle method by loading 9-hydroxy-2-methylphenalenone (MHPO) or 9-hydroxyphenalen (HPNP) from gas phase into the nanochannels of Ln(3+)-exchanged zeolite L (ZL) crystals (Ln=Gd or Eu). The resulting hybrids without lanthanide ions, MHPO-ZL, HPNP-ZL and the hybrids with lanthanide ions Ln-MHPO-ZL and Ln-HPNP-ZL are characterized with FT-IR, UV-vis DRS and photoluminescence spectroscopy. The photoluminescence properties of these hybrid materials have been analyzed and discussed, exhibiting the luminescence of Eu(3+) and ligands under the excitation at ultraviolet-visible region. These results provide useful data and can be expected to have potential application in the practical fields. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Structurally characterized luminescent lanthanide zinc carboxylate precursors for Ln-Zn-O nanomaterials.

    Science.gov (United States)

    Boyle, Timothy J; Raymond, Rebecca; Boye, Daniel M; Ottley, Leigh Anna M; Lu, Ping

    2010-09-14

    A novel family of lanthanide zinc carboxylate compounds was synthesized, characterized (structural determination and luminescent behavior), and investigated for utility as single-source precursors to Ln-Zn-O nanoparticles. Carboxylic acids [H-ORc = H-OPc (H-O(2)CCH(CH(3))(2), H-OBc (H-O(2)CC(CH(3))(3), H-ONc (H-O(2)CCH(2)C(CH(3))(3))] were individually reacted with diethyl zinc (ZnEt(2)) to yield a set of previously unidentified zinc carboxylates: (i) [Zn(mu-ORc)(3)Zn(mu-ORc)](n) [ORc = OPc (1), ONc (2)], (ii) [(py)Zn](2)(mu-ORc)(4) [ORc = OBc (3), ONc (4), and py = pyridine], or (iii) Zn(ORc)(2)(solv)(2) [ORc/solv = OPc/py (5), O(c)Nc/H(2)O (6) (O(c)Rc = chelating)]. Introduction of lanthanide cation [Ln[N(SiMe(3))(2)](3), ZnEt(2), and HOBc in py] yielded the mixed cationic species structurally characterized as: (i) (O(c)Bc)Ln[(mu-OBc)(3)Zn(py)](2) [Ln = Pr (7), Nd (8), Sm (9)] or (ii) (py)(2)Zn(mu-OBc)(3)Ln(O(c)Bc)(2)(py) [Ln = Tb (10), Dy (11), Er (12), Y (13), Yb (14)]. Exploration of alternative starting materials [Ln(NO(3))(3).nH(2)O, Zn(O(2)CCH(3))(2), HOBc in py] led to the isolation of (NO(3)(c))Ln[(mu-OBc)(3)Zn(py)](2) [Ln = La (15), Ce (16), Pr (17), Nd (18), Sm (19), Eu (20), Gd (21), Tb (22) Dy (23), and Er (24); NO(3)(c) = chelating]. The UV-vis spectra of 7-24 revealed standard absorption spectra for the Ln cations. Representative compounds were used to generate nanoparticles from an established 1,4-butanediol-based solution precipitation route. The nanoproducts isolated adopted either a mixed zincite/lanthanum oxide (18n or 22n) or pure zincite (8n or 10n) phase dependent on NO(3) or OBc moiety. Fluorescence was not observed for any of these nanomaterials possibly due to phase separation, low crystallinity, surface traps, and/or quenching based on elevated Ln cation content.

  12. Prototypes of Lanthanide(III) Agents Responsive to Enzymatic Activities in Three Complementary Imaging Modalities: Visible/Near-Infrared Luminescence, PARACEST-, and T1-MRI.

    Science.gov (United States)

    He, Jiefang; Bonnet, Célia S; Eliseeva, Svetlana V; Lacerda, Sara; Chauvin, Thomas; Retailleau, Pascal; Szeremeta, Frederic; Badet, Bernard; Petoud, Stéphane; Tóth, Éva; Durand, Philippe

    2016-03-09

    We report first prototypes of responsive lanthanide(III) complexes that can be monitored independently in three complementary imaging modalities. Through the appropriate choice of lanthanide(III) cations, the same reactive ligand can be used to form complexes providing detection by (i) visible (Tb(3+)) and near-infrared (Yb(3+)) luminescence, (ii) PARACEST- (Tb(3+), Yb(3+)), or (iii) T1-weighted (Gd(3+)) MRI. The use of lanthanide(III) ions of different natures for these imaging modalities induces only a minor change in the structure of complexes that are therefore expected to have a single biodistribution and cytotoxicity.

  13. Ratiometric near infrared luminescent thermometer based on lanthanide metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Yue, Dan; Zhang, Jun; Zhao, Dian; Lian, Xiusheng; Cui, Yuanjing, E-mail: cuiyj@zju.edu.cn; Yang, Yu; Qian, Guodong, E-mail: gdqian@zju.edu.cn

    2016-09-15

    A near infrared luminescent MOFs thermometer (Nd{sub 0.676}Yb{sub 0.324}BTC) was prepared via a simple solvothermal method using Ln{sup 3+} (Ln=Nd, Yb) ions and 1, 3, 5-benznenetricarboxylic acid (H{sub 3}BTC), and characterized by PXRD, TGA, ICP, and photoluminescence (PL) spectrum. These results indicate that the Nd{sub 0.676}Yb{sub 0.324}BTC displays high relative sensitivity and excellent repeatability in the physiological temperature range (288–323 K), and the maximum relative sensitivity is determined to be 1.187% K{sup −1} at 323 K. These NIR luminescent MOFs may have potential applications in physiological temperature sensing. - Graphical abstract: A near infrared luminescent MOFs thermometer (Nd{sub 0.054}Yb{sub 0.946}BTC ) displays high relative sensitivity and excellent repeatability in the physiological temperature range (288–323 K). Display Omitted - Highlights: • A ratiometric near infrared luminescent MOFs thermometer (Nd{sub 0.676}Yb{sub 0.324}BTC) was prepared via a simple solvothermal method. • The maximum relative sensitivity of Nd{sub 0.676}Yb{sub 0.324}BTC is determined to be 1.187% K{sup −1} at 323 K. • Nd{sub 0.676}Yb{sub 0.324}BTC showed excellent repeatability in the physiological temperature range (288–323 K).

  14. Luminescence studies on europium-strontium phthalate system.

    Science.gov (United States)

    Yang, Limin; Zhao, Ying; Su, Yunlan; Wu, Jinguang

    2002-11-01

    New lanthanide luminescence materials were prepared. The main component lanthanide chelates generally need a relatively high content of rare earth. Inorganic luminescence materials only need low rare earth concentration using doped method. Similarly, lanthanide chelates can be added to complex matrix by doped method. In this way, low rare earth concentration emission was successful in the lanthanide chelates system as well. The influence of europium ion concentration on luminescence intensities was discussed. When the europium ion weight in the complex is only about 0.6%, the sample exhibits good luminescence properties. The fluorescence, Fourier transform infrared spectra, micro-Raman and electron spin resonance spectra of the samples were measured. And a possible luminescence mechanism was suggested by the inorganic doped mechanism and the luminescence of lanthanide complexes together.

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

    Energy Technology Data Exchange (ETDEWEB)

    Monteiro, Jorge H.S.K.; Formiga, André L.B.; Sigoli, Fernando A., E-mail: fsigoli@iqm.unicamp.br

    2014-10-15

    The lanthanides(III) complexes [Ln(bza){sub 3}(H{sub 2}O){sub n}]·mH{sub 2}O, [Ln(ppa){sub 3}(H{sub 2}O){sub n}]·mH{sub 2}O and [Ln(abse){sub 3}(H{sub 2}O){sub n}]·mH{sub 2}O where Ln=Eu{sup 3+}, Gd{sup 3+} or Tb{sup 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{sup −1} between them. The [Eu(abse){sub 3}(H{sub 2}O)] complex shows the higher degree of covalence which was verified by the centroid of {sup 5}D{sub 0}→{sup 7}F{sub 0} transition (17,248 cm{sup −1}). On the other hand the [Ln(abse){sub 3}(H{sub 2}O){sub n}]·mH{sub 2}O complexes have an inefficient antenna effect verified by the low values of absolute emission quantum yields. The [Ln(ppa){sub 3}(H{sub 2}O){sub n}]·mH{sub 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){sub 3}] complex has the highest point symmetry around europium(III) among the synthesized complexes, followed by the [Eu(bza){sub 3}(H{sub 2}O){sub 2}]·3/2(H{sub 2}O) and [Eu(abse){sub 3}(H{sub 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

  16. Lanthanide–lanthanide and lanthanide–defect interactions in co-doped ceria revealed by luminescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Avram, Daniel; Gheorghe, Cristina [National Institute for Laser, Plasma and Radiation Physics, P.O. Box MG-36, RO 76900 Bucharest-Magurele (Romania); Rotaru, Codruta; Cojocaru, Bogdan; Florea, Mihaela; Parvulescu, Vasile [University of Bucharest, Department of Chemical Technology and Catalysis, 4–12 Regina Elisabeta Bvd., Bucharest (Romania); Tiseanu, Carmen, E-mail: tiseanuc@yahoo.com [National Institute for Laser, Plasma and Radiation Physics, P.O. Box MG-36, RO 76900 Bucharest-Magurele (Romania)

    2014-12-15

    Highlights: • (Sm, Nd) and (Sm, Eu) co-doped CeO{sub 2} are investigated by luminescence spectroscopy. • Local structure at Sm sites is not changed by Nd or Eu co-dopant. • Sm is not involved in non-radiative energy transfer to Nd or Eu co-dopant. • The excitation mode of perturbed Eu centre is modified by Sm co-dopant. - Abstract: Here, we present a first study on the local structure properties, lanthanide–lanthanide and lanthanide–defect interactions in lanthanide (Sm{sup 3+}/Nd{sup 3+} and Sm{sup 3+}/Eu{sup 3+}) co-doped CeO{sub 2} nanoparticles by use of luminescence spectroscopy. By comparing the emission/excitation spectra and decays measured with the single doped and co-doped ceria, it is established that the local structure at Sm{sup 3+} sites is not affected by the presence of the Nd{sup 3+} or Eu{sup 3+} co-dopant irrespective of concentration. The results suggest that the excess of oxygen vacancies generated by the co-dopant is not associated with Sm{sup 3+}, being more probably associated with the Nd{sup 3+}/Eu{sup 3+} or/and Ce{sup 4+} cations. It is also observed that Sm{sup 3+} is not involved in significant non-radiative energy transfer to Nd{sup 3+} or Eu{sup 3+} while the relative strong shortening of Nd{sup 3+} luminescence decay with concentration is most probably related to cross-relaxation in Nd{sup 3+}–Nd{sup 3+} pairs.

  17. On-the-fly decoding luminescence lifetimes in the microsecond region for lanthanide-encoded suspension arrays

    Science.gov (United States)

    Lu, Yiqing; Lu, Jie; Zhao, Jiangbo; Cusido, Janet; Raymo, Françisco M.; Yuan, Jingli; Yang, Sean; Leif, Robert C.; Huo, Yujing; Piper, James A.; Paul Robinson, J.; Goldys, Ewa M.; Jin, Dayong

    2014-05-01

    Significant multiplexing capacity of optical time-domain coding has been recently demonstrated by tuning luminescence lifetimes of the upconversion nanoparticles called ‘τ-Dots’. It provides a large dynamic range of lifetimes from microseconds to milliseconds, which allows creating large libraries of nanotags/microcarriers. However, a robust approach is required to rapidly and accurately measure the luminescence lifetimes from the relatively slow-decaying signals. Here we show a fast algorithm suitable for the microsecond region with precision closely approaching the theoretical limit and compatible with the rapid scanning cytometry technique. We exploit this approach to further extend optical time-domain multiplexing to the downconversion luminescence, using luminescence microspheres wherein lifetimes are tuned through luminescence resonance energy transfer. We demonstrate real-time discrimination of these microspheres in the rapid scanning cytometry, and apply them to the multiplexed probing of pathogen DNA strands. Our results indicate that tunable luminescence lifetimes have considerable potential in high-throughput analytical sciences.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-12-29

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

  19. Preparation and luminescent properties of lanthanide (Eu3+ and Tb3+) complexes grafted to 3-aminopropyltriethoxysilane by covalent bonds

    Science.gov (United States)

    Zhang, Wenjun; Wang, Haiyan

    2015-12-01

    A novel precursor PMA-Si was synthesized by modifying 1,2,4,5-benzene-tetracarboxylic acid (PMA) with 3-aminopropyltriethoxysilane (APTES). Then the hybrids were prepared by PMA-Si coordinating to lanthanide ions (Eu3+ and Tb3+) in sol-gel process. In order to improve luminescent efficiency, 1,10-Phenanthroline (Phen) was introduced to the system as the second ligand. As-prepared compounds in sol condition were coated on quartz plates to form a layer of thin film, which was different from other similar hybrids. The properties of the hybrids were characterized by FT-IR, fluorescence spectra, TG and SEM. The results showed that the obtained materials enhanced thermal stability, mechanical resistances, waterproofness as well as machining properties.

  20. Synthesis, crystal structure and effect of deuterated solvents and temperature on visible and near infrared luminescence of N4-donor Schiff base lanthanide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Shuo; Fan, Rui-Qing; Gao, Song; Wang, Xinming; Yang, Yu-Lin, E-mail: ylyang@hit.edu.cn

    2014-05-01

    A series of lanthanide complexes [LnL(NO{sub 3}){sub 3}]·CH{sub 3}CN [Ln=Ce, (1• Ce); Nd, (2• Nd); Tb, (3• Tb); Dy, (4• Dy); Ho, (5• Ho); Er, (6• Er); Tm, (7• Tm); Yb (8• Yb)] have been synthesized by the reaction of N4 chelate ligand N,N'-bis(2-pyridinylmethylene)cyclohexane-1,2-diamine (L) with lanthanide salts. Photoluminescence spectra of complexes 2• Nd, 3• Tb, 4• Dy, and 8• Yb show the strong characteristic luminescence from visible to near infrared (NIR) region. Further, the singlet state (32,467 cm{sup −1}) and the lowest triplet (23,202 cm{sup −1}) energy level of L are calculated, indicating that the energy transfer from L to Tb{sup 3+} ion is more effective than that to Dy{sup 3+} ion. An extended work is developed to discuss on the effect of deuterated reagent and temperature on luminescent properties of 3• Tb and 8• Yb. - Highlights: • A series of N4-donor Schiff base lanthanide complex are designed and synthesized. • The characteristic luminescence from visible to near infrared region could be revealed. • The influence of deuterated reagent and temperature on luminescent properties is described.

  1. Three-way partial least-squares/residual bilinearization study of second-order lanthanide-sensitized luminescence excitation-time decay data

    Energy Technology Data Exchange (ETDEWEB)

    Lozano, Valeria A.; Ibanez, Gabriela A. [Departamento de Quimica Analitica, Facultad de Ciencias Bioquimicas y Farmaceuticas, Universidad Nacional de Rosario, and Instituto de Quimica Rosario (IQUIR), Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET), Suipacha 531, Rosario S2002LRK (Argentina); Olivieri, Alejandro C. [Departamento de Quimica Analitica, Facultad de Ciencias Bioquimicas y Farmaceuticas, Universidad Nacional de Rosario, and Instituto de Quimica Rosario (IQUIR), Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET), Suipacha 531, Rosario S2002LRK (Argentina)], E-mail: aolivier@fbioyf.unr.edu.ar

    2008-03-10

    Lanthanide-sensitized luminescence excitation-time decay matrices were employed for achieving the second-order advantage using as chemometric algorithms parallel factor analysis (PARAFAC) and multidimensional partial least-squares with residual bilinearization (N-PLS/RBL). The second-order data were measured for a calibration set of samples containing the analyte benzoic acid in the concentration range from 0.00 to 5.00 mg L{sup -1}, for a validation set containing the analyte and the potential interferent saccharin (in the range 0.00-6.00 mg L{sup -1}), and for real samples of beverages containing benzoic acid as preservant, saccharin, and other potentially interfering compounds. All samples were treated with terbium(III), trioctylphosphine oxide as a synergistic ligand, and contained a suitable imidazol buffer, in order to ensure maximum intensity of the luminescence signals. The results indicate a slightly better predictive ability of the newly introduced N-PLS/RBL procedure over standard PARAFAC, both in what concerns the comparison with nominal analyte concentrations in the validation sample set and with results provided by the reference high-performance liquid chromatographic technique for the real sample set.

  2. Instant luminescence chronologies? High resolution luminescence profiles using a portable luminescence reader

    OpenAIRE

    Bateman, M. D.; Stein, S.; Ashurst, R.A.; Selby, K.

    2015-01-01

    Establishing a robust chronology is fundamental to most palaeoenvironmental studies. However, the number and positioning of dated points is critical. Using a portable luminescence reader, it is possible to rapidly generate high resolution down core relative age profiles. Profiles of portable luminescence data from two coastal dunes were evaluated and compared with the results of particle size analysis, stratigraphy, and an independent historical chronology. Results show that, even in young sa...

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

    Science.gov (United States)

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

    2010-06-28

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

  4. High Resolution Fluorescence Imaging of Cancers Using Lanthanide Ion-Doped Upconverting Nanocrystals

    Science.gov (United States)

    Naccache, Rafik; Rodríguez, Emma Martín; Bogdan, Nicoleta; Sanz-Rodríguez, Francisco; de la Cruz, Maria del Carmen Iglesias; de la Fuente, Ángeles Juarranz; Vetrone, Fiorenzo; Jaque, Daniel; Solé, José García; Capobianco, John A.

    2012-01-01

    During the last decade inorganic luminescent nanoparticles that emit visible light under near infrared (NIR) excitation (in the biological window) have played a relevant role for high resolution imaging of cancer. Indeed, semiconductor quantum dots (QDs) and metal nanoparticles, mostly gold nanorods (GNRs), are already commercially available for this purpose. In this work we review the role which is being played by a relatively new class of nanoparticles, based on lanthanide ion doped nanocrystals, to target and image cancer cells using upconversion fluorescence microscopy. These nanoparticles are insulating nanocrystals that are usually doped with small percentages of two different rare earth (lanthanide) ions: The excited donor ions (usually Yb3+ ion) that absorb the NIR excitation and the acceptor ions (usually Er3+, Ho3+ or Tm3+), that are responsible for the emitted visible (or also near infrared) radiation. The higher conversion efficiency of these nanoparticles in respect to those based on QDs and GNRs, as well as the almost independent excitation/emission properties from the particle size, make them particularly promising for fluorescence imaging. The different approaches of these novel nanoparticles devoted to “in vitro” and “in vivo” cancer imaging, selective targeting and treatment are examined in this review. PMID:24213500

  5. Photocytotoxic lanthanide complexes

    Indian Academy of Sciences (India)

    Akhtar Hussain; Akhil R Chakravarty

    2012-11-01

    Lanthanide complexes have recently received considerable attention in the field of therapeutic and diagnostic medicines. Among many applications of lanthanides, gadolinium complexes are used as magnetic resonance imaging (MRI) contrast agents in clinical radiology and luminescent lanthanides for bioanalysis, imaging and sensing. The chemistry of photoactive lanthanide complexes showing biological applications is of recent origin. Photodynamic therapy (PDT) is a non-invasive treatment modality of cancer using a photosensitizer drug and light. This review primarily focuses on different aspects of the chemistry of lanthanide complexes showing photoactivated DNA cleavage activity and cytotoxicity in cancer cells. Macrocyclic texaphyrin-lanthanide complexes are known to show photocytotoxicity with the PDT effect in near-IR light. Very recently, non-macrocyclic lanthanide complexes are reported to show photocytotoxicity in cancer cells. Attempts have been made in this perspective article to review and highlight the photocytotoxic behaviour of various lanthanide complexes for their potential photochemotherapeutic applications.

  6. On-the-fly decoding luminescence lifetimes in the microsecond region for lanthanide-encoded suspension arrays

    Science.gov (United States)

    Lu, Yiqing; Lu, Jie; Zhao, Jiangbo; Cusido, Janet; Raymo, Françisco M; Yuan, Jingli; Yang, Sean; Leif, Robert C.; Huo, Yujing; Piper, James A.; Paul Robinson, J; Goldys, Ewa M.; Jin, Dayong

    2014-01-01

    Significant multiplexing capacity of optical time-domain coding has been recently demonstrated by tuning luminescence lifetimes of the upconversion nanoparticles called ‘τ-Dots’. It provides a large dynamic range of lifetimes from microseconds to milliseconds, which allows creating large libraries of nanotags/microcarriers. However, a robust approach is required to rapidly and accurately measure the luminescence lifetimes from the relatively slow-decaying signals. Here we show a fast algorithm suitable for the microsecond region with precision closely approaching the theoretical limit and compatible with the rapid scanning cytometry technique. We exploit this approach to further extend optical time-domain multiplexing to the downconversion luminescence, using luminescence microspheres wherein lifetimes are tuned through luminescence resonance energy transfer. We demonstrate real-time discrimination of these microspheres in the rapid scanning cytometry, and apply them to the multiplexed probing of pathogen DNA strands. Our results indicate that tunable luminescence lifetimes have considerable potential in high-throughput analytical sciences. PMID:24796249

  7. 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)

  8. 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.

  9. A Versatile Imaging and Therapeutic Platform Based on Dual-Band Luminescent Lanthanide Nanoparticles toward Tumor Metastasis Inhibition.

    Science.gov (United States)

    Li, Yang; Tang, Jinglong; Pan, Dong-Xu; Sun, Ling-Dong; Chen, Chunying; Liu, Ying; Wang, Ye-Fu; Shi, Shuo; Yan, Chun-Hua

    2016-02-23

    Upconversion (UC) luminescent lanthanide nanoparticles (LNPs) are expected to play an important role in imaging and photodynamic therapy (PDT) in vitro and in vivo. However, with the absorption of UC emissions by photosensitizers (PSs) to generate singlet oxygen ((1)O2) for PDT, the imaging signals from LNPs are significantly weakened. It is important to activate another imaging route to track the location of the LNPs during PDT process. In this work, Nd(3+)-sensitized LNPs with dual-band visible and near-infrared (NIR) emissions under single 808 nm excitation were reported to address this issue. The UC emissions in green could trigger covalently linked rose bengal (RB) molecules for efficient PDT, and NIR emissions deriving from Yb(3+) and magnetic resonance imaging (MRI) were used for imaging simultaneously. Notably, the designed therapeutic platform could further effectively avoid the overheating effect induced by the laser irradiation, due to the minimized absorption of biological media at around 808 nm. TdT-mediated dUTP nick end labeling (TUNEL) assay showed serious cell apoptosis in the tumor after PDT for 2 weeks, leading to an effective tumor inhibition rate of 67%. Benefit from the PDT, the tumor growth-induced liver and spleen burdens were largely attenuated, and the liver injury was also alleviated. More importantly, pulmonary and hepatic tumor metastases were significantly reduced after PDT. The Nd(3+)-sensitized LNPs provide a multifunctional nanoplatform for NIR light-assisted PDT with minimized heating effect and an effective inhibition of tumor growth and metastasis.

  10. Synthesis, crystal structure, and luminescent properties of 2-(2,2,2-trifluoroethyl)-1-indone lanthanide complexes.

    Science.gov (United States)

    Li, Jingya; Li, Hongfeng; Yan, Pengfei; Chen, Peng; Hou, Guangfeng; Li, Guangming

    2012-05-07

    A new β-diketone, 2-(2,2,2-trifluoroethyl)-1-indone (TFI), which contains a trifluorinated alkyl group and a rigid indone group, has been designed and employed for the synthesis of two series of new TFI lanthanide complexes with a general formula [Ln(TFI)(3)L] [Ln = Eu, L = (H(2)O)(2) (1), bpy (2), and phen (3); Ln = Sm, L = (H(2)O)(2) (4), bpy (5), and phen (6); bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline]. X-ray crystallographic analysis reveals that complexes 1-6 are mononuclear, with the central Ln(3+) ion eight-coordinated by six oxygen atoms furnished by three TFI ligands and two O/N atoms from ancillary ligand(s). The room-temperature photoluminescence (PL) spectra of complexes 1-6 show strong characteristic emissions of the corresponding Eu(3+) and Sm(3+) ions, and the substitution of the solvent molecules by bidentate nitrogen ligands essentially enhances the luminescence quantum yields and lifetimes of the complexes.

  11. Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb).

    Science.gov (United States)

    Einkauf, Jeffrey D; Kelley, Tanya T; Chan, Benny C; de Lill, Daniel T

    2016-08-15

    A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

  12. Lanthanide metal-organic frameworks as multifunctional luminescent sensor for detecting cations, anions and organic solvent molecules in aqueous solution

    Science.gov (United States)

    Liu, Feng; Gao, Wei; Li, Peng; Zhang, Xiu-Mei; Liu, Jie-Ping

    2017-09-01

    A series of water-stable isostructural mono/bimetallic lanthanide metal-organic frameworks (Ln-MOFs) {[Eu5xTb5(1-x)(OH)6(TZI)3(DMA)1.5(H2O)10.5]·DMA·0.5H2O}n (x = 1.0 (1), 0.5 (3), 0.4 (4), 0.3 (5), 0.2 (6), 0.1 (7), 0.05 (8), 0 (2), H3TZI = 5-(1H-tetrazol-5-yl)isophthalic acid) were synthesized. These Ln-MOFs exhibit 3D frameworks in which 1D chains based on pentanuclear [Ln5(μ3-OH)6(COO)5]4+ clusters are linked by TZI backbones. The luminescent investigations revealed that compounds 1 and 2 not only exhibit characteristic Eu3+ and Tb3+ emissions in the red and green regions, respectively, but also can sensitively and selectively detect Fe3+ cations, CO32-, PO43-, AsO43- anions and acetone molecules in aqueous solution. In addition, the luminescent colors of the bimetallic (Tb5(1-x):Eu5x) compounds can easily be tuned by doping isostructural Ln- MOFs with Eu3+ and Tb3+ ions. This work presents some good candidate materials for the potential multifunctional sensors. Eight water-stable isostructural 3D Ln-MOFs {[Eu5xTb5(1-x)(OH)6(TZI)3(DMA)1.5(H2O)10.5]·DMA·0.5H2O}n based on pentanuclear clusters were prepared. The Ln-MOFs represented the rapid and drastic emission quenching induced by Fe3+ cations, CO32-, PO43-, AsO43- anions and acetone molecules in aqueous solution. the luminescence colors of the bimetallic (Tb5(1-x):Eu5x) compounds can easily be tuned by doping isostructural Ln-MOFs with Eu3+ and Tb3+ ions.

  13. Ready to use dry-reagent PCR assays for the four common bacterial pathogens using switchable lanthanide luminescence probe system.

    Science.gov (United States)

    Lehmusvuori, A; Soikkeli, M; Tuunainen, E; Seppä, T; Spangar, A; Rantakokko-Jalava, K; von Lode, P; Karhunen, U; Soukka, T; Wittfooth, S

    2015-11-01

    Ready to use dry-reagent PCR assays for Escherichia coli, Staphylococcus aureus, Streptococcus pneumoniae, Pseudomonas spp. and for broad-range bacteria detection were developed. The assays were based on novel switchable lanthanide probes that provide sensitive target DNA detection with exceptionally high signal-to-background ratio, thus enabling clear discrimination between positive and negative results. For example, sensitivity of three S. aureus and two S. pneumonia bacteria (colony forming units) per PCR assay was measured with fluorescence signal more than 30 times over the background signal level. The rapid and easy-to-use assays are suitable for routine clinical diagnostics without molecular biology expertise and facilities.

  14. Stabilization of actinides and lanthanides in unusually high oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Eller, P.G.; Penneman, R.A.

    1986-01-01

    Chemical environments can be chosen which stabilize actinides and lanthanides in unusually high or low oxidation states and in unusual coordination. In many cases, one can rationalize the observed species as resulting from strong charge/size influences provided by specific sites in host lattices (e.g., Tb(IV) in BaTbO/sub 3/ or Am(IV) in polytungstate anions). In other cases, the unusual species can be considered from an acid-base viewpoint (e.g., U(III) in AsF/sub 5//HF solution or Pu(VII) in Li/sub 5/PuO/sub 6/). In still other cases, an interplay of steric and redox effects can lead to interesting comparisons (e.g., instability of double fluoride salts of Pu(V) and Pu(VI) relative to U, Np, and Am analogues). Generalized ways to rationalize compounds containing actinides and lanthanides in unusual valences (particularly high valences), including the above and numerous other examples, will form the focus of this paper. Recently developed methods for synthesizing high valent f-element fluorides using superoxidizers and superacids at low temperatures will also be described. 65 refs., 8 figs., 9 tabs.

  15. 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.

  16. Study on the luminescence behavior of lanthanide ions with luminol by flow injection chemiluminescence analysis

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xiaoqing [College of Chemistry and Material Science, Northwest University, 710069 Xi' an (China); Wang, Zhuming [College of Earth Sciences and Land Resources, Chang' an University, 710054 Xi' an (China); Li, Yajuan [College of Chemistry and Material Science, Northwest University, 710069 Xi' an (China); Zhang, Yun [Department of pharmacy, Xi' an Medical University, 710021 Xi' an (China); Guo, Jie; Zhao, Jingchan [College of Chemistry and Material Science, Northwest University, 710069 Xi' an (China); Song, Zhenghua, E-mail: songzhenghua@hotmail.com [College of Chemistry and Material Science, Northwest University, 710069 Xi' an (China)

    2015-06-15

    This work first described the linear quenching of Ln{sup III} (including La{sup III}, Ce{sup III}, Pr{sup III}, Nd{sup III}, Sm{sup III}, Eu{sup III}, Gd{sup III}, Tb{sup III}, Dy{sup III}, Ho{sup III}, Er{sup III}, Tm{sup III}, Yb{sup III} and Lu{sup III}) on luminol–dissolved oxygen chemiluminescence system and possible quenching mechanism by flow injection analysis. The general equation of the decrement of CL intensity with Ln{sup III} concentration, ΔI=AlnC{sub Ln}+B, was given and the interaction model of Ln{sup III} with luminol, lg[(I{sub 0}−I)/I]=rlg[Ln]+lgK, was established. The sensitive factor A was found to be linear with the physical parameters (Z, γ{sub ±}, E{sup o} and ΔH{sub hyd}). By plotting A against Z, it could be seen light lanthanides (LL) and heavy lanthanides (HL) presented a good symmetry. The results showed that the reaction of Ln{sup III} with luminol was a spontaneous process by the electrostatic force with the association constants K at 10{sup 6}–10{sup 7} level. The binding constants K{sub D} (about 10{sup 4}–10{sup 5}) and the number of binding sites n (about 1) of Ln{sup III} (La{sup III}, Eu{sup III}, Gd{sup III}, Tb{sup III} and Lu{sup III}) to bovine serum albumin were first given by FI–CL, and the binding ability of Ln{sup III} followed the pattern: La{sup III}

  17. 六齿双Schiff碱稀土配合物的结构及发光%Structure and luminescence of hexa-bis-Schiff base lanthanide complexes

    Institute of Scientific and Technical Information of China (English)

    闫鹏飞; 杨帆; 李光明

    2011-01-01

    A large variety of multidentate ligands have been designed and synthesized for the preparation of lantha-nide complexes with desired functions. Hexa-bis-Schiff base, as one of the most known ligands with N2O4 cavity has been modified to various derivatives in respective to the expected functions. Correspondingly, a large number of Hexa-bis-Schiff base 3d- and/or 4f- metals complexes have been isolated, some of which exhibit intriguing luminescent properties. Especially, hexa-bis-Schiff base polynuclear lanthanide complexes with distinct luminescent properties are currently of interest because of their potential applications in the fabrication of novel materials and as probes in biological systems. In this paper, structure and luminescence of Hexa-bis-Schiff base lanthanide complexes are briefly summarized for those who are interested in this field.%稀土有机配合物作为重要的分子功能材料,由于具有光敏性强、发光效率高等特点,在生产生活的很多领域都具有广阔的应用前景.作为以分子发光材料和分子磁性材料为研究热点的Schiff碱稀土配合物,其合成、结构及其性能的研究吸引了大量国内外化学工作者的广泛关注.结合六齿Schiff碱稀土配合物结构及其性能的最新研究进展,对其新颖结构以及光学方面的性能研究进行概要介绍.

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

    Science.gov (United States)

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

    2010-04-21

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

  19. Hydrothermal synthesis, characterization and luminescent properties of lanthanide-doped NaLaF$_4$ nanoparticles

    Indian Academy of Sciences (India)

    JIGMET LADOL; HEENA KHAJURIA; SONIKA KHAJURIA; HAQ NAWAZ SHEIKH

    2016-08-01

    Nanoparticles of sodium lanthanum (III) fluoride-doped and co-doped with Eu$^{3+}/Tb$^{3+}$ were prepared by the hydrothermal method using citric acid as structure-directing agent. Structural aspects and optical properties of synthesized nanoparticles were studied by powder X-ray diffraction (XRPD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy-dispersive X-ray spectra (EDS), particle size by dynamic light scattering (DLS), Fourier transform infrared (FTIR) spectrum and photoluminescence (PL) techniques. Nanoparticles consist of well-crystallized hexagonal phase and the average crystallite size for undoped and doped-NaLaF$_4$ nanoparticles are in the range of 20–22 nm. TEM images show that nanoparticles have cylindrical shape and crystalline nature of nanoparticles was confirmed by SAED patterns. Downconversion(DC) luminescent properties of doped NaLaF4 were also investigated and impact of co-doping has been explored.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-12-15

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

  1. Sunlight activated lanthanide complex for luminescent solar collector applications: effect of waveguide matrix

    Science.gov (United States)

    Shahi, Praveen Kumar; Singh, Priyam; Bahadur Rai, Shyam

    2017-02-01

    The performance of Eu(DBM)3Phen complex (EDP) dispersed in PMMA poly-(methyl methacrylate) polymer matrix, as simple planner luminescent solar collectors (LSCs) is demonstrated using spectroscopic and photovoltaic (PV) measurements. The organic ligands absorb ultra-violet-blue (UV-blue) radiation (220–450 nm) very efficiently and transfer its energy to the Eu3+ ion, which gives an intense red emission even in sunlight exposure. The excellent optical properties of EDP in PMMA permit its coating on the front surface of c-Si solar cell (10  ×  10 cm2) for PV measurements. The PV characterizations reveal the improvement in the short circuit current density (J sc) of PV cell and maximum improvement is found to be 4.6% for 2.5 wt% EDP concentration in PMMA matrix. The efficiency of solar cell increases from 17.22% to 18.33% for bare and 2.5% EDP in PMMA. At a higher concentration of EDP, the thin film starts losing its transparency and hence PV efficiency decreases. These results illustrate that a EDP complex combined with a PV cell could work as a prototype of a new generation solar cell.

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

    Science.gov (United States)

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

    2017-01-01

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

  3. Efficient dual mode multicolor luminescence in a lanthanide doped hybrid nanostructure: a multifunctional material.

    Science.gov (United States)

    Singh, S K; Singh, A K; Rai, S B

    2011-07-08

    The present work deals with inorganic-organic hybrid nanostructures capable of producing intense visible emission via upconversion (UC), downconversion (DC), and energy transfer (ET) processes which show the potential of the material as a luminescent solar collector (LSC), particularly to improve the efficiency of silicon solar cells. To achieve this, Gd2O3:Yb3+/Er3+ phosphor (average particle size∼35 nm) and a Eu(DBM)3Phen organic complex have been synthesized separately and then the hybrid structure has been developed using a simple mixing procedure. Intense UC emission (in the red, green, and blue regions) due to Er3+ is observed on near infrared (976 nm) excitation which shows color tunability with input pump power. In contrast, intense red emission of Eu3+ is observed on ultaviolet (UV) (355 nm) excitation. The feasibility of energy transfer from Er3+ ions to Eu3+ ions has also been noted. These excellent optical properties are retained even if the particles of the hybrid nanostructure are dispersed in liquid medium, which also makes it suitable for security ink purposes.

  4. Multifunctional nanomesoporous materials with upconversion (in vivo) and downconversion (in vitro) luminescence imaging based on mesoporous capping UCNPs and linking lanthanide complexes

    Science.gov (United States)

    Sun, Lining; Ge, Xiaoqian; Liu, Jinliang; Qiu, Yannan; Wei, Zuwu; Tian, Bo; Shi, Liyi

    2014-10-01

    A series of new multifunctional nanomesoporous materials based on upconversion nanophosphors NaYF4:Yb,Tm@NaGdF4 (UCNPs) and lanthanide complexes were designed and synthesized through mesoporous capping UCNPs nanophosphors and linking lanthanide (Ln) complexes. The obtained UCNPs@mSiO2-Ln(dbm)4 (Ln = Eu, Sm, Er, Nd, Yb) materials can achieve downconversion and upconversion luminescence to show multicolor emission (covering the spectral region from 450 nm to 1700 nm) under visible-light excitation and 980 nm excitation, respectively. In addition, low cytotoxicity and good biocompatibility was found as determined by methyl thiazolyl tetrazolium assay, and the nanomesoporous materials were successfully applied to cell imaging in vitro based on Eu3+ luminescence (under 405 nm excitation) and small animal imaging based on Tm3+ luminescence (under 980 nm excitation). The doped Gd3+ ion endows the nanomesoporous materials UCNPs@mSiO2-Ln(dbm)4 with effective T1 signal enhancement, which affords them as potential magnetic resonance imaging (MRI) contrast agents. Therefore, our results may provide more exciting opportunities for multimodal bioimaging and multifunctional applications.A series of new multifunctional nanomesoporous materials based on upconversion nanophosphors NaYF4:Yb,Tm@NaGdF4 (UCNPs) and lanthanide complexes were designed and synthesized through mesoporous capping UCNPs nanophosphors and linking lanthanide (Ln) complexes. The obtained UCNPs@mSiO2-Ln(dbm)4 (Ln = Eu, Sm, Er, Nd, Yb) materials can achieve downconversion and upconversion luminescence to show multicolor emission (covering the spectral region from 450 nm to 1700 nm) under visible-light excitation and 980 nm excitation, respectively. In addition, low cytotoxicity and good biocompatibility was found as determined by methyl thiazolyl tetrazolium assay, and the nanomesoporous materials were successfully applied to cell imaging in vitro based on Eu3+ luminescence (under 405 nm excitation) and small

  5. Lanthanides post-functionalized indium metal-organic frameworks (MOFs) for luminescence tuning, polymer film preparation and near-UV white LED assembly.

    Science.gov (United States)

    Wu, Jing-Xing; Yan, Bing

    2016-11-22

    A class of hybrid materials based on indium 2,2'-bipyridine-5,5'-dicarboxylate metal-organic frameworks, In(OH)bpydc, was synthesized by postsynthetic introduction with lanthanide ions (Eu(3+), Tb(3+) and Sm(3+)). The structure, thermal stability, morphology and more detailed information about these materials were characterized by XRD, DSC, BET, FTIR, SEM and so forth. The further study of luminescent properties in detail showed that these compounds possess characteristic emission, and the In-MOF-Eu maintains different colors of light from blue-green to red under different excitation wavelengths (excited at 400 nm to 320 nm), which includes the near-white light region (the color coordinates are X = 0.34, Y = 0.36). It is a remarkable fact that the trend of ligand-central emission is opposite to that of the characteristic emission of Eu(3+). Moreover, a kind of thin film and assembled white light near-UV LED based on the optically lanthanide-functionalized MOFs was prepared in order to extend their potential applications; both of them lead to desirable white light (X = 0.34, Y = 0.36; X = 0.35, Y = 0.37). In addition, the matrix does not affect the white luminescence.

  6. Lanthanide-Potassium Biphenyl-3,3'-disulfonyl-4,4'-dicarboxylate Frameworks: Gas Sorption, Proton Conductivity, and Luminescent Sensing of Metal Ions.

    Science.gov (United States)

    Zhou, Li-Juan; Deng, Wei-Hua; Wang, Yu-Ling; Xu, Gang; Yin, Shun-Gao; Liu, Qing-Yan

    2016-06-20

    A novel sulfonate-carboxylate ligand of biphenyl-3,3'-disulfonyl-4,4'-dicarboxylic acid (H4-BPDSDC) and its lanthanide-organic frameworks {[LnK(BPDSDC)(DMF)(H2O)]·x(solvent)}n (JXNU-2, where JXNU denotes Jiangxi Normal University, DMF indicates dimethylformamide, and Ln = Sm(3+), Eu(3+), and Pr(3+)) were synthesized and structurally characterized. The three isomorphous lanthanide compounds feature three-dimensional frameworks constructed from one-dimensional (1D) rod-shaped heterometallic Ln-K secondary building units and are an illustration of a Kagome-like lattice with large 1D hexagonal channels and small 1D trigonal channels. The porous material of the representive JXNU-2(Sm) has an affinity to quadrupolar molecules such as CO2 and C2H2. In addition, the JXNU-2(Sm) compound exhibits humidity- and temperature-dependent proton conductivity with a large value of 1.11 × 10(-3) S cm(-1) at 80 °C and 98% relative humidity. The hydrophilic sulfonate group on the surface of channels facilitates enrichment of the solvate water molecules in the channels, which enhances the proton conductivity of this material. Moreover, the JXNU-2(Eu) material with the characteristic bright red color shows the potential for recognition of K(+) and Fe(3+) ions. The enhancing Eu(3+) luminescence with the K(+) ion and quenching Eu(3+) luminescence with the Fe(3+) ion can be associated with the functional groups of the organic ligand.

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

    Institute of Scientific and Technical Information of China (English)

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

    2016-01-01

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

  8. An alkaline one-pot reaction to synthesize luminescent Eu-BTC MOF nanorods, highly pure and water-insoluble, under room conditions

    Science.gov (United States)

    Medina-Velazquez, D. Y.; Alejandre-Zuniga, B. Y.; Loera-Serna, S.; Ortiz, E. M.; Morales-Ramirez, A. de J.; Garfias-Garcia, E.; Garcia-Murillo, A.; Falcony, C.

    2016-12-01

    The increasing demand for optoelectronic devices requires the development of luminescent materials with high luminescence efficiency and low energy demands, and the metalorganic frameworks (MOFs) with lanthanides ions offer great potential in this area. The metalorganic materials provide properties of flexibility, low density, low-cost methods of synthesis, and insolubility in water, which gives them an advantage over traditional phosphors. In this study, a benzenetricarboxylate ligand (BTC) with a Eu3+ MOF was synthesized, and its structural and luminescent properties were measured. The metalorganic compound was generated in a one-pot reaction from europium nitrate and trimesic acid precursors. Through characterization by X-ray diffraction powder, infrared spectroscopy, SEM structural characterization, and luminescent spectroscopy, the formation of Europium benzenetricarboxylate (Eu-BTC) MOF nanorods was tested and the calculated value was in the range of 30-60 nm. A red luminescent emission with high intensity was observed for all the procedures.

  9. Target-Triggered Switching on and off the Luminescence of Lanthanide Coordination Polymer Nanoparticles for Selective and Sensitive Sensing of Copper Ions in Rat Brain.

    Science.gov (United States)

    Huang, Pengcheng; Wu, Fangying; Mao, Lanqun

    2015-07-01

    Copper ions (Cu(2+)) in the central nervous system play a crucial role in the physiological and pathological events, so simple, selective, and sensitive detection of cerebral Cu(2+) is of great importance. In this work, we report a facile yet effective fluorescent method for sensing of Cu(2+) in rat brain using one kind of lanthanide coordination polymer nanoparticle, adenosine monophosphate (AMP) and terbium ion (Tb(3+)), i.e., AMP-Tb, as the sensing platform. Initially, a cofactor ligand, 5-sulfosalicylic acid (SSA), as the sensitizer, was introduced into the nonluminescent AMP-Tb suspension, resulting in switching on the luminescence of AMP-Tb by the removal of coordinating water molecules and concomitant energy transfer from SSA to Tb(3+). The subsequent addition of Cu(2+) into the resulting SSA/AMP-Tb can strongly quench the fluorescence because the specific coordination interaction between SSA and Cu(2+) rendered energy transfer from SSA to Tb(3+) inefficient. The decrease ratio of the fluorescence intensities of SSA/AMP-Tb at 550 nm show a linear relationship for Cu(2+) within the concentration range from 1.5 to 24 μM with a detection limit of 300 nM. The method demonstrated here is highly selective and is free from the interference of metal ions, amino acids, and the biological species commonly existing in the brain such as dopamine, lactate, and glucose. Eventually, by combining the microdialysis technique, the present method has been successfully applied in the detection of cerebral Cu(2+) in rat brain with the basal dialysate level of 1.91 ± 0.40 μM (n = 3). This method is very promising to be used for investigating the physiological and pathological events that cerebral Cu(2+) participates in.

  10. Novel lanthanide doped micro- and mesoporous solids. Characterization of ion-host-interactions, species distribution and luminescence properties using time-resolved luminescence spectroscopy; Neuartige Lanthanoid-dotierte mikro- und mesoporoese Feststoffe. Charakterisierung von Ion-Wirt-Wechselwirkungen, Speziesverteilung und Lumineszenzeigenschaften mittels zeitaufgeloester Lumineszenzspektroskopie

    Energy Technology Data Exchange (ETDEWEB)

    Gessner, Andre

    2010-12-15

    In this work lanthanide-doped microporous zeolites, microporous-mesoporous hybrid materials and mesoporous silicates were investigated regarding their luminescence properties and the ion-host-interactions using time-resolved luminescence spectroscopy. Thereby, time-resolved emission spectra (TRES) provide information in the wavelength and time domain. For the analysis of the TRES a broad set of analytic methods was applied and thus a corresponding ''toolbox'' developed. Fitting of the luminescence decays was performed with a discrete number of exponentials and supported by luminescence decay times distributions. Time-resolved area normalized emission spectra (TRANES), an advancement of TRES, could be used for the determination of the number of emissive lanthanide species in porous materials for the first time. Calculation of the decay-associated spectra (DAS) allowed the correlation of spectral information with luminescence decay times and thus delivered the luminescence spectra of the different europium species. For europium(III) we could use in addition the time-dependent asymmetry ratio and spectral evolution of the {sup 5}D{sub 0}-{sup 7}F{sub 0}-transition with time to obtain further information about the distribution of the lanthanide ions in the host material. Luminescence decay times and spectra allowed conclusions on the number of OH-oscillators in and the symmetry of the first coordination sphere. For the microporous and microporous-mesoporous materials were found different lanthanide species, which were characterized by the above mentioned methods. These lanthanide species can be found on different positions in the host material. One position is located deep in the pore system. Here, lanthanide ions are hardly accessible for water and mainly coordinated by framework oxygens. This results in long luminescence decay times and distorted coordination spheres. The second position can be found near or on the outer surface or in the

  11. Aromatic triamide-lanthanide complexes

    Science.gov (United States)

    Raymond, Kenneth N; Petoud, Stephane; Xu, Jide

    2013-10-08

    The present invention provides luminescent lanthanide metal chelates comprising a metal ion of the lanthanide series and a complexing agent comprising at least one phthalamidyl moiety. Also provided are probes incorporating the phthalamidyl ligands of the invention and methods utilizing the ligands of the invention and probes comprising the ligands of the invention.

  12. Three-way partial least-squares/residual bilinearization study of second-order lanthanide-sensitized luminescence excitation-time decay data: analysis of benzoic acid in beverage samples.

    Science.gov (United States)

    Lozano, Valeria A; Ibañez, Gabriela A; Olivieri, Alejandro C

    2008-03-10

    Lanthanide-sensitized luminescence excitation-time decay matrices were employed for achieving the second-order advantage using as chemometric algorithms parallel factor analysis (PARAFAC) and multidimensional partial least-squares with residual bilinearization (N-PLS/RBL). The second-order data were measured for a calibration set of samples containing the analyte benzoic acid in the concentration range from 0.00 to 5.00 mg L(-1), for a validation set containing the analyte and the potential interferent saccharin (in the range 0.00-6.00 mg L(-1)), and for real samples of beverages containing benzoic acid as preservant, saccharin, and other potentially interfering compounds. All samples were treated with terbium(III), trioctylphosphine oxide as a synergistic ligand, and contained a suitable imidazol buffer, in order to ensure maximum intensity of the luminescence signals. The results indicate a slightly better predictive ability of the newly introduced N-PLS/RBL procedure over standard PARAFAC, both in what concerns the comparison with nominal analyte concentrations in the validation sample set and with results provided by the reference high-performance liquid chromatographic technique for the real sample set.

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

    Science.gov (United States)

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

    1984-06-25

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

  14. Recent Advances in Near-Infrared Luminescent Lanthanide Porphyrin Complexes%稀土卟啉近红外发光配合物在生命科学领域中的应用研究进展

    Institute of Scientific and Technical Information of China (English)

    张涛; 郑举敦; 吴云霞

    2016-01-01

    Near-Infrared luminescent lanthanide complexes are well known for their unique 3d-4f electronic structures, which exhibit special photochemical and photophysical properties such as line-like emission spectra,large stoke shift and long luminescence lifetimes (micro-to milli-second scale),which has received much attention for their highlighted value in the applications of bio-sensing and imaging analysis.However,due to Laporte-forbidden 4f → 4f transitions of LnI I i-ons,direct excitation of LnI I ions rarely yields highly luminescent materials.To this end,indirect excitation,termed sensitization or antenna effect by chromophores,has to be used.Porphyrins with exceedingly delocalized πsystems and high stability,which undoubtedly represent one of the most studied macrocyclic rings,have been widely used to sensitize NIR emission of LnI I ions.In this review,the latest developments in the field of NIR emissive porphyrin lanthanide com-plexes were summarized.And the features,advantages,designed ideas and developing trends of these NIR complexes are also demonstrated in this review.%稀土近红外发光材料具有独特的光物理性质,如发光谱带窄、较大的 Stock 位移、荧光寿命长可达毫秒级等,在医学诊断和成像、免疫分析等热门领域具有重大的应用前景。但由于跃迁选择定则,稀土离子本身的吸收系数较小,需要用特定的生色团对其进行敏化,以增强其发光性能。在众多生色团中,卟啉化合物由于其激发态能级与近红外发光的稀土离子能级较为匹配,可以较好的敏化稀土离子,获得较高的近红外发光效率,因此,近年来受到了极大的关注。本文总结了近年来近红外发光卟啉稀土配合物在生命科学领域中的应用研究进展,并对其发展前景进行了展望。

  15. Synthesis, photophysical analysis, and in vitro cytotoxicity assessment of the multifunctional (magnetic and luminescent) core@shell nanomaterial based on lanthanide-doped orthovanadates

    Energy Technology Data Exchange (ETDEWEB)

    Szczeszak, Agata [Adam Mickiewicz University, Department of Rare Earths, Faculty of Chemistry (Poland); Ekner-Grzyb, Anna [Adam Mickiewicz University, Department of Behavioural Ecology, Faculty of Biology (Poland); Runowski, Marcin [Adam Mickiewicz University, Department of Rare Earths, Faculty of Chemistry (Poland); Mrówczyńska, Lucyna [Adam Mickiewicz University, Department of Cell Biology, Faculty of Biology (Poland); Grzyb, Tomasz; Lis, Stefan, E-mail: blis@amu.edu.pl [Adam Mickiewicz University, Department of Rare Earths, Faculty of Chemistry (Poland)

    2015-03-15

    Rare earths orthovanadates (REVO{sub 4}) doped with luminescent lanthanide ions (Ln{sup 3+}) play an important role as promising light-emitting materials. Gadolinium orthovanadate exhibits strong absorption of ultraviolet radiation and as a matrix doped with Eu{sup 3+} ions is well known for its efficient and intense red emission, induced by energy transfer from the VO{sub 4}{sup 3−} groups to Eu{sup 3+} ions. In the presented study, Fe{sub 3}O{sub 4}@SiO{sub 2}@GdVO{sub 4}:Eu{sup 3+} 5 % nanomaterial was investigated. The core@shell structures demonstrate attractive properties, such as higher thermal stability, enhanced water solubility, increased optical response, higher luminescence, longer decay times, and magnetic properties. Silica coating may protect nanocrystals from the surrounding environment. Therefore, such silica-covered nanoparticles (NPs) are successfully utilized in biomedical research. Multifunctional magnetic nanophosphors are very interesting due to their potential biomedical applications such as magnetic resonance imaging, hyperthermic treatment, and drug delivery. Therefore, the aim of our study was to investigate photophysical, chemical, and biological properties of multifunctional REVO{sub 4} doped with Ln{sup 3+}. Moreover, the studied NPs did not affect erythrocyte sedimentation rate, cell membrane permeability, and morphology of human red blood cells.

  16. Two-photon sensitized visible and near-IR luminescence of lanthanide complexes using a fluorene-based donor-π-acceptor diketonate.

    Science.gov (United States)

    Woodward, Adam W; Frazer, Andrew; Morales, Alma R; Yu, Jin; Moore, Anthony F; Campiglia, Andres D; Jucov, Evgheni V; Timofeeva, Tatiana V; Belfield, Kevin D

    2014-11-28

    A fluorene-based donor-acceptor ligand was successfully employed to sensitize visible and near-IR emitting lanthanide centers. The ligand construct is based on a donor-π-acceptor architecture with diphenylamino acting as the donor and a fluorenyl π bridge derivatized with a trifluoroacetonate moiety acting as both a strong acceptor and the classic bidentate scaffold for complexing metals. (1)H NMR analysis in the polar solvents THF and CDCl3 revealed the enolic form of the diketone dominant in solution equilibria at room temperature. This preferred cis-enol form binds strongly to the lanthanide(III) ions (Ln = Eu, Sm, Dy, Tb, Yb, Nd, Er, and Gd) in the presence of phenanthroline affording the resulting ternary tris(diketonates) complexes with 1,10-phenanthroline. Detailed characterization of these complexes was conducted, with particular emphasis on linear and nonlinear photophysical properties. Steady-state and time-resolved emission spectroscopy and overall photoluminescence quantum yield (PLQY) measurements were performed on all the complexes. Sizeable visible and near-IR efficiency for europium (room temperature, visible), samarium (low temperature, visible) and ytterbium, neodymium and erbium (room temperature, near-IR) was displayed, with long luminescent lifetimes for the europium and samarium complexes of 85 and 70 μs, respectively Measurement of the luminescence decay for the Yb complex at 976 nm, Nd complex at 874 nm, and Er complex at 1335 nm yielded mono-exponential decay curves, with lifetimes of ~13 μs, ~1.6 μs, and ~2.5 μs, respectively, inferring that the emission was generated by a single species. In addition, fluorescence anisotropy and two-photon absorption (2PA) spectra (via Z-scan) were obtained for the ligand and europium complex, revealing a maximum 2PA cross section of 340 GM for the latter upon excitation at 760 nm. A quadratic relationship was found by varying laser excitation power vs. luminescence intensity of the europium complex

  17. Crystal Structure and Luminescence Property of Lanthanide Complexes with 2-Fluorobenzoic Acid and 2,2'-Bipyridine

    Institute of Scientific and Technical Information of China (English)

    Li Xia; Zhang Zhuoyong; Song Haibin

    2005-01-01

    The two compounds of [Ln(2-FBA)3·2,2'-bpy]2 (2-FBA=2-fluorobenzoato, 2,2'-bpy=2,2'-bipyridine, Ln=Eu(1), Dy(2)) were synthesized and their structures were determined by X-ray diffraction method. Crystallized complexes 1 and 2 are isomorphous, monoclinic system with P21/n space group. The two complexes are binuclear molecule with an inversion center. The two lanthanide ions are linked by four bridged 2-FBA ligands and each lanthanide ion is further bonded to one chelated bidentate 2-FBA ligand and one 2,2'-bipyridine molecule. The coordination number of metal ion is eight. The europium complex exhibits strong red fluorescence. 5D0→7Fj (j= 1~4) transition emission of Eu3+ ion was observed.

  18. Upconversion luminescence of lanthanide-doped mixed CaMoO4-CaWO4 micro-/nano-materials.

    Science.gov (United States)

    Liu, Jing; Kaczmarek, Anna M; Billet, Jonas; Van Driessche, Isabel; Van Deun, Rik

    2016-08-14

    Uniform mixed CaMoO4-CaWO4 micro-/nano-materials have been successfully synthesised by a facile hydrothermal method. The morphology of these upconversion materials could be changed to different shapes and the size could also be decreased from the micro- to nano-scale by varying the type of surfactant used. It was observed that before heat treatment, the materials show relatively weak green light emission under excitation at 975 nm, whereas after heat treatment, the intensity of the upconversion luminescence increases dramatically while the intensity of the red component decreases relatively. By adjusting the molybdate/tungstate ratio, it was found that the samples with a higher molybdate content have stronger luminescence properties. XRD measurements have been done to investigate the structure of the mixed CaMoO4-CaWO4 upconversion materials. The effect of heat treatment at different temperatures on the emission spectra and XRD patterns has also been studied. TG-DTA was used to further confirm the most suitable temperature for heat treatment. The luminescence lifetimes and CIE coordinates for these samples were also determined. Additionally it was found that Gd(3+) co-doping could further increase the upconversion luminescence from these mixed CaMoO4-CaWO4 materials. Finally, monitoring the upconversion luminescence intensity as a function of laser pump power confirmed the upconversion process to be a two-photon absorption mechanism.

  19. Synthesis, characterization of the luminescent lanthanide complexes with ( Z)-4-(4-methoxyphenoxy)-4-oxobut-2-enoic acid

    Science.gov (United States)

    Duan, Guo-Jian; Yang, Ying; Liu, Tong-Huan; Gao, Ya-Ping

    2008-02-01

    ( Z)-4-(4-Methoxyphenoxy)-4-oxobut-2-enoic acid and its solid rare earth complexes LnL 3·2H 2O (Ln = La, Eu, Tb) were synthesized and characterized by means of MS, elemental analysis, FTIR, 13C NMR and TG-DTA. The IR and 13C NMR results show that the carboxylic groups in the complexes coordinated to the rare earth ions in the form of a bidentate ligand, but the ester carboxylic groups have not taken part in the coordination. The luminescence spectra of Eu(III) and Tb(III) complexes in solid state were also studied. The strong luminescence emitting peaks at 616 nm for Eu(III) and 547 nm for Tb(III) can be observed, which could be attributed to the ligand has an enhanced effect to the luminescence intensity of the Eu and Tb.

  20. Near infrared and visible luminescence from xerogels covalently grafted with lanthanide [Sm(3+), Yb(3+), Nd(3+), Er(3+), Pr(3+), Ho(3+)] β-diketonate derivatives using visible light excitation.

    Science.gov (United States)

    Sun, Lining; Qiu, Yannan; Liu, Tao; Zhang, Jin Z; Dang, Song; Feng, Jing; Wang, Zhijuan; Zhang, Hongjie; Shi, Liyi

    2013-10-09

    A series of ternary lanthanide β-diketonate derivatives covalently bonded to xerogels (named as Ln-DP-xerogel, Ln = Sm, Yb, Nd, Er, Pr, Ho) by doubly functionalized alkoxysilane (dbm-Si) was synthesized in situ via a sol-gel process. The properties of these xerogel materials were investigated by Fourier-transform infrared (FT-IR) spectroscopy, field-emission scanning electron microscopy (FE-SEM), diffuse reflectance (DR) spectroscopy, thermogravimetric analyses, and fluorescence spectroscopy. The data and analyses suggest that the lanthanide derivatives have been covalently grafted to the corresponding xerogels successfully. Of importance here is that, after excitation with visible light (400-410 nm), the xerogels all show characteristic visible (Sm(3+)) as well as near-infrared (NIR; Sm(3+), Yb(3+), Nd(3+), Er(3+), Pr(3+), Ho(3+)) luminescence of the corresponding Ln(3+) ions, which is attributed to the energy transfer from the ligands to the Ln(3+) ions via an antenna effect. Exciting with visible light is advantageous over UV excitation. Furthermore, to the best of our knowledge, it is the first observation of NIR luminescence with visible light excitation from xerogels covalently bonded with the Sm(3+), Pr(3+), and Ho(3+) derivatives. Compared to lanthanide complexes (Ln = Er, Nd, Yb) functionalized periodic mesoporous organosilica (PMO) materials that exhibit similar optical properties reported in our previous work, the Ln-DP-xerogel (Ln = Sm, Yb, Nd, Er, Pr, Ho) in this case offer advantages in terms of ease of synthesis and handling and potentially low cost for emerging technological applications. Development of near-infrared luminescence of the lanthanide materials with visible light excitation is of strong interest to emerging applications such as chemosensors, laser systems, and optical amplifiers.

  1. Spectroscopic, luminescence and in vitro biological studies of solid ketoprofen of heavier trivalent lanthanides and yttrium(III).

    Science.gov (United States)

    Gálico, D A; Lahoud, M G; Davolos, M R; Frem, R C G; Fraga-Silva, T F C; Venturini, J; Arruda, M S P; Bannach, G

    2014-11-01

    Solid-state compounds of the general formulae [ML3] (M=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y; L=ketoprofen) were synthesized and characterized using infrared, diffuse reflectance and luminescence spectroscopies. IR data suggested that the carboxylate group in ketoprofen is coordinated to the metals as a bidentate ligand. The triplet state energy level was determined using the Gd(3+) complex, which exhibited a ketoprofen blue luminescence when excited in the UV region. The compound containing Tb(3+) ion was sensitized by the ligand and emitted in the green region of the visible spectrum. On the other hand, for the analogous species containing the dysprosium ion, a competition for luminescence between the Dy(3+) and the ligand levels was observed. Finally, Tm(3+) complex exhibits only ligand luminescence. These optical behaviors are discussed based on rare earth energy diagrams. In addition, the compounds were evaluated for their anti-inflammatory activities. All the compounds showed a higher production of H2O2 and IL-10 than the ketoprofen, suggesting that the compounds exhibited an immunomodulatory effect and this opens up new perspectives for immunotherapeutic approaches. Copyright © 2014 Elsevier Inc. All rights reserved.

  2. A luminescent lanthanide coordination polymer based on energy transfer from metal to metal for hydrogen peroxide detection.

    Science.gov (United States)

    Zeng, Hui-Hui; Zhang, Li; Rong, Lian-Qing; Liang, Ru-Ping; Qiu, Jian-Ding

    2017-03-15

    A bimetal lanthanide coordination polymer nanoparticle (ATP-Ce/Tb-Tris CPNs) with good biocompatibility was synthesized in Tris-HCl buffer using adenosine triphosphate (ATP) molecules as the bridge ligands. The large absorption cross section and suitable emission energy of Ce(3+) matching to the adsorption energy of Tb(3+)((4)fn) results in the efficient energy transfer from Ce(3+) to Tb(3+), thus the synthesized ATP-Ce/Tb-Tris CPNs exhibit the characteristic green emission of Tb(3+). Such energy transfer from metal to metal in fluorescent lanthanide coordination polymer nanoparticles (Ln-CPNs) has been demonstrated. It is found that the oxidation of Ce(3+) in ATP-Ce/Tb-Tris CNPs to Ce(4+) would interrupt the energy transfer from Ce(3+) to Tb(3+), leading to fluorescence quenching of Tb(3+). On the basis of this quenching mechanism, ATP-Ce/Tb-Tris CPNs has been successfully used to detect reactive oxygen H2O2 with detection limit as low as 2nM. If glucose oxidase is present in the system, glucose can be determined using the ATP-Ce/Tb-Tris CNPs nanosensor.

  3. Tuning the decay time of lanthanide-based near infrared luminescence from micro- to milliseconds through d-->f energy transfer in discrete heterobimetallic complexes.

    Science.gov (United States)

    Torelli, Stéphane; Imbert, Daniel; Cantuel, Martine; Bernardinelli, Gérald; Delahaye, Sandra; Hauser, Andreas; Bünzli, Jean-Claude G; Piguet, Claude

    2005-05-20

    Inert and optically active pseudo-octahedral Cr(III)N6 and Ru(II)N6 chromophores have been incorporated by self-assembly into heterobimetallic triple-stranded helicates HHH-[CrLnL3]6+ and HHH-[RuLnL3]5+. The crystal structures of [CrLnL(3)](CF(3)SO(3))(6) (Ln=Nd, Eu, Yb, Lu) and [RuLnL3](CF3SO3)5 (Ln=Eu, Lu) demonstrate that the helical structure can accommodate metal ions of different sizes, without sizeable change in the intermetallic MLn distances. These systems are ideally suited for unravelling the molecular factors affecting the intermetallic nd-->4f communication. Visible irradiation of the Cr(III)N6 and Ru(II)N6 chromophores in HHH-[MLnL3]5/6+ (Ln=Nd, Yb, Er; M=Cr, Ru) eventually produces lanthanide-based near infrared (NIR) emission, after directional energy migration within the complexes. Depending on the kinetic regime associated with each specific d-f pair, the NIR luminescence decay times can be tuned from micro- to milliseconds. The origin of this effect, together with its rational control for programming optical functions in discrete heterobimetallic entities, are discussed.

  4. Novel heteroleptic lanthanide organic frameworks containing pyridine-2,5-dicarboxylic acid and in situ generated piperazine-2,5-dicarboxylic acid from piperazine: Hydrothermal synthesis and luminescent properties

    Energy Technology Data Exchange (ETDEWEB)

    Ay, Burak [Department of Chemistry, Arts and Science Faculty, Çukurova University, 01330, Adana (Turkey); Yildiz, Emel, E-mail: eeyildiz@cu.edu.tr [Department of Chemistry, Arts and Science Faculty, Çukurova University, 01330, Adana (Turkey); Kani, İbrahim [Department of Chemistry, Anadolu University,26470, Eskişehir (Turkey)

    2016-01-15

    Two novel 3D lanthanide metal-organic frameworks [Ln(pydc)(pip){sub 1/2}(H{sub 2}O] (Ln=Ce (1) and Pr (2), H{sub 2}pydc=2,5-pyridinedicarboxylic acid, H{sub 2}pip=2,5-piperazinedicarboxylic acid have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffractions (PXRD), and single-crystal X-ray diffractions. Field emission scanning electron microscopy (FESEM) was used for morphological analysis. Complexes are isostructural and feature interesting 3D frameworks. Both compounds crystallize in the monoclinic system, space group P2{sub 1}/c. Structural analyses of 1 and 2 show that Ln{sup 3+} ions connect with each other through H{sub 2}pydc and H{sub 2}pip. To the best of our knowledge, they are the first heteroleptic lanthanide polymers obtained through in situ 2,5-piperazinedicarboxylic acid syntheses. Moreover, thermal and luminescent properties of the compounds have been investigated. - Graphical abstract: Two novel 3D lanthanide metal-organic frameworks have been synthesized under hydrothermal conditions. Luminescent properties of the compounds in different temperatures have been also investigated. - Highlights: • New cerium and praseodymium coordination polymers based on N-O-bifunctional ligands have been synthesized In situ hydrothermal decarboxylation. • 2,5-pyridinedicarboxylic acid and piperazine were used as ligands. • In situ hydrothermal decarboxylation and formation of ligands were observed.

  5. Novel heteroleptic lanthanide organic frameworks containing pyridine-2,5-dicarboxylic acid and in situ generated piperazine-2,5-dicarboxylic acid from piperazine: Hydrothermal synthesis and luminescent properties

    Science.gov (United States)

    Ay, Burak; Yildiz, Emel; Kani, İbrahim

    2016-01-01

    Two novel 3D lanthanide metal-organic frameworks [Ln(pydc)(pip)1/2(H2O] (Ln=Ce (1) and Pr (2), H2pydc=2,5-pyridinedicarboxylic acid, H2pip=2,5-piperazinedicarboxylic acid have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffractions (PXRD), and single-crystal X-ray diffractions. Field emission scanning electron microscopy (FESEM) was used for morphological analysis. Complexes are isostructural and feature interesting 3D frameworks. Both compounds crystallize in the monoclinic system, space group P21/c. Structural analyses of 1 and 2 show that Ln3+ ions connect with each other through H2pydc and H2pip. To the best of our knowledge, they are the first heteroleptic lanthanide polymers obtained through in situ 2,5-piperazinedicarboxylic acid syntheses. Moreover, thermal and luminescent properties of the compounds have been investigated.

  6. Multicolour synthesis in lanthanide-doped nanocrystals through cation exchange in water

    KAUST Repository

    Han, Sanyang

    2016-10-04

    Meeting the high demand for lanthanide-doped luminescent nanocrystals across a broad range of fields hinges upon the development of a robust synthetic protocol that provides rapid, just-in-time nanocrystal preparation. However, to date, almost all lanthanide-doped luminescent nanomaterials have relied on direct synthesis requiring stringent controls over crystal nucleation and growth at elevated temperatures. Here we demonstrate the use of a cation exchange strategy for expeditiously accessing large classes of such nanocrystals. By combining the process of cation exchange with energy migration, the luminescence properties of the nanocrystals can be easily tuned while preserving the size, morphology and crystal phase of the initial nanocrystal template. This post-synthesis strategy enables us to achieve upconversion luminescence in Ce3+ and Mn2+-activated hexagonal-phased nanocrystals, opening a gateway towards applications ranging from chemical sensing to anti-counterfeiting.

  7. Design of efficient electroluminescent lanthanide(III) complexes

    CERN Document Server

    You, B R; Park, N G; Kim, Y S

    2001-01-01

    The lanthanide complexes have been anticipated to exhibit high efficiency along with a narrow emission spectrum. Photoluminescence for the lanthanide complex is characterized by a high efficiency since both single and triplet excitons are involved in the luminescence process. However, the maximum external electroluminescence quantum efficiencies have exhibited values around 1% due to triplet-triplet annihilation at high current. Here, we proposed a new energy transfer mechanism to overcome triplet-triplet annihilation by the Eu complex doped into phosphorescent materials with triplet levels that were higher than single levels of the Eu complex. In order to show the feasibility of the proposed energy transfer mechanism and to obtain the optimal ligands and host material, we have calculated the effect depending on ligands as a factor that controls emission intensity in lanthanide complexes. The calculation shows that triplet state as well as singlet state of anion ligand affects on absorption efficiency indirec...

  8. Lanthanide-doped nanoparticles as the active optical medium in polymer-based devices

    OpenAIRE

    Stouwdam, Jan Willem

    2004-01-01

    The luminescence of lanthanide ions in organic environment is greatly reduced compared to inorganic materials. This thesis describes the doping of the lanthanide ions in the core of inorganic nanoparticles that are soluble in organic solvents as a way to shield the lanthanide ions from the organic environment and thus to increase the luminescence properties.

  9. 3,4,3-LI(1,2-HOPO): In Vitro Formation of Highly Stable Lanthanide Complexes Translates into Efficacious In Vivo Europium Decorporation

    Energy Technology Data Exchange (ETDEWEB)

    Sturzbecher-Hoehne, Manuel; Ng Pak Leung, Clara; Daleo, Anthony; Kullgren, Birgitta; Prigent, Anne-Laure; Shuh, David K.; Raymond, Kenneth N.; Abergel, Rebecca J.

    2011-07-13

    The spermine-based hydroxypyridonate octadentate chelator 3,4,3-LI(1,2-HOPO) was investigated for its ability to act as an antennae that sensitizes the emission of Sm{sup III}, Eu{sup III}, and Tb{sup III} in the Visible range (Φ{sub tot} = 0.2 - 7%) and the emission of Pr{sup III}, Nd{sup III}, Sm{sup III}, and Yb{sup III} in the Near Infra-Red range, with decay times varying from 1.78 μs to 805 μs at room temperature. The particular luminescence spectroscopic properties of these lanthanide complexes formed with 3,4,3-LI(1,2-HOPO) were used to characterize their respective solution thermodynamic stabilities as well as those of the corresponding La{sup III}, Gd{sup III}, Dy{sup III}, Ho{sup III}, Er{sup III}, Tm{sup III}, and Lu{sup III} complexes. The remarkably high affinity of 3,4,3-LI(1,2-HOPO) for lanthanide metal ions and the resulting high complex stabilities (pM values ranging from 17.2 for La{sup III} to 23.1 for Yb{sup III}) constitute a necessary but not sufficient criteria to consider this octadentate ligand an optimal candidate for in vivo metal decorporation. The in vivo lanthanide complex stability and decorporation capacity of the ligand were assessed, using the radioactive isotope {sup 152}Eu as a tracer in a rodent model, which provided a direct comparison with the in vitro thermodynamic results and demonstrated the great potential of 3,4,3-LI(1,2-HOPO) as a therapeutic metal chelating agent.

  10. Basic TRLFS data of some lanthanides using a tunable laser system and a red-optimized detection system

    Energy Technology Data Exchange (ETDEWEB)

    Heller, Anne [Dresden Technische Univ. (Germany). Inst. for Zoology, Molecular Cell Physiology and Endocrinology; Barkleit, Astrid [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Chemistry of the F-Elements; Geipel, Gerhard [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Biogeochemistry

    2016-07-01

    Lanthanides are crucial raw materials for modern high-tech products and used in medicine, especially as contrast enhancing agents for magnetic resonance imaging [1]. To study their interactions in the geo- and biosphere, Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS), which is a non-invasive, very sensitive, and versatile state of the art method, is used. Up to now, TRLFS is well established for actinides but only some lanthanides (especially Eu and Tb). To extent this scope, we investigate the basic luminescence properties of all lanthanide elements.

  11. Luminescence, magnetocaloric effect and single-molecule magnet behavior in lanthanide complexes based on a tridentate ligand derived from 8-hydroxyquinoline.

    Science.gov (United States)

    Shen, Hai-Yun; Wang, Wen-Min; Bi, Yan-Xia; Gao, Hong-Ling; Liu, Shuang; Cui, Jian-Zhong

    2015-11-21

    A new family of lanthanide complexes, [Ln2(hfac)4L2] (Ln = Eu (1), Gd (2), Tb (3), Dy (4), Ho (5), Er (6), Lu (7); hfac = hexafluoroacetylacetonate, HL = 2-(2′-benzothiazole)-8-hydroxyquinoline), was synthesized and characterized using single-crystal X-ray diffraction, elemental analysis (EA), thermal gravimetric analysis (TGA), powder X-ray diffraction (PXRD) and UV-vis spectra. X-ray crystallographic analyses reveal that 1–7 are isomorphous and crystallize in the monoclinic space group C2/c. In these dinuclear complexes, each LnШ ion is eight-coordinated with two bidentate hfac and two μ-phenol bridging L ligands. The TGA results show that the complexes have relatively high thermal stabilities. Complexes 1 and 3 show the characteristic transitions of the corresponding lanthanide ions with ligand-related emission peaks. Meanwhile, complexes 4 and 7 exhibit ligand-centered fluorescence at room temperature. Magnetic measurements were carried out on complexes 2–6. The magnetic study reveals that 2 displays a magnetocaloric effect, with a maximum −ΔSm value of 16.89 J K−1 kg−1 at 2 K for ΔH = 8 T. Dynamic magnetic studies reveal single-molecule magnet (SMM) behavior for complex 4. Fitting the dynamic magnetic data to the Arrhenius law gives an energy barrier ΔE/kB = 50.33 K and pre-exponential factor τ0 = 1.05 × 10(-8)s.

  12. Lanthanide chelate complementation and hydrolysis enhanced luminescent chelate in real-time reverse transcription polymerase chain reaction assays for KLK3 transcripts.

    Science.gov (United States)

    Alinezhad, Saeid; Väänänen, Riina-Minna; Lehmusvuori, Ari; Karhunen, Ulla; Soukka, Tero; Kähkönen, Esa; Taimen, Pekka; Alanen, Kalle; Pettersson, Kim

    2014-01-01

    The requirement for high-performance reporter probes in real-time detection of polymerase chain reaction (PCR) has led to the use of time-resolved fluorometry of lanthanide chelates. The aim of this study was to investigate the applicability of the principle of lanthanide chelate complementation (LCC) in comparison with a method based on hydrolysis enhancement and quenching of intact probes. A real-time reverse transcription (RT) PCR assay for kallikrein-related peptidase 3 (KLK3, model analyte) was developed by using the LCC detection method. Both detection methods were tested with a standard series of purified PCR products, 20 prostatic tissues, 20 healthy and prostate cancer patient blood samples, and female blood samples spiked with LNCaP cells. The same limit of detection was obtained with both methods, and two cycles earlier detection with the LCC method was observed. KLK3 messenger RNA (mRNA) was detected in all tissue samples and in 1 of 20 blood samples identically with both methods. The background was 30 times lower, and the signal-to-background (S/B) ratio was 3 times higher, when compared with the reference method. Use of the new reporter method provided similar sensitivity and specificity as the reference method. The lower background, the improved S/B ratio, and the possibility of melting curve analysis and single nucleotide polymorphism (SNP) detection could be advantages for this new reporter probe.

  13. Study of the Discrepancies between Crystallographic Porosity and Guest Access into Cadmium-Imidazolate Frameworks and Tunable Luminescence Properties by Incorporation of Lanthanides.

    Science.gov (United States)

    Mondal, Suvendu Sekhar; Bhunia, Asamanjoy; Attallah, Ahmed G; Matthes, Philipp R; Kelling, Alexandra; Schilde, Uwe; Müller-Buschbaum, Klaus; Krause-Rehberg, Reinhard; Janiak, Christoph; Holdt, Hans-Jürgen

    2016-05-10

    An extended member of the isoreticular family of metal-imidazolate framework structures, IFP-6 (IFP=imidazolate framework Potsdam), based on cadmium metal and an in situ functionalized 2-methylimidazolate-4-amide-5-imidate linker is reported. A porous 3D framework with 1D hexagonal channels with accessible pore windows of 0.52 nm has been synthesized by using an ionic liquid (IL) linker precursor. IFP-6 shows significant gas uptake capacity only for CO2 and CH4 at elevated pressure, whereas it does not adsorb N2 , H2 , and CH4 under atmospheric conditions. IFP-6 is assumed to deteriorate at the outside of the material during the activation process. This closing of the metal-organic framework (MOF) pores is proven by positron annihilation lifetime spectroscopy (PALS), which revealed inherent crystal defects. PALS results support the conservation of the inner pores of IFP-6. IFP-6 has also been successfully loaded with luminescent trivalent lanthanide ions (Ln(III) =Tb, Eu, and Sm) in a bottom-up one-pot reaction through the in situ generation of the linker ligand and in situ incorporation of photoluminescent Ln ions into the constituting network. The results of photoluminescence investigations and powder XRD provide evidence that the Ln ions are not doped as connectivity centers into the frameworks, but are instead located within the pores of the MOFs. Under UV light irradiation, Tb@IFP-6 and Eu@IFP-6 (λexc =365 nm) exhibit observable emission changes to a greenish and reddish color, respectively, as a result of strong Ln 4 f emissions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Solvothermal synthesis and spectroscopic characterization of three lanthanide complexes with high luminescent properties [H2NMe2]3[Ln(III)(2,6-pyridinedicarboxylate)3] (Ln = Sm, Eu, Tb): In the presence of 4,4‧-Bipyridyl

    Science.gov (United States)

    Viveros-Andrade, Alan G.; Colorado-Peralta, Raúl; Flores-Alamo, Marcos; Castillo-Blum, Silvia E.; Durán-Hernández, Jesús; Rivera, José María

    2017-10-01

    Three lanthanide complexes, [H2NMe2]3[Ln(III)(2,6-pyridinedicarboxylate)3] (Ln = Sm, Eu, Tb) have been successfully synthesized using a solvothermal method in the presence of a base and they were prepared from inexpensive and readily available reactants. Infrared, ultraviolet-visible absorption spectroscopies, elemental analyses and thermogravimetric analysis were employed for the characterization. Crystals suitable for X-ray diffraction were isolated in good yields by a simple filtration, their crystal structures were analyzed; the samarium structure has orthorhombic symmetry with space group Pbcn, exhibiting three-dimensional supramolecular architecture through hydrogen bonding interactions. The metal center is coordinated to nine atoms corresponding to three pyridine-2,6-dicarboxylic acid molecules. These compounds are thermally stable up to 270 °C.

  15. NIR-luminescence from ternary lanthanide [Ho{sup III}, Pr{sup III} and Tm{sup III}] complexes with 1-(2-naphthyl)-4,4,4-trifluoro-1,3-butanedionate

    Energy Technology Data Exchange (ETDEWEB)

    Dang Song [State Key Laboratory of Rare Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Graduate School of the Chinese Academy of Sciences, Beijing (China); Yu Jiangbo [State Key Laboratory of Rare Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Wang Xiaofei [State Key Laboratory of Rare Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Graduate School of the Chinese Academy of Sciences, Beijing (China); Sun Lining [Research Center of Nano Science and Technology, Shanghai University, Shanghai 200444 (China); Deng Ruiping; Feng Jing [State Key Laboratory of Rare Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Fan Weiqiang [State Key Laboratory of Rare Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Graduate School of the Chinese Academy of Sciences, Beijing (China); Zhang Hongjie, E-mail: hongjie@ciac.jl.cn [State Key Laboratory of Rare Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China)

    2011-09-15

    The ligand 1-(2-naphthyl)-4,4,4-trifluoro-1,3-butanedionate (Htfnd) has been employed to synthesize six novel ternary-lanthanide complexes in which the synergic ligands were 1,10-phenanthroline-5,6-dione (dione) and 4,5-diazafluoren-9-one (dafone), respectively. Two series of complexes Ln(tfnd){sub 3}dione and Ln(tfnd){sub 3}dafone (Ln=Ho, Pr, Tm) were obtained. These complexes were characterized by elemental analysis, Fourier Transform Infrared spectra and diffused reflectance. After ligand-mediated excitation, Ln(tfnd){sub 3}dione and Ln(tfnd){sub 3}dafone all show the characteristic NIR luminescence of the corresponding Ln{sup 3+} ions (Ln=Ho, Pr, Tm). This can be attributed to the efficient energy transfer from ligands to central Ln{sup 3+} ions, via an antenna effect. The indirect energy transfer in the complexes has been investigated and the differences in the luminescence intensity between Ln(tfnd){sub 3}dione and Ln(tfnd){sub 3}dafone were discussed in detail. The excellent luminescent performances enable these NIR-luminescent complexes to have potential applications in optical amplification operating at 1300 or 1500 nm. - Highlights: > We study on Ln(tfnd){sub 3}dione and Ln(tfnd){sub 3}dafone complexes (Ln=Ho, Pr, Tm) based on different synergistic ligands. > Characteristic NIR luminescence of complexes has been obtained upon excitation of the ligand absorption bands. > Differences in the luminescence intensity of complexes were further discussed. > Dione ligand with lower triplet-state energy level than that of Htfnd discourage the luminescence of Ln(tfnd){sub 3}dione.

  16. Efficient visible and near-infrared photoluminescent attapulgite-based lanthanide one-dimensional nanomaterials assembled by ion-pairing interactions.

    Science.gov (United States)

    Xu, Jun; Zhang, Ye; Chen, Hao; Liu, Weisheng; Tang, Yu

    2014-06-07

    Attapulgite, a one-dimensional fibrillar nanomaterial present in nature, with its extreme stability, is a promising material to act as a new carrier of luminescent lanthanide complexes for further applications. Herein, a series of lanthanide complexes Na[Ln(TTA)4] have been attached to attapulgite (Atta) via ion-pairing interactions, generating the first example of attapulgite-based visible and near-infrared (NIR) luminescent lanthanide one-dimensional nanomaterials, where TTA is 2-thenoyltrifluoroacetonate and Ln is Eu, Sm, Nd, Er or Yb. The hybrid materials were characterized by CHN elemental analysis, inductively coupled plasma-atomic emission spectroscopy (ICP), powder X-ray diffraction (PXRD), thermogravimetry (TG), transmission electron microscopy (TEM), and UV-vis absorption spectra. In order to investigate the photophysical behaviours of these materials, the visible and NIR luminescent spectra and the energy transfer process have been systematically investigated. Moreover, efforts have been made to produce Eu- and Sm-based plastic attapulgite materials by utilizing poly(methyl methacrylate) (PMMA) matrices, and the dispersibility of the lanthanide-doped hybrids in PMMA provides them with a high mechanical strength. The lanthanide-doped attapulgite appears to be an interesting material for photophysical applications. The results of this work would have potential significance for the design and assembly of luminescent lanthanide materials for light-emitting diodes (LED), sunlight-conversion films, optical amplifiers, solar concentrators, and lasers.

  17. Lanthanide-containing polymer microspheres by multiple-stage dispersion polymerization for highly multiplexed bioassays.

    Science.gov (United States)

    Abdelrahman, Ahmed I; Dai, Sheng; Thickett, Stuart C; Ornatsky, Olga; Bandura, Dmitry; Baranov, Vladimir; Winnik, Mitchell A

    2009-10-28

    We describe the synthesis and characterization of metal-encoded polystyrene microspheres by multiple-stage dispersion polymerization with diameters on the order of 2 mum and a very narrow size distribution. Different lanthanides were loaded into these microspheres through the addition of a mixture of lanthanide salts (LnCl(3)) and excess acrylic acid (AA) or acetoacetylethyl methacrylate (AAEM) dissolved in ethanol to the reaction after about 10% conversion of styrene, that is, well after the particle nucleation stage was complete. Individual microspheres contain ca. 10(6)-10(8) chelated lanthanide ions, of either a single element or a mixture of elements. These microspheres were characterized one-by-one utilizing a novel mass cytometer with an inductively coupled plasma (ICP) ionization source and time-of-flight (TOF) mass spectrometry detection. Microspheres containing a range of different metals at different levels of concentration were synthesized to meet the requirements of binary encoding and enumeration encoding protocols. With four different metals at five levels of concentration, we could achieve a variability of 624, and the strategy we report should allow one to obtain much larger variability. To demonstrate the usefulness of element-encoded beads for highly multiplexed immunoassays, we carried out a proof-of-principle model bioassay involving conjugation of mouse IgG to the surface of La and Tm containing particles and its detection by an antimouse IgG bearing a metal-chelating polymer with Pr.

  18. High Stokes shift perylene dyes for luminescent solar concentrators.

    Science.gov (United States)

    Sanguineti, Alessandro; Sassi, Mauro; Turrisi, Riccardo; Ruffo, Riccardo; Vaccaro, Gianfranco; Meinardi, Francesco; Beverina, Luca

    2013-02-25

    Highly efficient plastic based single layer Luminescent Solar Concentrators (LSCs) require the design of luminophores having complete spectral separation between absorption and emission spectra (large Stokes shift). We describe the design, synthesis and characterization of a new perylene dye possessing Stokes shift as high as 300 meV, fluorescent quantum yield in the LSC slab of 70% and high chemical and photochemical stability.

  19. A multifunctional chemical sensor based on a three-dimensional lanthanide metal-organic framework

    Science.gov (United States)

    Du, Pei-Yao; Liao, Sheng-Yun; Gu, Wen; Liu, Xin

    2016-12-01

    A 3D lanthanide MOF with formula [Sm2(abtc)1.5(H2O)3(DMA)]·H2O·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.

  20. Preparation and photophysical properties of luminescent nanoparticles based on lanthanide doped fluorides (LaF{sub 3}:Ce{sup 3+}, Gd{sup 3+}, Eu{sup 3+}), obtained in the presence of different surfactants

    Energy Technology Data Exchange (ETDEWEB)

    Runowski, Marcin; Lis, Stefan, E-mail: blis@amu.edu.pl

    2014-06-01

    Highlights: • Synthesis of nanocrystalline lanthanide fluorides doped with Eu{sup 3+} ions. • Inorganic nanomaterials exhibiting bright red luminescence. • Luminescence enhancement by energy transfer (ET) from Ce{sup 3+} → Gd{sup 3+} to Eu{sup 3+} ions. • Decreased agglomeration and morphology control using organic modifiers/surfactants. • Absolute and relative quantum yield (QY) comparison. - Abstract: A series of nanomaterials composed of LaF{sub 3}:Ce{sup 3+} 10%, Gd{sup 3+} 30%, Eu{sup 3+} 1% was synthesized via a facile co-precipitation approach. The reaction between appropriate lanthanide (Ln{sup 3+}) and fluoride ions resulted in the formation of crystalline, Ln{sup 3+} doped fluorides and was performed in the presence of a series of organic modifiers, acting as surfactants and anti-agglomeration agents. Modifiers such as polyacrylic acid (PAA), ethylenediaminetetraacetic acid (EDTA), citric acid and oleylamine most significantly influenced the morphology and spectroscopic properties of the products. The product obtained in the presence of PAA was composed of the smallest nanoparticles (ca. 5–6 nm), with narrow size/shape distribution. All fluorides synthesized exhibited intensive, bright red luminescence under UV irradiation (λ{sub ex} ≈ 250 nm), because of the presence of Eu{sup 3+} ions in their structure. The efficient intensity of luminescence was a result of indirect excitation, via energy transfer (ET) phenomena occurring in the system (Ce{sup 3+} → Gd{sup 3+} → Eu{sup 3+}). The structure and morphology of the obtained nanomaterials were established by powder X-ray Diffraction (XRD) and Transmission Electron Microscopy (TEM) measurements. Optical properties of the obtained compounds were studied and discussed on the basis of excitation emission spectra and luminescence decay curves. On the basis of the performed measurements, luminescence quantum yield (absolute and relative) and radiative lifetimes were calculated and analyzed

  1. Thermally Stable White Emitting Eu(3+) Complex@Nanozeolite@Luminescent Glass Composite with High CRI for Organic-Resin-Free Warm White LEDs.

    Science.gov (United States)

    Zhang, Jinhui; Gong, Shuming; Yu, Jinbo; Li, Peng; Zhang, Xuejie; He, Yuwei; Zhou, Jianbang; Shi, Rui; Li, Huanrong; Peng, Aiyun; Wang, Jing

    2017-03-01

    Nowadays, it is still a great challenge for lanthanide complexes to be applied in solid state lighting, especially for high-power LEDs because they will suffer severe thermal-induced luminescence quenching and transmittance loss when LEDs are operated at high current. In this paper, we have not only obtained high efficient and thermally chemical stable red emitting hybrid material by introducing europium complex into nanozeolite (NZ) functionalized with the imidazolium-based stopper but also abated its thermal-induced transmittance loss and luminescence quenching behavior via coating it onto a heat-resistant luminescent glass (LG) with high thermal conductivity (1.07 W/mK). The results show that the intensity at 400 K for Eu(PPO)n-C4Si@NZ@LG remains 21.48% of the initial intensity at 300 K, which is virtually 153 and 13 times the intensity of Eu(PPO)3·2H2O and Eu(PPO)n-C4Si@NZ, respectively. Moreover, an organic-resin-free warm white LEDs device with a low CCT of 3994K, a high Ra of 90.2 and R9 of 57.9 was successfully fabricated simply by combining NUV-Chip-On-Board with a warm white emitting glass-film composite (i.e., yellowish-green emitting luminescent glass coated with red emitting hybrid film). Our method and results provide a feasible and promising way for lanthanide complexes to be used for general illumination in the future.

  2. Lanthanide Label Array Method for Identification and Adulteration of Honey and Cacao.

    Science.gov (United States)

    Härmä, Harri; Peltomaa, Riikka; Pihlasalo, Sari

    2015-07-07

    A generic, cost-effective, and simple method has been developed to fingerprint liquids to differentiate food brands and ingredients. The method is based on a label array using nonspecific long lifetime unstable luminescent lanthanide labels. The interaction between the liquid sample and the label is typically detrimental to the luminescence of the unstable chelate leading to a sample-dependent luminescence-intensity array. The label-array method is a unique approach as the array of unstable chelates is extremely inexpensive to produce and possesses high sensitivity due to spectral as well as unstable structural properties of the lanthanide label. The global method has been applied to distinguish commercial honey and cacao brands to demonstrate its feasibility as honey and cacao are among the most adulterated food products.

  3. 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)

  4. Secret lanthanides.

    Science.gov (United States)

    Sturza, C M

    2014-09-15

    Lanthanides are a group of 15 chemical elements which, together with their salts, have come to be used in the last decade as homoeopathic remedies. The effective introduction of lanthanides and their salts into the clinical use, as homoeopathic remedies was based on the idea of Jan Scholten, MD to relate their physicochemical properties shown in the periodic table of elements to their homoeopathic potential. The lanthanides and their salts were prepared as homoeopathic remedies by Pharmacist Robert Münz.

  5. Lanthanide complexes of azidophenacyl-DO3A as new synthons for click chemistry and the synthesis of heterometallic lanthanide arrays.

    Science.gov (United States)

    Tropiano, Manuel; Kenwright, Alan M; Faulkner, Stephen

    2015-04-07

    Lanthanide complexes of azidophenacyl DO3A are effective substrates for click reactions with ethyne derivatives, giving rise to aryl triazole appended lanthanide complexes, in which the aryl triazole acts as an effective sensitising chromophore for lanthanide luminescence. They also undergo click chemistry with propargylDO3A derivatives, giving rise to heterometallic complexes.

  6. Triheterometallic Lanthanide Complexes Prepared from Kinetically Inert Lanthanide Building Blocks

    DEFF Research Database (Denmark)

    Sørensen, Thomas Just; Tropiano, Manuel; Kenwright, Alan M.

    2017-01-01

    . The photophysical properties of these heterotrimetallic complexes were investigated and are discussed by comparison with simpler, but related, heterodimetallic compounds. It was found that an aminonaphthalene unit inhibits the sensitisation of terbium, and that the spatial arrangement of the chromophores......Three molecular structures, each containing three different lanthanide(III) centres, have been prepared by coupling three kinetically inert lanthanide(III) complexes in an Ugi reaction. These 2 kDa molecules were purified by dialysis and characterised by NMR and luminescence techniques...

  7. Construction of three lanthanide metal-organic frameworks: Synthesis, structure, magnetic properties and highly selective sensing of metal ions

    Science.gov (United States)

    Zhang, Xiu-Mei; Li, Peng; Gao, Wei; Liu, Feng; Liu, Jie-Ping

    2016-12-01

    Three lanthanide metal-organic frameworks (Ln-MOFs), [Ln(TZI)(H2O)4]·3H2O (Ln=Gd (1) and Tb (2) and Dy (3), H3TZI=5-(1H-tetrazol-5-yl)isophthalic acid), have been synthesized under hydrothermal conditions. Single crystal X-ray diffraction reveals that 1-3 are isostructural and display a 1D double chain based on dinuclear motifs with (μ-COO)2 double bridges. Magnetic studies indicate antiferromagnetic interactions in 1, ferromagnetic interactions in 2 and 3. Furthermore, compound 3 displays a slow relaxation behavior. Compound 2 exhibits intense characteristic green emission of Tb(III) ions in the solid state, which can be observed by the naked eye under UV light. Interestingly, 2 can selectively sense Pb2+ and Fe3+ ions through luminescence enhancement and quenching, respectively. The luminescence quenching mechanisms have been investigated in detail. The study on luminescence Ln-MOFs as a probe for sensing Pb2+ and Fe3+ ions is exceedingly rare example.

  8. Lanthanide single molecule magnets

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Jinkui; Zhang, Peng [Chinese Academy of Sciences, Changchun (China). Changchun Inst. of Applied Chemistry

    2015-10-01

    This book begins by providing basic information on single-molecule magnets (SMMs), covering the magnetism of lanthanide, the characterization and relaxation dynamics of SMMs and advanced means of studying lanthanide SMMs. It then systematically introduces lanthanide SMMs ranging from mononuclear and dinuclear to polynuclear complexes, classifying them and highlighting those SMMs with high barrier and blocking temperatures - an approach that provides some very valuable indicators for the structural features needed to optimize the contribution of an Ising type spin to a molecular magnet. The final chapter presents some of the newest developments in the lanthanide SMM field, such as the design of multifunctional and stimuli-responsive magnetic materials as well as the anchoring and organization of the SMMs on surfaces. In addition, the crystal structure and magnetic data are clearly presented with a wealth of illustrations in each chapter, helping newcomers and experts alike to better grasp ongoing trends and explore new directions.

  9. Lanthanide single molecule magnets

    CERN Document Server

    Tang, Jinkui

    2015-01-01

    This book begins by providing basic information on single-molecule magnets (SMMs), covering the magnetism of lanthanide, the characterization and relaxation dynamics of SMMs, and advanced means of studying lanthanide SMMs. It then systematically introduces lanthanide SMMs ranging from mononuclear and dinuclear to polynuclear complexes, classifying them and highlighting those SMMs with high barrier and blocking temperatures – an approach that provides some very valuable indicators for the structural features needed to optimize the contribution of an Ising type spin to a molecular magnet. The final chapter presents some of the newest developments in the lanthanide SMM field, such as the design of multifunctional and stimuli-responsive magnetic materials as well as the anchoring and organization of the SMMs on surfaces. In addition, the crystal structure and magnetic data are clearly presented with a wealth of illustrations in each chapter, helping newcomers and experts alike to better grasp ongoing trends and...

  10. Lanthanide-doped upconversion nano-bioprobes: electronic structures, optical properties, and biodetection.

    Science.gov (United States)

    Zheng, Wei; Huang, Ping; Tu, Datao; Ma, En; Zhu, Haomiao; Chen, Xueyuan

    2015-03-21

    Lanthanide-doped upconversion nanoparticles (UCNPs) have attracted considerable interest due to their superior physicochemical features, such as large anti-Stokes shifts, low autofluorescence background, low toxicity and high penetration depth, which make them extremely suitable for use as alternatives to conventional downshifting luminescence bioprobes like organic dyes and quantum dots for various biological applications. A fundamental understanding of the photophysics of lanthanide-doped UCNPs is of vital importance for discovering novel optical properties and exploring their new applications. In this review, we focus on the most recent advances in the development of lanthanide-doped UCNPs as potential luminescent nano-bioprobes by means of our customized lanthanide photophysics measurement platforms specially designed for upconversion luminescence, which covers from their fundamental photophysics to bioapplications, including electronic structures (energy levels and local site symmetry of emitters), excited-state dynamics, optical property designing, and their promising applications for in vitro biodetection of tumor markers. Some future prospects and efforts towards this rapidly growing field are also envisioned.

  11. High-Efficient Excitation-Independent Blue Luminescent Carbon Dots

    Science.gov (United States)

    Liu, Hongzhen; Zhao, Xin; Wang, Fei; Wang, Yunpeng; Guo, Liang; Mei, Jingjing; Tian, Cancan; Yang, Xiaotian; Zhao, Dongxu

    2017-06-01

    Blue luminescent carbon dots (CDs) were synthesized by the hydrothermal method. Blue-shifts of the maximum emission wavelength from 480 to 443 nm were observed when the concentration of CD solution decreased. The photoluminescence (PL) spectra of CDs at low concentration showed an excitation-independent behaviour, which is very different from the previous reports. Two different emitting mechanisms might work: the intrinsic luminescence from sp2-carbon networks can be responsible for the shorter wavelength part of emission (excitation-independent) at low concentration and the high polarity of nanosized clusters led to the excitation-dependent behaviour of the longer wavelength part at high concentration of CD solution. The photophysical property and concentration-dependent behaviour of the CDs offered new insights into CDs from the viewpoints of both experiments and mechanisms, which will promote diverse potential applications of CDs in the near future.

  12. Structural investigation and luminescence of nanocrystalline lanthanide doped NaNbO{sub 3} and Na{sub 0.5}K{sub 0.5}NbO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Pin, Sonia [Paul Scherrer Institute, General Energy Research (ENE), Laboratory for Bioenergy and Catalysis, CH-5232 Villigen PSI (Switzerland); Piccinelli, Fabio [Dipartimento di Biotecnologie, Universita di Verona and INSTM, UdR Verona, Strada Le Grazie 15, I-37134 Verona (Italy); Upendra Kumar, Kagola [Grupo de Fotonica e Fluidos Complexos, Instituto de Fisica, Universidade Federal de Alagoas (UFAL), Maceio-AL (Brazil); Enzo, Stefano [Dipartimento di Chimica, Universita di Sassari, 07100 Sassari (Italy); Ghigna, Paolo [Dipartimento di Chimica, Universita di Pavia, V.le Taramelli 16, I-27100 Pavia (Italy); Cannas, Carla; Musinu, Anna [Dipartimento di Scienze Chimiche, Universita di Cagliari, Cittadella Universitaria Monserrato, I-09042 Cagliari (Italy); Mariotto, Gino [Dipartimento di Informatica, Universita di Verona, Strada Le Grazie 15, I-37134 Verona (Italy); Bettinelli, Marco [Dipartimento di Biotecnologie, Universita di Verona and INSTM, UdR Verona, Strada Le Grazie 15, I-37134 Verona (Italy); Speghini, Adolfo, E-mail: adolfo.speghini@univr.it [Dipartimento di Biotecnologie, Universita di Verona and INSTM, UdR Verona, Strada Le Grazie 15, I-37134 Verona (Italy)

    2012-12-15

    Nd{sup 3+} and Eu{sup 3+} doped NaNbO{sub 3} and Na{sub 0.5}K{sub 0.5}NbO{sub 3} nanostructured multiferroics (nanoparticles or nanorods) were prepared by a sol-gel route. X-Ray powder diffraction results evidence that the sodium and mixed sodium-potassium niobates show orthorhombic (Pmc2{sub 1} space group), and monoclinic structure (Pm space group), respectively, confirmed by the Raman spectra. The local structure around the trivalent lanthanides was investigated with Extended X-ray Absorption Fine Structure spectroscopy at the Ln-K edge and luminescence spectroscopy. The Ln{sup 3+} ions enter the structure by substituting the alkali metals, with a 12-fold oxygen coordination, and inducing a large amount of static disorder. The visible emission bands of the Eu{sup 3+} ions indicate that multiple sites exist for the lanthanide ions, in agreement with the EXAFS results showing the largest amount of static disorder in these samples. A possible indication of clustering of oxygen vacancies around the Ln{sub Na} Double-Prime defect is obtained by VBS calculations. - Graphical Abstract: Ln{sup 3+} doped NaNbO{sub 3} and Na{sub 0.5}K{sub 0.5}NbO{sub 3} nanoparticles or nanorods can be prepared by a simple sol-gel procedure. The synergy of X-ray diffraction, EXAFS and luminescence spectroscopy gives important information on the Ln{sup 3+} local environment. Highlights: Black-Right-Pointing-Pointer Nd{sup 3+} and Eu{sup 3+} doped NaNbO{sub 3} and Na{sub 0.5}K{sub 0.5}NbO{sub 3} nanoparticles or nanorods are prepared by sol-gel. Black-Right-Pointing-Pointer EXAFS indicates that the Ln{sup 3+} ions substitutes the Na{sup +} and K{sup +} ions, inducing a large amount of static disorder. Black-Right-Pointing-Pointer The visible emission bands of the Eu{sup 3+} ions confirm that multiple sites exist for the lanthanide ions.

  13. Lanthanide-doped nanoparticles as the active optical medium in polymer-based devices

    NARCIS (Netherlands)

    Stouwdam, Jan Willem

    2004-01-01

    The luminescence of lanthanide ions in organic environment is greatly reduced compared to inorganic materials. This thesis describes the doping of the lanthanide ions in the core of inorganic nanoparticles that are soluble in organic solvents as a way to shield the lanthanide ions from the organic e

  14. 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.

  15. Development of a novel europium complex-based luminescent probe for time-gated luminescence imaging of hypochlorous acid in living samples

    Science.gov (United States)

    Liu, Xiangli; Guo, Lianying; Song, Bo; Tang, Zhixin; Yuan, Jingli

    2017-03-01

    Luminescent lanthanide complexes are key reagents used in the time-gated luminescence bioassay technique, but functional lanthanide complexes that can act as luminescent probes for specifically responding to analytes are very limited. In this work, we designed and synthesized a novel Eu3+ complex-based luminescence probe for hypochlorous acid (HOCl), NPPTTA-Eu3+, by using terpyridine polyacid-Eu3+, dinitrophenyl, and hydrazine as luminophore, quencher and HOCl-recognizer moieties, respectively. In the absence of HOCl, the probe is non-luminescent due to the strong luminescence quenching of the dinitrophenyl group in the complex. However, upon reaction with HOCl, the dinitrophenyl moiety is rapidly cleaved from the probe, which affords a strongly luminescent Eu3+ complex CPTTA-Eu3+, accompanied by a ∼900-fold luminescence enhancement with a long luminescence lifetime of 1.41 ms. This unique luminescence response of NPPTTA-Eu3+ to HOCl allowed NPPTTA-Eu3+ to be conveniently used as a probe for highly selective and sensitive detection of HOCl under the time-gated luminescence mode. In addition, by loading NPPTTA-Eu3+ into RAW 264.7 macrophage cells and Daphnia magna, the generation of endogenous HOCl in RAW 264.7 cells and the uptake of exogenous HOCl by Daphnia magna were successfully imaged on a true-color time-gated luminescence microscope. The results demonstrated the practical applicability of NPPTTA-Eu3+ as an efficient probe for time-gated luminescence imaging of HOCl in living cells and organisms.

  16. Synthesis and luminescent properties of novel lanthanide(III) beta-diketone complexes with nitrogen p,p'-disubstituted aromatic ligands.

    Science.gov (United States)

    Bellusci, Anna; Barberio, Giovanna; Crispini, Alessandra; Ghedini, Mauro; La Deda, Massimo; Pucci, Daniela

    2005-03-21

    Tris-beta-diketonate lanthanide(III) complexes (Ln = Eu, Er, Yb, Tb), of general formula [Ln(acac)3 L(m)], with chelating ligands such as 4,7-disubstituted-1,10-phenanthrolines and 4,4'-disubstituted-2,2'-bipyridines, have been synthesized and fully characterized. The inductive effects of the para-substituents on the aromatic N-donor ligands have been investigated both in the solid and in the solution states. Single-crystal X-ray structures have been determined for the diethyl 1,10-phenanthroline-4,7-dicarboxylate europium and 4,4'-dimethoxy-2,2'-bipyridine erbium derivatives, revealing a distorted square antiprismatic geometry around the lanthanide atom in both cases. The influence exerted by the p,p'-substituents with respect to the nitrogen coordinating atoms on the Ln-N bond distances is discussed comparing the geometrical parameters with those found for the crystal structures containing the fragments [Ln(III)(phen)] and [Ln(III)(bipy)] obtained from the Cambridge Structural Database. The influence exerted by the electron-attracting groups on the coordination ability of the ligands, that in some cases becomes lack of coordination of the lanthanide ions, has been also detected in solution where the loss of the ligand has been followed by UV-vis spectroscopy. Moreover, the use of relatively long alkoxy chains as substituents on the 1,10-phenanthroline ligand led to the formation of a promesogenic lanthanide complex, whose thermal behavior is encouraging for the synthesis of new lanthanide liquid-crystalline species.

  17. Measurement of luminescence decays: High performance at low cost

    Science.gov (United States)

    Sulkes, Mark; Sulkes, Zoe

    2011-11-01

    The availability of inexpensive ultra bright LEDs spanning the visible and near-ultraviolet combined with the availability of inexpensive electronics equipment makes it possible to construct a high performance luminescence lifetime apparatus (˜5 ns instrumental response or better) at low cost. A central need for time domain measurement systems is the ability to obtain short (˜1 ns or less) excitation light pulses from the LEDs. It is possible to build the necessary LED driver using a simple avalanche transistor circuit. We describe first a circuit to test for small signal NPN transistors that can avalanche. We then describe a final optimized avalanche mode circuit that we developed on a prototyping board by measuring driven light pulse duration as a function of the circuit on the board and passive component values. We demonstrate that the combination of the LED pulser and a 1P28 photomultiplier tube used in decay waveform acquisition has a time response that allows for detection and lifetime determination of luminescence decays down to ˜5 ns. The time response and data quality afforded with the same components in time-correlated single photon counting are even better. For time-correlated single photon counting an even simpler NAND-gate based LED driver circuit is also applicable. We also demonstrate the possible utility of a simple frequency domain method for luminescence lifetime determinations.

  18. High pressure luminescence studies of europium doped GaN

    Institute of Scientific and Technical Information of China (English)

    K.Wisniewski; W.Jadwisie(n)czak; T.Thomas; M.Spencer

    2009-01-01

    We reported on the high pressure luminescence spectra of polycrystalline Eu-doped GaN material synthesized in the reaction tween alloys of gallium,bismuth and europium in ammonia atmosphere.The integrated luminescence intensity of the dominant Eu3+ ion transition (5D0→7F2) at 622 nm increased approximately one order of magnitude whereas its spectral position and line width did not change significantly between ambient and 6.8 GPa pressure,respectively.Moreover,material was characterized with photo- and cathodo-luminescence,and photoluminescence excitation spectra at different temperatures.It was found that the Eu3+ ions occupying substitutional Ga site created different centers which could be effectively excited with above band gap excitation and from excitons resonantly photoexcited at the I2 bound exciton energy.Furthermore,the less efficient Eu3+ ions excitation path existed through intrinsic impurities and defects generating shallow energy levels in the forbidden gap.It was proposed that reduction of the thermal quenching and consequent enhancement of Eu3+ ion emission intensity resulted from stronger localization of bound exciton on RESI trap induced by applied pressure.

  19. Visible luminescence of lanthanide ions in Ca3Sc2Si3O12 and Ca3Y2Si3O12

    Institute of Scientific and Technical Information of China (English)

    Fabio Piccinelli; Adolfo Speghini; Gino Mariotto; Laura Bovo; Marco Bettinelli

    2009-01-01

    The crystalline materials Ca3Sc2Si3O12 and Ca3Y2Si3O12 were characterized by different crystal structures,as the former is a cubic garnet,while the latter is an orthorhombic compound.We investigated the optical spectroscopy of these materials doped with several trivalent lanthanide ions and compared the results for the two hosts.Polycrystalline samples were prepared by solid state reaction,both undoped and doped with the trivalent lanthanide ions Eu3+,Tb3+ and Sm3+.Emission,excitation and Raman spectra of these materials were measured at temperatures ranging from 300 to 10 K.The optical spectra were assigned and discussed,and the effects of the crystal structure of the host on the spectroscopic behaviour were addressed.The technological potential of these compounds in the field of optical materials and devices was discussed.

  20. Optical Properties of Lanthanides in Condensed Phase, Theory and Applications

    Directory of Open Access Journals (Sweden)

    Renata Reisfeld

    2015-04-01

    Full Text Available The basic theories of electronic levels and transition probabilities of lanthanides are summarized. Their interpretation allows practical preparation of new materials having application in lighting, solar energy utilization, optoelectronics, biological sensors, active waveguides and highly sensitive bioassays for in vitro detection in medical applications. The ways by which the weak fluorescence arising from electronic transition within the four f-configurations can be intensified will be discussed. This includes the intermixing of the four f-states with ligands of the host matrix, excitation to higher d-electronic states. Additional intensification of luminescence by plasmonic interaction with gold, silver and copper nanoparticles will be discussed. A short history of the time development of the research and the names of the scientists who made the major contribution of our understanding of lanthanides spectroscopy are presented.

  1. Complexing mechanism of the lanthanide cations Eu3+, Gd3+, and Tb3+ with 1,4,7,10-tetrakis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (dota)-characterization of three successive complexing phases: study of the thermodynamic and structural properties of the complexes by potentiometry, luminescence spectroscopy, and EXAFS.

    Science.gov (United States)

    Moreau, Juliette; Guillon, Emmanuel; Pierrard, Jean-Claude; Rimbault, Jean; Port, Marc; Aplincourt, Michel

    2004-10-11

    Complexation of the lanthanides Eu3+, Gd3+, and Tb3+ with 1,4,7,10-tetrakis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (dota) has been studied in solution by using potentiometry, luminescence spectrometry, and EXAFS. Three series of successive complexes were characterized by at least two of these methods: the immediate [LnHn(dota)](n-1)+** and intermediate [LnHn(dota)](n-1)+* complexes with 0 potentiometry. From the results, a complexation mechanism involving three steps has been proposed. In the [LnHn(dota)](n-1)+** complexes that are instantaneously formed, the lanthanide is bound to four oxygen atoms of the carboxylate groups and to five water molecules. These species evolve rapidly: the lanthanide moves into the macrocycle cavity, two new bonds are formed with two nitrogen atoms diametrically opposed in the tetraaza cycle and only three water molecules remain bound to the lanthanide in the [LnHn(dota)](n-1)+* (0 lanthanide is bound to four nitrogen atoms, four carboxylate oxygen atoms, and one water molecule.

  2. Nanocrystalline lanthanide-doped Lu3Ga5O12 garnets: interesting materials for light-emitting devices.

    Science.gov (United States)

    Venkatramu, V; Giarola, M; Mariotto, G; Enzo, S; Polizzi, S; Jayasankar, C K; Piccinelli, F; Bettinelli, M; Speghini, A

    2010-04-30

    Nanocrystalline Lu(3)Ga(5)O(12), with average particle sizes of 40 nm, doped with a wide variety of luminescent trivalent lanthanide ions have been prepared using a sol-gel technique. The structural and morphological properties of the powders have been investigated by x-ray powder diffraction, high resolution transmission electron microscopy and Raman spectroscopy. Structural data have been refined and are presented for Pr(3+), Eu(3+), Gd(3+), Ho(3+), Er(3+) and Tm(3+) dopants, while room temperature excited luminescence spectra and emission decay curves of Eu(3+)-, Tm(3+)- and Ho(3+)-doped Lu(3)Ga(5)O(12) nanocrystals have been measured and are discussed. The Eu(3+) emission spectrum shows typical bands due to 5D(0)-->7F(J) (J = 0, 1, 2, 3, 4) transitions and the broadening of these emission bands with the non-exponential behaviour of the decay curves indicates the presence of structural disorder around the lanthanide ions. Lanthanide-doped nanocrystalline Lu(3)Ga(5)O(12) materials show better luminescence intensities compared to Y(2)O(3), Gd(3)Ga(5)O(12) and Y(3)Al(5)O(12) nanocrystalline hosts. Moreover, the upconversion emission intensity in the blue-green region for the Tm(3+)- and Ho(3+)-doped samples shows a significant increase upon 647.5 nm excitation with respect to other common oxide hosts doped with the same lanthanide ions.

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

    Science.gov (United States)

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

    2014-05-07

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

  4. Luminescent Lanthanide Cyclen-Based Enzymatic Assay Capable of Diagnosing the Onset of Catheter-Associated Urinary Tract Infections Both in Solution and within Polymeric Hydrogels.

    Science.gov (United States)

    Surender, Esther M; Bradberry, Samuel J; Bright, Sandra A; McCoy, Colin P; Williams, D Clive; Gunnlaugsson, Thorfinnur

    2017-01-11

    Herein we present a supramolecular (delayed luminescent) Eu(III)-based pH-responsive probe/sensor with the ability to detect the urease-mediated hydrolysis of urea in aqueous solution. A series of photophysical titrations show this Eu(III) chelate behaves as an "on-off" luminescent switching probe, with its luminescence being quenched upon urea being enzymatically converted into ammonia and carbon dioxide. Calculation of the rate constant (k) and activation energy (Ea) for this hydrolysis reaction are detailed; the results demonstrate a direct observation of enzymatic activity in solution by the sensor. The potential application of this probe in detecting the onset of catheter-associated urinary tract infections (CAUTIs) is also demonstrated by incorporating 1.Eu into water-permeable hydrogels that can be utilized as an alternative coating for catheters.

  5. Borate glasses with high lanthanide oxids solubility for the cold crucible induction melter(CCIM) applications

    Energy Technology Data Exchange (ETDEWEB)

    Kim, M.; Heo, J. [POSTECH, Pohang (Korea, Republic of)

    2016-05-15

    Pyro-processing is being investigated to reuse radioactive uranium and trans-uranium elements from the spent fuels. Previous researches regarding waste forms for rare-earth oxides waste generated from pyro-processing reported low elemental release (< 10{sup 4} g/m2) of RE ions at the product consistency test (PCT). Current work reports the continuing effort on the enhancement of the waste loading and process-ability using cold crucible induction melter(CCIM). Borate glasses are well-known for their low melting temperatures with high rare-earth oxide solubility compared to silicate glasses. Borate glasses were investigated as potential waste forms with high waste loading for immobilization of lanthanide ion wastes produced by pyro-processing. Process-ability of them was investigated by characterizing several important processing parameters for cold crucible induction melter (CCIM) process. Borate glasses containing 0 - 20 mol% Nd{sub 2}O{sub 3} were fabricated by melting the starting powders at 1300 .deg. C for 30 min with maximum loading of 56.8 wt % (22 mol %). The released concentration of Nd were < 0.1 ppm. Crystallization did not appear at the temperature below 800 .deg. C. Viscosity and electric conductivity of these glasses meet requirements to apply to CCIM.

  6. H4octapa: highly stable complexation of lanthanide(III) ions and copper(II).

    Science.gov (United States)

    Kálmán, Ferenc Krisztián; Végh, Andrea; Regueiro-Figueroa, Martín; Tóth, Éva; Platas-Iglesias, Carlos; Tircsó, Gyula

    2015-03-02

    The acyclic ligand octapa(4-) (H4octapa = 6,6'-((ethane-1,2-diylbis((carboxymethyl)azanediyl))bis(methylene))dipicolinic acid) forms stable complexes with the Ln(3+) ions in aqueous solution. The stability constants determined for the complexes with La(3+), Gd(3+), and Lu(3+) using relaxometric methods are log KLaL = 20.13(7), log KGdL = 20.23(4), and log KLuL = 20.49(5) (I = 0.15 M NaCl). High stability constants were also determined for the complexes formed with divalent metal ions such as Zn(2+) and Cu(2+) (log KZnL = 18.91(3) and log KCuL = 22.08(2)). UV-visible and NMR spectroscopic studies and density functional theory (DFT) calculations point to hexadentate binding of the ligand to Zn(2+) and Cu(2+), the donor atoms of the acetate groups of the ligand remaining uncoordinated. The complexes formed with the Ln(3+) ions are nine-coordinated thanks to the octadentate binding of the ligand and the presence of a coordinated water molecule. The stability constants of the complexes formed with the Ln(3+) ions do not change significantly across the lanthanide series. A DFT investigation shows that this is the result of a subtle balance between the increased binding energies across the 4f period, which contribute to an increasing complex stability, and the parallel increase of the absolute values of the hydration free energies of the Ln(3+) ions. In the case of the [Ln(octapa)(H2O)](-) complexes the interaction between the amine nitrogen atoms of the ligand and the Ln(3+) ions is weakened along the lanthanide series, and therefore the increased electrostatic interaction does not overcome the increasing hydration energies. A detailed kinetic study of the dissociation of the [Gd(octapa)(H2O)](-) complex in the presence of Cu(2+) shows that the metal-assisted pathway is the main responsible for complex dissociation at pH 7.4 and physiological [Cu(2+)] concentration (1 μM).

  7. Zirconia-based luminescent organic-inorganic hybrid materials with ternary europium (III) complexes bonded

    Science.gov (United States)

    Yang, Jing; Li, Zhiqiang; Xu, Yang; Wang, Yige

    2016-05-01

    In this work, a novel red-emitting organic-inorganic hybrid material with europium (III) lanthanide β-diketonate complexes linked to a zirconia was reported, which was realized by adduct formation with zirconia-tethered terpyridine moieties. Luminescence enhancement of the hybrid material has been observed compared with pure Eu(tta)3·2H2O. Transparent and strongly luminescent thin films based on PMMA were also prepared at room temperature, which are highly luminescent under UV-light irradiation and possess a promising prospect in the area of optics.

  8. Enhancement of anion binding in lanthanide optical sensors.

    Science.gov (United States)

    Cable, Morgan L; Kirby, James P; Gray, Harry B; Ponce, Adrian

    2013-11-19

    In the design of molecular sensors, researchers exploit binding interactions that are usually defined in terms of topology and charge complementarity. The formation of complementary arrays of highly cooperative, noncovalent bonding networks facilitates protein-ligand binding, leading to motifs such as the "lock-and-key". Synthetic molecular sensors often employ metal complexes as key design elements as a way to construct a binding site with the desired shape and charge to achieve target selectivity. In transition metal complexes, coordination number, structure and ligand dynamics are governed primarily by a combination of inner-sphere covalent and outer-sphere noncovalent interactions. These interactions provide a rich variable space that researchers can use to tune structure, stability, and dynamics. In contrast, lanthanide(III)-ligand complex formation and ligand-exchange dynamics are dominated by reversible electrostatic and steric interactions, because the unfilled f shell is shielded by the larger, filled d shell. Luminescent lanthanides such as terbium, europium, dysprosium, and samarium display many photophysical properties that make them excellent candidates for molecular sensor applications. Complexes of lanthanide ions act as receptors that exhibit a detectable change in metal-based luminescence upon binding of an anion. In our work on sensors for detection of dipicolinate, the unique biomarker of bacterial spores, we discovered that the incorporation of an ancillary ligand (AL) can enhance binding constants of target anions to lanthanide ions by as much as two orders of magnitude. In this Account, we show that selected ALs in lanthanide/anion systems greatly improve sensor performance for medical, planetary science, and biodefense applications. We suggest that the observed anion binding enhancement could result from an AL-induced increase in positive charge at the lanthanide ion binding site. This effect depends on lanthanide polarizability, which can be

  9. Controlled synthesis, asymmetrical transport behavior and luminescence properties of lanthanide doped ZnO mushroom-like 3D hierarchical structures.

    Science.gov (United States)

    Yue, Dan; Lu, Wei; Jin, Lin; Li, Chunyang; Luo, Wen; Wang, Mengnan; Wang, Zhenling; Hao, Jianhua

    2014-11-21

    Lanthanide doped ZnO mushroom-like 3D hierarchical structures have been fabricated by polyol-mediated method and characterized by various microstructural and optical techniques. The results indicate that the as-prepared ZnO:Ln(3+) (Ln = Tb, Eu) samples have a hexagonal phase structure and possess a mushroom-like 3D hierarchical morphology. The length of the whole mushroom from stipe bottom to pileus top is about 1.0 μm, and the diameters of pileus and stipe are about 0.8 μm and 0.4 μm, respectively. It is found that the flow of N2 is the key parameter for the formation of the novel ZnO structure and the addition of (NH4)2HPO4 has a prominent effect on the phase structure and the growth of mushroom-like morphology. The potential mechanism of forming this morphology is proposed. The pileus of the formed mushroom is assembled by several radial ZnO:Ln(3+) nanorods, whereas the stipe is composed of over layered ZnO:Ln(3+) nanosheets. Moreover, asymmetrical I-V characteristic curves of ZnO:Ln(3+) mushrooms indicate that the texture composition of the 3D hierarchical morphology might lead to the asymmetrical transport behavior of electrical conductivity. Lanthanide doped ZnO samples can exhibit red or green emission under the excitation of UV light.

  10. Syntheses, crystal structures, and luminescence of two lanthanide coordination polymers based on 5-(3‧,4‧-bis(tetrazol-5″-yl)phenoxy)isophthalic acid and 1,10-phenanthroline

    Science.gov (United States)

    Chen, Xiaoli; Li, Congcong; Ai, Fengfeng; Qu, Xu; Liu, Kang

    2017-04-01

    Two new lanthanide coordination polymers, [Ln(btpa)(phen)2(OH)]n·nH2O (Ln= Tb 1, Pr 2) (H2btpa=5-(3‧,4‧-bis(tetrazol-5″-yl)phenoxy)isophthalic acid, phen=1,10-phenanthroline), have been successfully synthesized and structurally characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction, TGA and powder X-ray diffraction analyses. Coordination polymers 1-2 are isomorphism structures, showing a 1D chain bearing hooks structure. LnⅢ ion in 1-2 adopt nine-coordinated mode to construct a tricapped trigonal prism configuration. The adjacent chains form a 2D supramolecular network via π … π stacking interactions between the pyridine rings of phen ligands. Then the neighbouring 2D supramolecular networks recognizing each other form a 3D supramolecular structure through π … π interaction between benzene rings of (btpa)2- ligands. The luminescence experiments show that TbIII complex exhibits typical metal-centered emissions in the visible region in the solid state.

  11. A Highly Efficient and Environmentally Friendly CMC-Supported Lanthanide Catalyst for One-pot Synthesis of Substituted Imidazoles

    Institute of Scientific and Technical Information of China (English)

    WANG Limin; YAO Yinfang; WANG Yonghong; ZOU Gang

    2009-01-01

    A CMC-supported lanthanide catalyst was prepared from CMC and isopropoxy lanthanide. This solid Lewis acid catalyst was used in synthesis of substituted imidazoles under mild conditions, showing catalytic activity com-parable to the expensive lanthanide Lewis acid Ln(Otf)3. Furthermore, the catalyst could be readily recycled and reused for five times without any appreciable loss in catalytic activity.

  12. Luminescence characteristic of RE (RE = Pr, Sm, Eu, Tb, Dy) and energy levels of lanthanide ions in Gd5Si3O12N

    Science.gov (United States)

    Zhang, Zhi-Jun; Yang, Woochul

    2017-10-01

    Polycrystalline Gd5Si3O12N: RE (RE = Pr, Sm, Eu, Tb and Dy) phosphors have been synthesized via a solid-state reaction method at high temperature, and their photoluminescence properties were studied. The absorption peak at about 230 nm is attributed to the host absorption. For the Pr3+-doped sample, the typical excitation lines located at 273 nm originating from the 8S7/2 → 6IJ (J = 5/2, 7/2) transitions of the Gd3+ ions were observed in the excitation spectra. Upon excitation at 227 nm UV light, the 4f15d → 4f2 emission band (350-450 nm) and typical 4f2 → 4f2 emission lines (450-700 nm) assigned to Pr3+ were observed. The Sm3+-doped sample exhibits a bright red emission owing to the 4G5/2 → 6HJ (J = 5/2, 7/2 and 9/2) transitions. However, the charge transfer band of Sm3+ was not observed in the excitation spectrum. There is a broad band from 200 to 350 nm originating from the charge transfer transition (CT) of the Eu3+ (O2-/N3- → Eu3+) in the excitation spectra, and the strongest peak in the emission spectra located at 615 nm is due to the electric-dipole 5D0 → 7F2 transition of Eu3+. For the Tb3+-doped sample, it shows 5D3 →7FJ (J = 5, 4, 3, 2) blue line emissions and 5D4 → 7FJ (J = 6, 5, 4, 3) green line emissions under the excitation of Tb3+. The Dy3+-activated sample upon excitation at 349 and 386 nm UV light shows blue-green and orange-red emission lines originating from 4F9/2 → 6HJ (J = 15/2, 13/2) transitions. In addition, the energy transfer from the host lattice to the luminescence activators (i.e. Pr3+, Sm3+, Eu3+, Tb3+, Dy3+) has been confirmed. In addition, the energy level diagram including the 4f and 5d energy levels of all Ln2+ and Ln3+ ions relative to the valence and conduction band of Gd5Si3O12N were constructed and discussed.

  13. A Eu/Tb-mixed MOF for luminescent high-temperature sensing

    Science.gov (United States)

    Wang, Huizhen; Zhao, Dian; Cui, Yuangjing; Yang, Yu; Qian, Guodong

    2017-02-01

    Temperature measurements and thermal mapping using luminescent MOF operating in the high-temperature range are of great interest in the micro-electronic diagnosis. In this paper, we report a thermostable Eu/Tb-mixed MOF Eu0.37Tb0.63-BTC-a exhibiting strong luminescence at elevated temperature, which can serve as a ratiometric luminescent thermometer for high-temperature range. The high-temperature operating range (313-473 K), high relative sensitivity and accurate temperature resolution, make such a Eu/Tb-mixed MOF useful for micro-electronic diagnosis.

  14. Isotopic fingerprints of Pt-containing luminescence centers in highly enriched Si-28

    CERN Document Server

    Steger, M; Godisov, O N; Alves, E; Kaliteevskii, A K; Saeedi, K; Abrosimov, N V; Churbanov, M F; Gusev, A V; Johnston, K; Thewalt, M L W; Sekiguchi, T; Yang, A; Riemann, H; Henry, M O; Pohl, H -J; Wahl, U

    2010-01-01

    Recently we have shown that the reduction in the photoluminescence linewidth of many deep luminescence centers in highly enriched Si-28 results in well-resolved isotopic fingerprints. This allows for a better characterization of a defect center, as not only the involvement of a specific element but also the number of atoms of that element within the complex can be determined. Surprisingly, we have found that many well-known luminescence centers have a different composition than originally supposed. In addition, we have found a large number of four- and five-atom luminescence centers involving the elements Cu, Au, and Li. Here we introduce series of four- and five-atom deep luminescence centers involving a single Pt atom together with Cu and Li, similar to what has been seen previously for Au-containing luminescence centers.

  15. Lanthanide-based imaging of protein-protein interactions in live cells.

    Science.gov (United States)

    Rajendran, Megha; Yapici, Engin; Miller, Lawrence W

    2014-02-17

    In order to deduce the molecular mechanisms of biological function, it is necessary to monitor changes in the subcellular location, activation, and interaction of proteins within living cells in real time. Förster resonance energy-transfer (FRET)-based biosensors that incorporate genetically encoded, fluorescent proteins permit high spatial resolution imaging of protein-protein interactions or protein conformational dynamics. However, a nonspecific fluorescence background often obscures small FRET signal changes, and intensity-based biosensor measurements require careful interpretation and several control experiments. These problems can be overcome by using lanthanide [Tb(III) or Eu(III)] complexes as donors and green fluorescent protein (GFP) or other conventional fluorophores as acceptors. Essential features of this approach are the long-lifetime (approximately milliseconds) luminescence of Tb(III) complexes and time-gated luminescence microscopy. This allows pulsed excitation, followed by a brief delay, which eliminates nonspecific fluorescence before the detection of Tb(III)-to-GFP emission. The challenges of intracellular delivery, selective protein labeling, and time-gated imaging of lanthanide luminescence are presented, and recent efforts to investigate the cellular uptake of lanthanide probes are reviewed. Data are presented showing that conjugation to arginine-rich, cell-penetrating peptides (CPPs) can be used as a general strategy for the cellular delivery of membrane-impermeable lanthanide complexes. A heterodimer of a luminescent Tb(III) complex, Lumi4, linked to trimethoprim and conjugated to nonaarginine via a reducible disulfide linker rapidly (∼10 min) translocates into the cytoplasm of Maden Darby canine kidney cells from the culture medium. With this reagent, the intracellular interaction between GFP fused to FK506 binding protein 12 (GFP-FKBP12) and the rapamycin binding domain of mTOR fused to Escherichia coli dihydrofolate reductase (FRB

  16. Biological toxicity of lanthanide elements on algae.

    Science.gov (United States)

    Tai, Peidong; Zhao, Qing; Su, Dan; Li, Peijun; Stagnitti, Frank

    2010-08-01

    The biological toxicity of lanthanides on marine monocellular algae was investigated. The specific objective of this research was to establish the relationship between the abundance in the seawater of lanthanides and their biological toxicities on marine monocellular algae. The results showed that all single lanthanides had similar toxic effects on Skeletonema costatum. High concentrations of lanthanides (29.04+/-0.61 micromol L(-1)) resulted in 50% reduction in growth of algae compared to the controls (0 micromol L(-1)) after 96 h (96 h-EC50). The biological toxicity of 13 lanthanides on marine monocellular algae was unrelated with the abundance of different lanthanide elements in nature, and the "Harkins rule" was not appropriate for the lanthanides. A mixed solution that contained equivalent concentrations of each lanthanide element had the same inhibition effect on algae cells as each individual lanthanide element at the same total concentration. This phenomenon is unique compared to the groups of other elements in the periodic table. Hence, we speculate that the monocellular organisms might not be able to sufficiently differentiate between the almost chemically identical lanthanide elements.

  17. Controllable Synthesis of Highly Luminescent Boron Nitride Quantum Dots.

    Science.gov (United States)

    Li, Hongling; Tay, Roland Yingjie; Tsang, Siu Hon; Zhen, Xu; Teo, Edwin Hang Tong

    2015-12-22

    Boron nitride quantum dots (BNQDs), as a new member of heavy metal-free quantum dots, have aroused great interest in fundamental research and practical application due to their unique physical/chemical properties. However, it is still a challenge to controllably synthesize high-quality BNQDs with high quantum yield (QY), uniform size and strong fluorescent. In this work, BNQDs have been successfully fabricated by the liquid exfoliation and the subsequent solvothermal process with respect to its facileness and easy large scale up. Importantly, BNQDs with high-quality can be controllably obtained by adjusting the synthetic parameters involved in the solvothermal process including filling factor, synthesis temperature, and duration time. Encouragingly, the as-prepared BNQDs possess strong blue luminescence with QY as high as 19.5%, which can be attributed to the synergetic effect of size, surface chemistry and edge defects. In addition, this strategy presented here provides a new reference for the controllable synthesis of other heavy metal-free QDs. Furthermore, the as-prepared BNQDs are non-toxic to cells and exhibit nanosecond-scaled lifetimes, suggesting they have great potential biological and optoelectronic applications.

  18. Highly efficient avalanche multiphoton luminescence from coupled Au nanowires in the visible region

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    We report highly efficient avalanche multiphoton luminescence(MPL)from ordered-arrayed gold nanowires(NWs).The time-average excitation intensity I_(exc) is as low as 5.0-9.1 kW/cm~2.The intensity of avalanche MPL I_(MPL) is about 10~4 times larger than that of three-photon luminescence,the slope ■logI_(MPL)/■logI_(exc) of avalanche MPL reaches as high as 18.3 and the corresponding polarization dependence of I_(MPL) has a form of cos~(50)■_p.The emission dynamics of avalanche MPL and three-photon luminesc...

  19. Color-coded multilayer photopatterned microstructures using lanthanide (III) ion co-doped NaYF{sub 4} nanoparticles with upconversion luminescence for possible applications in security

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Won Jin; Nyk, Marcin; Prasad, Paras N [Department of Chemistry, Institute for Lasers, Photonics and Biophotonics, University at Buffalo, State University of New York, Buffalo, NY 14260 (United States)], E-mail: pnprasad@buffalo.edu

    2009-05-06

    We report a method for fabricating predefined photopatterns of upconversion nanophosphors using a chemical amplification reaction for direct writing of films with multilayer color-coded patterning for security applications. To photopattern the nanocrystal film we have synthesized rare-earth ion (Er{sup 3+}/Yb{sup 3+} or Tm{sup 3+}/Yb{sup 3+}) co-doped sodium yttrium fluoride ({alpha}-NaYF{sub 4}) nanophosphors and functionalized the nanocrystal surfaces by incorporation of a photopatternable ligand such as t-butoxycarbonyl (t-BOC). The surface modification allows photopatterning of the nanophosphor solid state film. Furthermore, upconversion nanophosphors show a nearly quadratic dependence of the upconversion photoluminescence (PL) intensity on the excitation light power, and tailoring of the PL wavelength is possible by changing the lanthanide ions. We have demonstrated the capability of anchoring nanophosphors at desirable locations by a photolithography technique. The photopatterned films exhibit fixed nanophosphor structures clearly identifiable by strong upconversion photoluminescence under IR illumination which is useful for a number of applications in security.

  20. Highly selective recovery of phosphopeptides using trypsin-assisted digestion of precipitated lanthanide-phosphoprotein complexes.

    Science.gov (United States)

    Güzel, Yüksel; Rainer, Matthias; Mirza, Munazza R; Messner, Christoph B; Bonn, Günther K

    2013-05-21

    The basic idea of this study was to recover phosphopeptides after trypsin-assisted digestion of precipitated phosphoproteins using trivalent lanthanide ions. In the first step, phosphoproteins were extracted from the protein solution by precipitation with La(3+) and Ce(3+) ions, forming stable pellets. Additionally, the precipitated lanthanide-phosphoprotein complexes were suspended and directly digested on-pellet using trypsin. Non-phosphorylated peptides were released into the supernatants by enzymatic cleavage and phosphopeptides remained bound on the precipitated pellet. Further washing steps improved the removal of non-phosphorylated peptides. For the recovery of phosphopeptides the precipitated pellets were dissolved in 3.7% hydrochloric acid. The performance of this method was evaluated by several experiments using MALDI-TOF MS measurements and delivered the highest selectivity for phosphopeptides. This can be explained by the overwhelming preference of lanthanides for binding to oxygen-containing anions such as phosphates. The developed enrichment method was evaluated with several types of biological samples, including fresh milk and egg white. The uniqueness and the main advantages of the presented approach are the enrichment on the protein-level and the recovery of phosphopeptides on the peptide-level. This allows much easier handling, as the number of molecules on the peptide level is unavoidably higher, by complicating every enrichment strategy.

  1. Highly luminescent half-lantern cyclometalated platinum(II) complex: synthesis, structure, luminescence studies, and reactivity.

    Science.gov (United States)

    Sicilia, Violeta; Forniés, Juan; Casas, José Ma; Martín, Antonio; López, José A; Larraz, Carmen; Borja, Pilar; Ovejero, Carmen; Tordera, Daniel; Bolink, Henk

    2012-03-19

    that 1 is a very efficient and stable (3)MMLCT emitter, even in solution. The high luminescence quantum yield of its red emission, added to its neutral character and the thermal stability of 1, make it a potential compound to be incorporated as phosphorescent dopant in multilayer organic light-emitting devices (OLEDs).

  2. Lanthanide dithiocarbamate complexes: efficient catalysts for the cyanosilylation of aldehydes

    OpenAIRE

    VALE, JULIANA A.; FAUSTINO, WAGNER M.; Menezes, Paulo H.; Sá,Gilberto F. de

    2006-01-01

    A new class of lanthanide dithiocarbamate complexes was used to promote the cyanosilylation of aldehydes at high yields at room temperature. This represents the first application of lanthanide dithiocarbamate acting as Lewis acid.

  3. Design and synthesis of a new terbium complex-based luminescent probe for time-resolved luminescence sensing of zinc ions.

    Science.gov (United States)

    Ye, Zhiqiang; Xiao, Yunna; Song, Bo; Yuan, Jingli

    2014-09-01

    Luminescent probes/chemosensors based on lanthanide complexes have shown great potentials in various bioassays due to their unique long-lived luminescence property for eliminating short-lived autofluorescence with time-resolved detection mode. In this work, we designed and synthesized a new dual-chelating ligand {4'-[N,N-bis(2-picolyl)amino]methylene-2,2':6',2'-terpyridine-6,6'-diyl} bis(methylenenitrilo) tetrakis(acetic acid) (BPTTA), and investigated the performance of its Tb(3+) complex (BPTTA-Tb(3+)) for the time-resolved luminescence sensing of Zn(2+) ions in aqueous media. Weakly luminescent BPTTA-Tb(3+) can rapidly react with Zn(2+) ions to display remarkable luminescence enhancement with high sensitivity and selectivity, and such luminescence response can be realized repeatedly. Laudably, the dose-dependent luminescence enhancement shows a good linear response to the concentration of Zn(2+) ions with a detection limit of 4.1 nM. To examine the utility of the new probe for detecting intracellular Zn(2+) ions, the performance of BPTTA-Tb(3+) in the time-resolved luminescence imaging of Zn(2+) ions in living HeLa cells was investigated. The results demonstrated the applicability of BPTTA-Tb(3+) as a probe for the time-resolved luminescence sensing of intracellular Zn(2+) ions.

  4. Luminescent solutions and powders of new samarium complexes with N,N',O,O'-chelating ligands

    Science.gov (United States)

    Kharcheva, Anastasia V.; Nikolskiy, Kirill S.; Borisova, Nataliya E.; Ivanov, Alexey V.; Reshetova, Marina D.; Yuzhakov, Viktor I.; Patsaeva, Svetlana V.

    2016-04-01

    Imaging techniques in biology and medicine are crucial tools to obtain information on structural and functional properties of living cells and organisms. To fulfill the requirements associated with application of these techniques it appears necessary to design markers with specific characteristics. Luminescent complexes of trivalent lanthanide ions with chelating ligands are of increasing importance in biomedical applications because of their millisecond luminescence lifetime, narrow emission band, high signal-to-noise ratio and minimal photodamage to biological samples. In order to extend the available emission wavelength range the luminescent samarium chelates are highly desirable. In this study the ligands with diamides of 2,2'-bipyridin-6,6'-dicarboxylic acid were used to improve photophysical characteristics of samarium complexes. We report the luminescence characteristics of samarium complexes with novel ligands. All complexes exhibited the characteristic emission of Sm (III) ion with the lines at 565, 597, 605, 645 and 654 nm, the intensity strongly depended on the ligand. Absorption and luminescence excitation spectra of Sm (III) complexes showed main peaks in the UV range demonstrating lanthanide coordination to the ligand. The absolute lumenescence quantum yield was measured for solutions in acetonitrile with excitation at 350 nm. The largest luminescence quantum yield was found for the samarium complex Bipy 6MePy Sm (3%) being much higher that for samarium complexes reported in the literature earlier. These results prove as well that samarium chelates are potential markers for multiparametric imaging techniques.

  5. Modification on upconversion luminescence of Er3 +-Yb3 + co-doped BiOCl semiconductor nanosheets through interaction between nanohost and doping lanthanide

    Science.gov (United States)

    Xu, Zuyuan; Li, Yongjin; Song, Yapai; Zhang, Xiangzhou; Hu, Rui; Qiu, Jianbei; Yang, Zhengwen; Song, Zhiguo

    2017-04-01

    We reported the upconversion luminescence (UCL) properties of Er3 +-Yb3 + co-doped BiOCl semiconductor nanosheets synthesized by hydrothermal method. Under 980 nm excitation, the red and green UCL of Er3 + ions were observed to be populated by a four and three-photon process in the case of absent or low concentration Yb3 + dopant. However, an increase of Yb3 + dopants show a completely opposite effect on the emission intensity of red and green one, accompanying with the change of upconverting process. It indicates that the red-shifting absorption edge of semiconductor and the super saturation UC processes involved with Yb3 + and Er3 + doping in BiOCl semiconductor nanosheets, respectively, are mainly responsible for the above UC phenomena.

  6. Understanding the complexation of Eu3 + with potential ligands used for preferential separation of lanthanides and actinides in various stages of nuclear fuel cycle: A luminescence investigation

    Science.gov (United States)

    Sengupta, Arijit; Kadam, R. M.

    2017-02-01

    A systematic photoluminescence based investigation was carried out to understand the complexation of Eu3 + with different ligands (TBP: tri-n-butyl phosphate, DHOA: di-n-hexyl octanamide, Cyanex 923: tri-n-alkyl phosphine oxide and Cyanex 272: Bis (2,4,4 trimethyl) pentyl phosphinic acid) used for preferential separation of lanthanides and actinides in various stages of nuclear fuel cycle. In case of TBP and DHOA complexes, 3 ligand molecules coordinated in monodentate fashion and 3 nitrate ion in bidentate fashion to Eu3 + to satisfy the 9 coordination of Eu. In case of Cyanex 923 and Cyanex 272 complexes, 3 ligand molecules, 3 nitrate ion and 3 water molecules coordinated to Eu3 + in monodentate fashion. The Eu complexes of TBP and DHOA were found to have D3h local symmetry while that for Cyanex 923 and Cyanex 272 were C3h. Judd-Ofelt analysis of these systems revealed that the covalency of Eusbnd O bond followed the trend DHOA > TBP > Cyanex 272 > Cyanex 923. Different photophysical properties like radiative and non-radiative life time, branching ratio for different transitions, magnetic and electric dipole moment transition probabilities and quantum efficiency were also evaluated and compared for these systems. The magnetic dipole transition probability was found to be almost independent of ligand field perturbation while electric dipole transition probability for 5D0-7F2 transition was found to be hypersensitive with ligand field with a trend DHOA > TBP > Cyanex 272 > Cyanex 923. Supplementary Table 2: Determination of inner sphere water molecules from the different empirical formulae reported in the literature.

  7. Highly Nonlinear Luminescence Induced by Gold Nanoparticles on Glass Surfaces with Continuous-Wave Laser Illumination

    CERN Document Server

    Wu, Yong; Toro, Ligia; Stefani, Enrico

    2015-01-01

    We report on highly nonlinear luminescence being observed from individual spherical gold nanoparticles immobilized on a borosilicate glass surface and illuminated by continuous-wave (CW) lasers with relatively low power. The nonlinear luminescence shows optical super-resolution beyond the diffraction limit in three dimensions compared to the scatting of the excitation laser light. The luminescence intensity from most nanoparticles is proportional to the 5th--7th power of the excitation laser power and has wide excitation and emission spectra across the visible wavelength range. Strong nonlinear luminescence is only observed near the glass surface. High optical nonlinearity excited by low CW laser power is related to a long-lived dark state of the gold nanoparticles, where the excitation light is strongly absorbed. This phenomenon has potential biological applications in super-resolution and deep tissue imaging.

  8. Controlled Synthesis of a Novel Heteropolymetallic Complex with Selectively Incorporated Lanthanide(III) Ions

    OpenAIRE

    Debroye, Elke; Ceulemans, Matthias; Vander Elst, Luce; Laurent, Sophie; Muller, Robert N.; Parac-Vogt, Tatjana

    2014-01-01

    A novel synthetic strategy toward a heteropolymetallic lanthanide complex with selectively incorporated gadolinium and europium ions is outlined. Luminescence and relaxometric measurements suggest possible applications in bimodal (magnetic resonance/optical) imaging.

  9. 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

  10. 搀杂镧系离子的纳米绝缘材料的合成与发光特性%Synthesis and Luminescence of Nano-insulators Doped with Lanthanids Ions

    Institute of Scientific and Technical Information of China (English)

    P.A.; Tanner

    2005-01-01

    @@ The general characteristics of f-f and f-d emission spectra of lanthanide ions in insulators are discussed. The current status of energy level and intensity calculations is evaluated. Taking typical examples, the methods of synthesis of lanthanide ion-doped insulating nanomaterials are presented and their characterizations and unusual optical properties are compared.

  11. Three novel lanthanide metal-organic frameworks (Ln-MOFs) constructed by unsymmetrical aromatic dicarboxylatic tectonics: synthesis, crystal structures and luminescent properties.

    Science.gov (United States)

    Wu, Ya-Pan; Li, Dong-Sheng; Xia, Wei; Guo, Sha-Sha; Dong, Wen-Wen

    2014-09-11

    Three novel Ln(III)-based coordination polymers, {[Ln2 (2,4-bpda)3 (H2O)x]·yH2O}n (Ln = La (III) (1), x = 2, y = 0, Ce (III) (2), Pr (III) (3), x = 4, y = 1) (2,4-H2bpda = benzophenone-2,4-dicarboxylic acid) have been prepared via a solvothermal method and characterized by elemental analysis, IR, and single-crystal X-ray diffraction techniques. Complex 1 exhibits a 3D complicated framework with a new 2-nodal (3,7)-connected (42·5) (44·51·66·8) topology. Complexes 2 and 3 are isomorphous, and feature a 3D 4-connected (65·8)-CdSO4 network. Moreover, solid-state properties such as thermal stabilities and luminescent properties of 1 and 2 were also investigated. Complex 1 crystallized in a monoclinic space group P21/c with a = 14.800 (3), b = 14.500 (3), c = 18.800 (4) Å, β = 91.00 (3), V = 4033.9 (14) Å3 and Z = 4. Complex 2 crystallized in a monoclinic space group Cc with a = 13.5432 (4), b = 12.9981 (4), c = 25.7567 (11) Å, β = 104.028 (4), V = 1374.16 (7) Å3 and Z = 4.

  12. Three Novel Lanthanide Metal-Organic Frameworks (Ln-MOFs Constructed by Unsymmetrical Aromatic Dicarboxylatic Tectonics: Synthesis, Crystal Structures and Luminescent Properties

    Directory of Open Access Journals (Sweden)

    Ya-Pan Wu

    2014-09-01

    Full Text Available Three novel Ln(III-based coordination polymers, {[Ln2 (2,4-bpda3 (H2Ox]·yH2O}n (Ln = La (III (1, x = 2, y = 0, Ce (III (2, Pr (III (3, x = 4, y = 1 (2,4-H2bpda = benzophenone-2,4-dicarboxylic acid have been prepared via a solvothermal method and characterized by elemental analysis, IR, and single-crystal X-ray diffraction techniques. Complex 1 exhibits a 3D complicated framework with a new 2-nodal (3,7-connected (42·5 (44·51·66·8 topology. Complexes 2 and 3 are isomorphous, and feature a 3D 4-connected (65·8-CdSO4 network. Moreover, solid-state properties such as thermal stabilities and luminescent properties of 1 and 2 were also investigated. Complex 1 crystallized in a monoclinic space group P21/c with a = 14.800 (3, b = 14.500 (3, c = 18.800 (4 Å, β = 91.00 (3, V = 4033.9 (14 Å3 and Z = 4. Complex 2 crystallized in a monoclinic space group Cc with a = 13.5432 (4, b = 12.9981 (4, c = 25.7567 (11 Å, β = 104.028 (4, V = 1374.16 (7 Å3 and Z = 4.

  13. A sensitive fluorescent sensor of lanthanide ions

    CERN Document Server

    Bekiari, V; Lianos, P

    2003-01-01

    A fluorescent probe bearing a diazostilbene chromophore and a benzo-15-crown-5 ether moiety is a very efficient sensor of lanthanide ions. The ligand emits strong fluorescence only in the presence of specific ions, namely lanthanide ions, while the emission wavelength is associated with a particular ion providing high sensitivity and resolution.

  14. Luminescence as a new detection method for non-relativistic highly ionizing particles in water/ice neutrino telescopes

    Energy Technology Data Exchange (ETDEWEB)

    Pollmann, Anna [Bergische Universitaet Wuppertal (Germany); Collaboration: IceCube-Collaboration

    2016-07-01

    Cosmic ray detectors use air as a radiator for luminescence. In water and ice detectors Cherenkov light is the dominant light producing mechanism when the particle velocity exceeds the Cherenkov threshold, approximately three quarters of the speed of light. Luminescence is produced by highly ionizing particles passing through matter due to the excitation of the surrounding atoms. The observables of luminescence, such as the wavelength spectrum and decay times, are highly dependent on the properties of the medium. Therefore, the results of measurements, in which luminescence was produced by particles passing through water or ice, vary by two orders of magnitude in intensity. It is shown that, even for the most conservative intensity value, luminescence can be used as a detection method for highly ionizing particles with velocities below the Cherenkov threshold. These could be magnetic monopoles or other massive and highly penetrating exotic particles. In the most optimistic case, luminescence contributes even to the light output of standard model particles.

  15. Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination.

    Science.gov (United States)

    Liu, Baoxia; Huang, Yankai; Zhu, Xu; Hao, Yuanqiang; Ding, Yujie; Wei, Wei; Wang, Qi; Qu, Peng; Xu, Maotian

    2016-03-17

    Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg(2+) detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb(3+) from the quenching effect of O-H vibration in water molecules. The subsequent addition of Hg(2+) into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg(2+). As a kind of Hg(2+) nanosensor, the probe exhibited excellent selectivity for Hg(2+) and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg(2+) in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging.

  16. Material and Optical Design Rules for High Performance Luminescent Solar Concentrators

    Science.gov (United States)

    Bronstein, Noah Dylan

    This dissertation will highlight a path to achieve high photovoltaic conversion efficiency in luminescent solar concentrators, devices which absorb sunlight with a luminescent dye and then re-emit it into a waveguide where it is ultimately collected by a photovoltaic cell. Luminescent concentrators have been studied for more than three decades as potential low-cost but not high efficiency photovoltaics. Astute application of the blackbody radiation law indicates that photonic design is necessary to achieve high efficiency: a reflective filter must be used to trap luminescence at all angles while allowing higher energy photons to pass through. In addition, recent advances in the synthesis of colloidal nanomaterials have created the possibility for lumophores with broad absorption spectra, narrow-bandwidth emission, high luminescence quantum yield, tunable Stokes shifts and tunable Stokes ratios. Together, these factors allow luminescent solar concentrators to achieve the optical characteristics necessary for high efficiency. We have fabricated and tested the first generation of these devices. Our experiments demonstrate that the application of carefully matched photonic mirrors and luminescent quantum dots can allow luminescent concentration factors to reach record values while maintaining high photon collection efficiency. Finally, the photonic mirror dramatically mitigates the negative impact of scattering in the waveguide, allowing efficient photon collection over distances much longer than the scattering length of the waveguide. After demonstrating the possibility for high performance, we theoretically explore the efficacy of luminescent concentrators with dielectric reflectors as the high-bandgap top-junctions in two-junction devices. Simple thermodynamic calculations indicate that this approach can be nearly as good as a traditional vertically stacked tandem. The major barriers to such a device are the optical design of narrow-bandwidth, angle

  17. A series of tetrathiafulvalene-based lanthanide complexes displaying either single molecule magnet or luminescence-direct magnetic and photo-physical correlations in the ytterbium analogue.

    Science.gov (United States)

    Pointillart, Fabrice; Le Guennic, Boris; Cauchy, Thomas; Golhen, Stéphane; Cador, Olivier; Maury, Olivier; Ouahab, Lahcène

    2013-05-20

    The reaction between (4,5-bis(2-pyridyl-N-oxidemethylthio)-4',5')-ethylenedithiotetrathiafulvene (L(1)) or -methyldithiotetrathiafulvene (L(2)) ligands and Ln(hfac)3·nH2O precursors (Ln(III) = Pr, Tb, Dy, Er, and Yb) leads to the formation of seven dinuclear complexes of formula [Ln2(hfac)6(H2O)x(L(y))2] (x = 2 and y = 1 for Ln(III) = Pr (1); x = 0 and y = 1 for Ln(III) = Tb (2), Dy (3), Er (4) and Yb (5); x = 0 and y = 2 for Ln(III) = Tb (6) and Dy (7)). Their X-ray structures reveal that the coordination environment of each Ln(III) center is filled by two N-oxide groups coming from two different ligands L(y). UV-visible absorption properties have been experimentally measured and rationalized by TD-DFT calculations. The temperature dependences of static magnetic measurements have been fitted. The ground state corresponds to the almost pure |M(J) = ±13/2〉 while the first excited state (±0.77|±11/2〉 ± 0.50|±3/2〉 ± 0.39|±5/2〉) is located at 19 cm(-1) and 26.9 cm(-1) respectively for 3 and 7. Upon irradiation at 77 K and at room temperature, in the range 25,000-20,835 cm(-1), both compounds 4 and 5 display a metal-centered luminescence attributed to (4)I(13/2) → (4)I(15/2) (6660 cm(-1)) and (2)F(5/2) → (2)F(7/2) (9972 cm(-1)) transitions, respectively. Emission spectroscopy provides a direct probe of the |±5/2〉 ground state multiplet splitting, which has been confronted to magnetic data. The energy separation of 225 cm(-1) between the ground state and the first excited level (M(J) = ±3/2) fits exactly the second emission line (234 cm(-1)). While no out-phase-signal is detected for 3, the change of ligand L(1) → L(2) induces a change of coordination sphere symmetry around the Dy(III) increasing the energy splitting between the ground and first excited states, and 7 displays a single molecule magnet behavior.

  18. Nanometrization of Lanthanide-Based Coordination Polymers.

    Science.gov (United States)

    Neaime, Chrystelle; Daiguebonne, Carole; Calvez, Guillaume; Freslon, Stéphane; Bernot, Kevin; Grasset, Fabien; Cordier, Stéphane; Guillou, Olivier

    2015-11-23

    Heteronuclear lanthanide-based coordination polymers are microcrystalline powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare-earth ions. In this study, we demonstrate that such materials can also be obtained as stable solutions of nanoparticles in non-toxic polyols. Bulk powders of the formula [Ln2-2x Ln'2x (bdc)3 ⋅4 H2 O]∞ (where H2 bdc denotes 1,4-benzene-dicarboxylic acid, 0≤x≤1, and Ln and Ln' denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light-scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities versus time and versus dilution with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide-based coordination polymers.

  19. Synthesis, Tunable Multicolor Output, and High Pure Red Upconversion Emission of Lanthanide-Doped Lu2O3 Nanosheets

    Directory of Open Access Journals (Sweden)

    Lingzhen Yin

    2013-01-01

    Full Text Available Yb3+ and Ln3+ (Ln = Er, Ho codoped Lu2O3 square nanocubic sheets were successfully synthesized via a facile hydrothermal method followed by a subsequent dehydration process. The crystal phase, morphology, and composition of hydroxide precursors and target oxides were characterized by X-ray diffraction (XRD, field emission scanning electron microscope (FE-SEM, and energy-dispersive X-ray spectroscope (EDS. Results present the as-prepared Lu2O3 crystallized in cubic phase, and the monodispersed square nanosheets were maintained both in hydroxide and oxides. Moreover, under 980 nm laser diode (LD excitation, multicolor output from red to yellow was realized by codoped different lanthanide ions in Lu2O3. It is noteworthy that high pure strong red upconversion emission with red to green ratio of 443.3 of Er-containing nanocrystals was obtained, which is beneficial for in vivo optical bioimaging.

  20. Factors Affecting the Efficiency of Excited-States Interactions of Complexes between Some Visible Light-Emitting Lanthanide Ions and Cyclophanes Containing Spirobiindanol Phosphonates

    Directory of Open Access Journals (Sweden)

    M. S. Attia

    2007-01-01

    Full Text Available The efficiency of excited-states interactions between lanthanide ions Tb3+ and Eu3+ and some new cyclophanes (I, II, and III has been studied in different media. High luminescence quantum yield values for terbium and europium complexes in DMSO and PMMA were obtained. The photophysical properties of the green and red emissive Tb3+ and Eu3+ complexes have been elucidated, respectively.

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

    Science.gov (United States)

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

    2011-09-05

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

  2. 双核稀土配合物的合成表征及其光学性能%Synthesis, Characterization and Luminescence Properties of Dinuclear Lanthanide Complexes

    Institute of Scientific and Technical Information of China (English)

    颜剑波; 豆丽靖; 段春光; 王云友; 孙波

    2010-01-01

    Two new complexes of Eu(Ⅲ) and Tb(Ⅲ) chelated with bis(β-diketone) terephthaloyl-diacetophenone (TDAP) were successfully synthesized. The samples were characterized by the element analysis, infrared spectra, UV-Vis spectra, 1H NMR and fluorescence spectra. The results indicated that their compositions are Eu2(TDAP)3· (H2O)2 and Tb2 (TDAP)3 · (H2O)6, respectively. Photoluminescence measurement indicated that TDAP is a good indigo emitter under UV radiation. The average triplet state energy of the ligand was obtained by analyzing the phos-phorescence spectrum of TDAP. The Eu(Ⅲ) complexes display characteristic metal-centered luminescence, while the ligand emissions are completely quenched. The results indicated that the efficient ligand-to-metal energy transfer (antenna effect) occurs. The characteristic red emission appears due to the 5D0 → 7Fj transitions of the 4f electrons of the central Eu3+ ions. Tb2(TDAP)3 ·(H2O)6 has poor fluorescence property, this is because the triplet state energy of the ligand does not match with the lowest excited state energy of Tb3+ ions. The possible energy transfer mechanism was investigated.%合成了一种新的双β二酮配体1,4-二苯甲酰乙酰苯(TDAP),并成功合成了它的两个双核稀土配合物Eu2(TDAP)3·(H2O)z和Tb2(TDAP)3·(H2O)6.通过元素分析、红外光谱、紫外可见光谱和荧光光谱对配合物进行了表征与性能研究.荧光分析表明,在紫外灯下配体本身就发出蓝紫色荧光,通过对配体 TDAP的磷光光谱分析计算得到了配体的平均三重态能级.配合物Eu2(TDAP)3·(H2O):的发射光谱分析表明,配体自身的发射几乎完全被淬灭,能量成功传递给了中心离子,因此配合物发出了明显的特征峰,主发射峰为Eu3+的5D0-7F2发射.由荧光分析知,配合物Eu2(TDAP)3·(H2O)2的激发光谱与配体发射光谱的重叠,这验证了配体TDAP对于Eu3+能量传递的有效性.此外,还详细分析了两种配合物的能

  3. Photofunctional hybrids of lanthanide functionalized bio-MOF-1 for fluorescence tuning and sensing.

    Science.gov (United States)

    Shen, Xiang; Yan, Bing

    2015-08-01

    A series of luminescent Ln(3+)@bio-MOF-1 (Ln=Eu, Tb, bio-MOF-1=Zn8(ad)4(BPDC)6O⋅2Me2NH2 (ad=adeninate, BPDC=biphenyldicarboxylate)) are synthesized via postsynthetic cation exchange by encapsulating lanthanide ions into an anionic metal-organic framework (MOF), and their photophysical properties are studied. After loading 2-thenoyltrifluroacetone (TTA) as sensitized ligand by a gas diffusion ("ship-in-bottle") method, it is found that the luminescent intensity of Eu(3+) is enhanced. Especially, when loading two different lanthanide cations into bio-MOF-1, the luminescent color can be tuned to close white (light pink) light output. Additionally, bio-MOF-1 and Eu(3+)@bio-MOF-1 are selected as representative samples for sensing metal ions. When bio-MOF-1 is immersed in the aqueous solutions of different metal ions, it shows highly sensitive sensing for Fe(3+) as well as Eu(3+)@bio-MOF-1 immersed in the DMF solutions of different metal ion. The results are benefit for the further application of functionalized bio-MOFs in practical fields. Copyright © 2015 Elsevier Inc. All rights reserved.

  4. Using lanthanide chelates and uranyl compounds for diagnostic by fluoroimmunoassays

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Elen G.; Tomiyama, Claudia S.; Kodaira, Claudia A.; Felinto, Maria C.F.C., E-mail: mfelinto@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Lourenco, Ana V. S.; Brito, Hermi F., E-mail: hefbrito@iq.usp.b [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica. Lab. de Elementos do Bloco f; Brito, Maria E.F., E-mail: britomef@cpqam.fiocruz.b [Centro de Pesquisas Aggeu Magalhaes (CPqAM/Fiocruz), Recife, PE (Brazil)

    2009-07-01

    The importance of the luminescence of lanthanide ions and UO{sub 2}{sup 2+} is related to its peculiar characteristics, e.g. long lifetime and line-like emission bands in the visible, which make these ions unique among the species that are known to luminescence. Recent developments in the field of supramolecular chemistry have allowed the design of ligands capable of encapsulating lanthanide ions, thus forming kinetically inert complexes. By introduction of chromophoric groups in these ligands, an intense luminescence of the ion can be obtained via the 'antenna effect', defined as a light conversion process involving distinct absorbing (ligand) and emitting (metal ion) components. In such a process, the quantities that contribute to the luminescence intensity are the efficiency of the absorption, the efficiency of the ligand-metal energy transfer, and the efficiency of the metal luminescence. Encapsulation of lanthanide ions with suitable ligands may therefore give rise to 'molecular devices' capable to emit strong, long-lived luminescence. Besides the intrinsic interest in their excited state properties, compounds of lanthanide ions, in particular of the Eu{sup 3+} and Tb{sup 3+} ions, and now UO{sub 2}{sup 2+} are important for their potential use as luminescent labels for biological species in fluoroimmunoassays (FIAs). This is most interesting because fluorimetric labeling represents an alternative method to the use of radioactive labels, which has long been the most common way of quantifying immunoreactions. In this article we report information about luminescent materials, which gave a good signal to quantify biological molecules by TR-FIA, DELFIA , DSLFIA, RIA and FRET. (author)

  5. High-Temperature Thermometer Using Cr-Doped GdAlO3 Broadband Luminescence

    Science.gov (United States)

    Eldridge, Jeffrey; Chambers, Matthew

    2011-01-01

    A new concept has been developed for a high-temperature luminescence-based optical thermometer that both shows the desired temperature sensitivity in the upper temperature range of present state-of-the-art luminescence thermometers (above 1,300 C), while maintaining substantial stronger luminescence signal intensity that will allow these optical thermometers to operate in the presence of the high thermal background radiation typical of industrial applications. This objective is attained by using a Cr-doped GdAlO3 (Cr:GdAlO3) sensor with an orthorhombic perovskite structure, resulting in broadband luminescence that remains strong at high temperature due to the favorable electron energy level spacing of Cr:GdAlO3. The Cr:GdAlO3 temperature (and pressure) sensor can be incorporated into, or applied onto, a component s surface when a non-contact surface temperature measurement is desired, or alternatively, the temperature sensor can be attached to the end of a fiber-optic probe that can then be positioned at the location where the temperature measurement is desired. In the case of the fiber-optic probe, both the pulsed excitation and the luminescence emission travel through the fiber-optic light guide. In either case, a pulsed light source provides excitation of the luminescence, and the broadband luminescence emission is collected. Real-time temperature measurements are obtain ed using a least-squares fitting algorithm that determines the luminescence decay time, which has a known temperature dependence established by calibration. Due to the broad absorption and emission bands for Cr:GdAlO3, there is considerable flexibility in the choice of excitation wavelength and emission wavelength detection bands. The strategic choice of the GdAlO3 host is based on its high crystal field, phase stability, and distorted symmetry at the Cr3+ occupation sites. The use of the broadband emission for temperature sensing at high temperatures is a key feature of the invention and is

  6. Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Baoxia [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Huang, Yankai [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China); Zhu, Xu; Hao, Yuanqiang [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Ding, Yujie [College of Biochemical Engineering, Anhui Polytechnic University, Wuhu 241000 (China); Wei, Wei; Wang, Qi [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Qu, Peng, E-mail: qupeng0212@163.com [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China); Xu, Maotian, E-mail: xumaotian@sqnc.edu.cn [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China)

    2016-03-17

    Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg{sup 2+} detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb{sup 3+} from the quenching effect of O–H vibration in water molecules. The subsequent addition of Hg{sup 2+} into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg{sup 2+}. As a kind of Hg{sup 2+} nanosensor, the probe exhibited excellent selectivity for Hg{sup 2+} and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg{sup 2+} in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging. - Highlights: • Lanthanide coordination polymer of Tb-CIP/AMP was synthesized via a simple self-assembly process. • AMP was employed as a bifunctional molecule for both fluorescence sensitization and target recognition. • Hypersensitive detection of Hg{sup 2+} was achieved based on time-resolved spectroscopy.

  7. Lanthanide-containing polyimides

    Science.gov (United States)

    Stoakley, D. M.; St. Clair, Anne K.

    1987-01-01

    The preparation of a variety of lanthanide-containing polyimide films is described, and results of their characterization are presented. The properties investigated include the glass transition temperature, thermooxidative stability, magnetic susceptibility, and electrical conductivity of the polymer. Films containing lanthanide chlorides, fluorides, and sulfides are flexible, but those containing lanthanide nitrates are extremely brittle. The addition of lanthanide acetates and acetylacetonates caused immediate gelation of two of the synthesis-mixture ingredients. It was found that, in general, the addition of lanthanide to the polyimide increases the density and glass transition temperature of the polymer but slightly decreases the thermooxidative stability.

  8. Visible-light-excited and europium-emissive nanoparticles for highly-luminescent bioimaging in vivo.

    Science.gov (United States)

    Wu, Yongquan; Shi, Mei; Zhao, Lingzhi; Feng, Wei; Li, Fuyou; Huang, Chunhui

    2014-07-01

    Europium(III)-based material showing special milliseconds photoluminescence lifetime has been considered as an ideal time-gated luminescence probe for bioimaging, but is still limited in application in luminescent small-animal bioimaging in vivo. Here, a water-soluble, stable, highly-luminescent nanosystem, Ir-Eu-MSN (MSN = mesoporous silica nanoparticles, Ir-Eu = [Ir(dfppy)2(pic-OH)]3Eu·2H2O, dfppy = 2-(2,4-difluorophenyl)pyridine, pic-OH = 3-hydroxy-2-carboxypyridine), was developed by an in situ coordination reaction to form an insoluble dinuclear iridium(III) complex-sensitized-europium(III) emissive complex within mesoporous silica nanoparticles (MSNs) which had high loading efficiency. Compared with the usual approach of physical adsorption, this in-situ reaction strategy provided 20-fold the loading efficiency (43.2%) of the insoluble Ir-Eu complex in MSNs. These nanoparticles in solid state showed bright red luminescence with high quantum yield of 55.2%, and the excitation window extended up to 470 nm. These Ir-Eu-MSN nanoparticles were used for luminescence imaging in living cells under excitation at 458 nm with confocal microscopy, which was confirmed by flow cytometry. Furthermore, the Ir-Eu-MSN nanoparticles were successfully applied into high-contrast luminescent lymphatic imaging in vivo under low power density excitation of 5 mW cm(-2). This synthetic method provides a universal strategy of combining hydrophobic complexes with hydrophilic MSNs for in vivo bioimaging.

  9. Temperature-dependent photoluminescence of highly luminescent water-soluble CdTe quantum dots

    Institute of Scientific and Technical Information of China (English)

    Ji Wei Liu; Yu Zhang; Cun Wang Ge; Yong Long Jin; Sun Ling Hu; Ning Gu

    2009-01-01

    Highly luminescent water-soluble CdTe quantum dots (QDs) have been synthesized with an electrogenerated precursor. The obtained CdTe QDs can possess good crystallizability, high quantum yield (QY) and favorable stability. Furthermore, a detection system is designed firstly for the investigation of the temperature-dependent PL of the QDs.

  10. Strong Circularly Polarized Luminescence from Highly Emissive Terbium Complexes in Aqueous Solution

    Energy Technology Data Exchange (ETDEWEB)

    Samuel, Amanda; Lunkley, Jamie; Muller, Gilles; Raymond, Kenneth

    2010-03-15

    Two luminescent terbium(III) complexes have been prepared from chiral ligands containing 2-hydroxyisophthalamide (IAM) antenna chromophores and their non-polarized and circularly-polarized luminescence properties have been studied. These tetradentate ligands, which form 2:1 ligand/Tb{sup III} complexes, utilize diaminocyclohexane (cyLI) and diphenylethylenediamine (dpenLI) backbones, which we reasoned would impart conformational rigidity and result in Tb{sup III} complexes that display both large luminescence quantum yield ({phi}) values and strong circularly polarized luminescence (CPL) activities. Both Tb{sup III} complexes are highly emissive, with {phi} values of 0.32 (dpenLI-Tb) and 0.60 (cyLI-Tb). Luminescence lifetime measurements in H{sub 2}O and D{sub 2}O indicate that while cyLI-Tb exists as a single species in solution, dpenLI-Tb exists as two species: a monohydrate complex with one H{sub 2}O molecule directly bound to the Tb{sup III} ion and a complex with no water molecules in the inner coordination sphere. Both cyLI-Tb and dpenLI-Tb display increased CPL activity compared to previously reported Tb{sup III} complexes made with chiral IAM ligands. The CPL measurements also provide additional confirmation of the presence of a single emissive species in solution in the case of cyLI-Tb, and multiple emissive species in the case of dpenLI-Tb.

  11. Preparation of Lanthanide-Polymer Composite Material via Click Chemistry.

    Science.gov (United States)

    Chen, Bin; Wen, Guian; Wu, Jiajie; Feng, Jiachun

    2015-10-01

    Covalently attaching lanthanide complexes to the polymer backbone can effectively reduce the clustering of lanthanides and thus become an important strategy to fully unleash their potential. In this Communication, a metal-free click reaction is used for the first time to link a lanthanide complex to the polymer matrix. A diene-bearing copolymer with anthracenylmethyl methacrylate as a monomer and a dienophile-bearing lanthanide complex with 5-maleimido-1,10-phenanthroline as the second ligand are synthesized and coupled together through a Diels-Alder cycloaddition (DA). A comparative investigation demonstrates that the composite material prepared by DA click reaction shows the highest quantum yields in the same lanthanide concentration as compared to materials prepared by widely used "directly doping" and "in situ coordinating lanthanide ions with macromolecular ligand" approaches. This work suggests that the "metal-free" DA click reaction can be a promising tool in the synthesis of high efficient lanthanide functionalized polymeric materials.

  12. Up-Conversion Luminescence of a High Soluble Zinc Phthalocyanine-Epoxy Derivative

    Institute of Scientific and Technical Information of China (English)

    沈悦; 夏义本; 陈精纬; 顾峰; 焦凤华; 张建成

    2004-01-01

    Synthesis and photoelectric properties of a high soluble zinc phthalocyanine-epoxy derivative are investigated.The derivative can be solubilized in convenient solvents, such as CH3OH, CH3CH2OH and H2O. The fluorescence and UV-visible analyses indicate that the ZnPc-epoxy derivative still maintains the plane structure which comes from Zn(4,4',4",4″′-ta)Pc and the derivative has obvious up-conversion luminescence in room temperature. The up-conversion luminescence can be explained by the selection rule depending on the two-photon absorption.

  13. Highly selective luminescent nanostructures for mitochondrial imaging and targeting

    Science.gov (United States)

    Fanizza, E.; Iacobazzi, R. M.; Laquintana, V.; Valente, G.; Caliandro, G.; Striccoli, M.; Agostiano, A.; Cutrignelli, A.; Lopedota, A.; Curri, M. L.; Franco, M.; Depalo, N.; Denora, N.

    2016-02-01

    Here a luminescent hybrid nanostructure based on functionalized quantum dots (QDs) is used as a fluorescent imaging agent able to target selectively mitochondria thanks to the molecular recognition of the translocator protein (TSPO). The selective targeting of such an 18 kDa protein mainly located in the outer mitochondrial membrane and overexpressed in several pathological states including neurodegenerative diseases and cancers may provide valuable information for the early diagnosis and therapy of human disorders. In particular, the rational design of amino functionalized luminescent silica coated QD nanoparticles (QD@SiO2 NPs) provides a versatile nanoplatform to anchor a potent and selective TSPO ligand, characterized by a 2-phenyl-imidazo[1,2-a]pyridine acetamide structure along with a derivatizable carboxylic end group, useful to conjugate the TSPO ligand and achieve TSPO-QD@SiO2 NPs by means of a covalent amide bond. The colloidal stability and optical properties of the proposed nanomaterials are comprehensively investigated and their potential as mitochondrial imaging agents is fully assessed. Sub-cellular fractionation, together with confocal laser scanning fluorescence microscopy and co-localization analysis of targeted TSPO-QD@SiO2 NPs in C6 glioma cells overexpressing the TSPO, proves the great potential of these multifunctional nanosystems as in vitro selective mitochondrial imaging agents.Here a luminescent hybrid nanostructure based on functionalized quantum dots (QDs) is used as a fluorescent imaging agent able to target selectively mitochondria thanks to the molecular recognition of the translocator protein (TSPO). The selective targeting of such an 18 kDa protein mainly located in the outer mitochondrial membrane and overexpressed in several pathological states including neurodegenerative diseases and cancers may provide valuable information for the early diagnosis and therapy of human disorders. In particular, the rational design of amino

  14. Luminescent metal-organic framework films as highly sensitive and fast-response oxygen sensors.

    Science.gov (United States)

    Dou, Zhongshang; Yu, Jiancan; Cui, Yuanjing; Yang, Yu; Wang, Zhiyu; Yang, Deren; Qian, Guodong

    2014-04-16

    Luminescent metal-organic framework films, CPM-5⊃Tb(3+) and MIL-100(In)⊃Tb(3+), have been constructed by postfunctionalization of two porous indium-organic frameworks with different structures, respectively. The MIL-100(In)⊃Tb(3+) film shows high oxygen sensitivity (KSV = 7.59) and short response/recovery time (6 s/53 s).

  15. Highly luminescent CdTe/CdSe colloidal heteronanocrystals with temperature-dependent emission color

    NARCIS (Netherlands)

    Chin, P.T.K.; de Mello Donega, C.; van Bavel, S.S.; Meskers, S.C.J.; Sommerdijk, N.A.J.M.; Jansen, R.A.J.

    2007-01-01

    In this work we present the preparation of highly luminescent anisotropic CdTe/CdSe colloidal heteronanocrystals. The reaction conditions used (low temperature, slow precursor addition, and surfactant composition) resulted in a tunable shape from prolate to branched CdTe/CdSe nanocrystals. Upon CdSe

  16. Simple Lanthanide Amides [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 as Highly Efficient Catalysts for the Nitroaldol Reaction

    Institute of Scientific and Technical Information of China (English)

    LIU,Yu-yu; WANG,Shao-Wu; ZHANG,Li-Jun; WU,Yun-Jun; LI,Qing-Hai; YANG,Gao-Sheng; XIE,Mei-Hua

    2008-01-01

    This contribution is to report the application of simple lanthanide amides [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 exhib-iting a high activity toward catalyzing Henry reaction of aromatic aldehydes with nitroalkanes to give β-nitroalcohols or β-nitroolefins with a very good chemoselectivity by controlling the reaction temperatures and by selecting aromatic aldehydes. It was found that this catalytic system was compatible with a wide range of substrates of aldehydes.

  17. Lanthanide Complexes as a Test for Evidence of Life

    Science.gov (United States)

    Benavides, Jeannette

    1998-01-01

    The objective of this research is to advance the understanding of the interaction of lanthanide metals with biological organic molecules and to develop a technique to detect these compounds in the solid state and in situ in Mars and other planetary bodies. The detection of these complexes should provide evidence of life past or present. In addition, detection of the metals alone will provide important information about the geological history of a planetary body. Lanthanides were chosen as our focus of interest because they form very stable complexes with organic molecules in solution and they produce intense luminescence in the ultraviolet and visible spectra. The rare earth complexes available are mostly synthetic for diverse applications in medicine. There is not much work done on the complexes that form in nature. Lanthanides have many applications and they are mined aR over the world, however, since the interest has been only in the elements, the analytical techniques employed destroy any organic ligands that may be present. In order to determine if and which lanthanide complexes form in nature and their concentration, soil samples have been collected from areas rich in soluble lanthanide compounds like phosphates and also rich in vegetation. The soil samples will be analyzed and the lanthanide complexes if present will be isolated and characterized. A spectrometer to detect the lanthanide complexes in situ and in the solid state will be designed. In this workshop, the research approach and its implications will be discussed.

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

    Science.gov (United States)

    Kesava Raju, Ch Siva; Subramanian, M S

    2007-06-25

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

  19. Poly (acrylic acid)-capped lanthanide-doped BaFCl nanocrystals: synthesis and optical properties.

    Science.gov (United States)

    Ju, Qiang; Luo, Wenqin; Liu, Yongsheng; Zhu, Haomiao; Li, Renfu; Chen, Xueyuan

    2010-07-01

    Water-soluble lanthanide-doped BaFCl nanophosphors with the surface functionalized by a layer of poly (acrylic acid) are synthesized via a facile one-step solvothermal method. Intense long-lived luminescence is realized from visible to near-infrared (NIR) by doping with different lanthanide ions. The emission and excitation spectra of Eu(3+) indicate that the doped lanthanide ions occupy a site close to the surface of the nanoparticles. Strong NIR emissions of Nd(3+) and green luminescence of Tb(3+) using Ce(3+) as sensitizers are also achieved in BaFCl nanoparticles. The synthesized nanoparticles featuring long-lived luminescence in either visible or NIR regions may have potential applications as luminescent labels for biological applications.

  20. Standard addition analysis of fluoroquinolones in human serum in the presence of the interferent salicylate using lanthanide-sensitized excitation-time decay luminescence data and multivariate curve resolution.

    Science.gov (United States)

    Lozano, Valeria A; Tauler, Romà; Ibañez, Gabriela A; Olivieri, Alejandro C

    2009-03-15

    Three fluoroquinolone antibiotics (ciprofloxacin, norfloxacin and danofloxacin) have been determined in human serum in the presence of the potential interferent salicylate, by processing lanthanide-sensitized excitation-time decay matrix data for their terbium (III) complexes. The algorithm employed, multivariate curve resolution-alternating least-squares, is one of the few methodologies which permit the achievement of the second-order advantage in the presence of a high degree of overlapping between the time decay profiles for the analyte and the interferent complexes. Furthermore, the presence of analyte-background interactions makes it necessary to employ the standard addition method for successful quantitation. Both simulations and experiments showed that the modified standard addition method was suitable for this purpose, in which the test data matrix was subtracted from the standard addition matrices, and quantitation proceeded using classical external calibration procedure. The analyte concentration ranges were all within the therapeutic range, i.e., 0-6 mgL(-1) in serum, with final concentrations in the measuring cell in the order of 0.2 mgL(-1).

  1. High-Performance Near-Infrared Luminescent Solar Concentrators.

    Science.gov (United States)

    Rondão, Raquel; Frias, Ana R; Correia, Sandra F H; Fu, Lianshe; de Zea Bermudez, Verónica; André, Paulo S; Ferreira, Rute A S; Carlos, Luís D

    2017-04-12

    Luminescent solar concentrators (LSCs) appear as candidates to enhance the performance of photovoltaic (PV) cells and contribute to reduce the size of PV systems, decreasing, therefore, the amount of material needed and thus the cost associated with energy conversion. One way to maximize the device performance is to explore near-infrared (NIR)-emitting centers, resonant with the maximum optical response of the most common Si-based PV cells. Nevertheless, very few examples in the literature demonstrate the feasibility of fabricating LSCs emitting in the NIR region. In this work, NIR-emitting LSCs are reported using silicon 2,3-naphthalocyanine bis(trihexylsilyloxide) (SiNc or NIR775) immobilized in an organic-inorganic tri-ureasil matrix (t-U(5000)). The photophysical properties of the SiNc dye incorporated into the tri-ureasil host closely resembled those of SiNc in tetrahydrofuran solution (an absolute emission quantum yield of ∼0.17 and a fluorescence lifetime of ∼3.6 ns). The LSC coupled to a Si-based PV device revealed an optical conversion efficiency of ∼1.5%, which is among the largest values known in the literature for NIR-emitting LSCs. The LSCs were posteriorly coupled to a Si-based commercial PV cell, and the synergy between the t-U(5000) and SiNc molecules enabled an effective increase in the external quantum efficiency of PV cells, exceeding 20% in the SiNc absorption region.

  2. Europium Luminescence Used for Logic Gate and Ions Sensing with Enoxacin As the Antenna.

    Science.gov (United States)

    Lu, Lixia; Chen, Chuanxia; Zhao, Dan; Sun, Jian; Yang, Xiurong

    2016-01-19

    Luminescent lanthanide ion complexes have received increasing attention because of their unique optical properties. Herein, we discovered that the luminescence of europium(III) (Eu(3+)) could be regulated by Ag(+) and SCN(-) in seconds with enoxacin (ENX) as the antenna. Under given conditions, only the simultaneous introduction of Ag(+) and SCN(-) could remarkably enhance the luminescence intensity of Eu(3+)-ENX complexes. This phenomenon has been exploited to design an "AND" logic gate and specific luminescence turn-on assays for sensitively sensing Ag(+) and SCN(-) for the first time. Furthermore, the addition of S(2-) resulted in efficient luminescence quenching of the Eu(3+)/ENX/Ag(+)/SCN(-) system due to the strong affinity between Ag(+) and S(2-). Thus, a new luminescent sensing platform for S(2-) was established, which exhibited excellent selectivity and high sensitivity. S(2-) could be detected within the concentration range of 100 nM to 12.5 μM with a detection limit of 60 nM. Such sensing system features simplicity, rapidity, and flexibility. Moreover, this proposed Eu(3+)-based luminescent assay could be successfully applied in the real environmental water sample analysis.

  3. Hysteresis in Lanthanide Zirconium Oxides Observed Using a Pulse CV Technique and including the Effect of High Temperature Annealing

    Directory of Open Access Journals (Sweden)

    Qifeng Lu

    2015-07-01

    Full Text Available A powerful characterization technique, pulse capacitance-voltage (CV technique, was used to investigate oxide traps before and after annealing for lanthanide zirconium oxide thin films deposited on n-type Si (111 substrates at 300 °C by liquid injection Atomic Layer Deposition (ALD. The results indicated that: (1 more traps were observed compared to the conventional capacitance-voltage characterization method in LaZrOx; (2 the time-dependent trapping/de-trapping was influenced by the edge time, width and peak-to-peak voltage of a gate voltage pulse. Post deposition annealing was performed at 700 °C, 800 °C and 900 °C in N2 ambient for 15 s to the samples with 200 ALD cycles. The effect of the high temperature annealing on oxide traps and leakage current were subsequently explored. It showed that more traps were generated after annealing with the trap density increasing from 1.41 × 1012 cm−2 for as-deposited sample to 4.55 × 1012 cm−2 for the 800 °C annealed one. In addition, the leakage current density increase from about 10−6 A/cm2 at Vg = +0.5 V for the as-deposited sample to 10−3 A/cm2 at Vg = +0.5 V for the 900 °C annealed one.

  4. Lanthanide near infrared imaging in living cells with Yb3+ nano metal organic frameworks.

    Science.gov (United States)

    Foucault-Collet, Alexandra; Gogick, Kristy A; White, Kiley A; Villette, Sandrine; Pallier, Agnès; Collet, Guillaume; Kieda, Claudine; Li, Tao; Geib, Steven J; Rosi, Nathaniel L; Petoud, Stéphane

    2013-10-22

    We have created unique near-infrared (NIR)-emitting nanoscale metal-organic frameworks (nano-MOFs) incorporating a high density of Yb(3+) lanthanide cations and sensitizers derived from phenylene. We establish here that these nano-MOFs can be incorporated into living cells for NIR imaging. Specifically, we introduce bulk and nano-Yb-phenylenevinylenedicarboxylate-3 (nano-Yb-PVDC-3), a unique MOF based on a PVDC sensitizer-ligand and Yb(3+) NIR-emitting lanthanide cations. This material has been structurally characterized, its stability in various media has been assessed, and its luminescent properties have been studied. We demonstrate that it is stable in certain specific biological media, does not photobleach, and has an IC50 of 100 μg/mL, which is sufficient to allow live cell imaging. Confocal microscopy and inductively coupled plasma measurements reveal that nano-Yb-PVDC-3 can be internalized by cells with a cytoplasmic localization. Despite its relatively low quantum yield, nano-Yb-PVDC-3 emits a sufficient number of photons per unit volume to serve as a NIR-emitting reporter for imaging living HeLa and NIH 3T3 cells. NIR microscopy allows for highly efficient discrimination between the nano-MOF emission signal and the cellular autofluorescence arising from biological material. This work represents a demonstration of the possibility of using NIR lanthanide emission for biological imaging applications in living cells with single-photon excitation.

  5. Highly sensitive nonlinear luminescent ceramics for volumetric and multilayer data carriers

    Energy Technology Data Exchange (ETDEWEB)

    Martynovich, E F; Dresvyanskiy, V P [Irkutsk Branch of Institute of Laser Physics, Siberian Branch, Russian Academy of Sciences, Irkutsk (Russian Federation); Voitovich, A P [B.I. Stepanov Institute of Physics, National Academy of Sciences of Belarus, Minsk (Belarus); Bagayev, S N [Institute of Laser Physics, Siberian Branch, Russian Academy of Sciences, Novosibirsk (Russian Federation)

    2015-10-31

    The interaction of optical ceramics based on wide-bandgap crystals with near-IR femtosecond laser radiation is studied experimentally. The formation of luminescent centres in LiF and MgF{sub 2} ceramics under the action of single laser pulses is considered. Two interaction regimes are used. In the regime of low-aperture focusing of laser radiation (800 nm, 30 fs, 0.3 mJ), multiple selffocusing and filamentation in the samples are observed. The luminescent centres are formed in thin channels induced by light filaments. The average effective self-focusing length is ∼100 μm; the formation of luminescent centres begins at this length and ceases at a wavelength of about 380 mm. The luminescent trace (spur) induced by a single laser filament was ∼30 μm long and 1.3 μm in diameter. The second regime of light interaction with the sample was based on high-aperture focusing with a simultaneous decrease in the laser pulse energy. This led to the formation of single pits with a diameter smaller than the optical diffraction limit. The luminescent centres induced by the laser radiation were aggregated colour centres. The mechanism of their creation included the highly-nonlinear generation of electron – hole pairs in the filamentation region, their recombination with the formation of anion excitons and the decay of excitons into Fresnel defects by the Lushchik – Vitol – Hersh – Pooley mechanism, as well as their recharging, migration and aggregation. (laser applications and other topics in quantum electronics)

  6. Fabrication and spectroscopic studies on highly luminescent CdSe/CdS nanorod polymer composites.

    Science.gov (United States)

    Bomm, Jana; Büchtemann, Andreas; Fiore, Angela; Manna, Liberato; Nelson, James H; Hill, Diana; van Sark, Wilfried G J H M

    2010-01-01

    Highly luminescent nanocomposites were prepared by incorporating CdSe/CdS core/shell nanorods into different polymer matrices. The resulting nanocomposites show high transparency of up to 93%. A photoluminescence quantum efficiency of 70% was obtained, with an optimum combination of nanorod (0.05 wt %) and at a UV-initiator concentration of 0.1 wt % for poly(lauryl methacrylate). Nanorods tend to agglomerate in cellulose triacetate.

  7. Fabrication and spectroscopic studies on highly luminescent CdSe/CdS nanorod polymer composites

    Directory of Open Access Journals (Sweden)

    Jana Bomm

    2010-11-01

    Full Text Available Highly luminescent nanocomposites were prepared by incorporating CdSe/CdS core/shell nanorods into different polymer matrices. The resulting nanocomposites show high transparency of up to 93%. A photoluminescence quantum efficiency of 70% was obtained, with an optimum combination of nanorod (0.05 wt % and at a UV-initiator concentration of 0.1 wt % for poly(lauryl methacrylate. Nanorods tend to agglomerate in cellulose triacetate.

  8. Ionization Energies of Lanthanides

    Science.gov (United States)

    Lang, Peter F.; Smith, Barry C.

    2010-01-01

    This article describes how data are used to analyze the pattern of ionization energies of the lanthanide elements. Different observed pathways of ionization between different ground states are discussed, and the effects of pairing, exchange, and orbital interactions on ionization energies of the lanthanides are evaluated. When all the above…

  9. Photochromic Terbium Phosphonates with Photomodulated Luminescence and Metal Ion Sensitive Detection.

    Science.gov (United States)

    Yang, Weiting; Tian, Hong-Rui; Li, Jian-Ping; Hui, Yuan-Feng; He, Xiang; Li, Jiyang; Dang, Song; Xie, Zhigang; Sun, Zhong-Ming

    2016-10-17

    Rational selection and modification of rare earth metal centers and photoactive organic linkers enables designable multiphotofunctionality to come to fruition in new hybrid coordination polymer materials. By using a viologen-functionalized diphosphonate linker, two terbium phosphonate compounds (Tb-1 and Tb-2) have been constructed, which display reversible photochromic reactions in response to UV light and soft X-ray irradiation. In addition, the photo-induced electron-transfer reaction can modulate the luminescent emission to thus realize photoluminescence switching behavior. Furthermore, both terbium phosphonates can serve as highly sensitive sensors to probe Cu(2+) in solution through their luminescence. Thus, they represent the first photochromic examples of lanthanide phosphonate-based materials with photomodulated luminescence and sensitive detection of metal ions.

  10. Highly luminescent mono- and multilayers of immobilized CdTe nanocrystals: controlling optical properties through post chemical surface modification.

    Science.gov (United States)

    Tsuruoka, Takaaki; Takahashi, Rena; Nakamura, Toshihiro; Fujii, Minoru; Akamatsu, Kensuke; Nawafune, Hidemi

    2008-04-14

    The significant fluorescence enhancement of immobilized CdTe nanocrystals through chemical surface modifications is described, enabling us to fabricate stable, highly luminescent thin films and patterns of nanocrystal mono- and mutilayers.

  11. Aromatic Lateral Substituents Influence the Excitation Energies of Hexaaza Lanthanide Macrocyclic Complexes: A Wave Function Theory and Density Functional Study.

    Science.gov (United States)

    Rabanal-León, Walter A; Murillo-López, Juliana A; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

    2015-09-24

    The high interest in lanthanide chemistry, and particularly in their luminescence, has been encouraged by the need of understanding the lanthanide chemical coordination and how the design of new luminescent materials can be affected by this. This work is focused on the understanding of the electronic structure, bonding nature, and optical properties of a set of lanthanide hexaaza macrocyclic complexes, which can lead to potential optical applications. Here we found that the DFT ground state of the open-shell complexes are mainly characterized by the manifold of low lying f states, having small HOMO-LUMO energy gaps. The results obtained from the wave function theory calculations (SO-RASSI) put on evidence the multiconfigurational character of their ground state and it is observed that the large spin-orbit coupling and the weak crystal field produce a strong mix of the ground and the excited states. The electron localization function (ELF) and the energy decomposition analysis (EDA) support the idea of a dative interaction between the macrocyclic ligand and the lanthanide center for all the studied systems; noting that, this interaction has a covalent character, where the d-orbital participation is evidenced from NBO analysis, leaving the f shell completely noninteracting in the chemical bonding. From the optical part we observed in all cases the characteristic intraligand (IL) (π-π*) and ligand to metal charge-transfer (LMCT) bands that are present in the ultraviolet and visible regions, and for the open-shell complexes we found the inherent f-f electronic transitions on the visible and near-infrared region.

  12. Particle image velocimetry of highly luminescent, pressurized combustion flows of aero engine combustors

    OpenAIRE

    Schroll, Michael; Klinner, Joachim; Lange, Lena; Willert, Christian

    2013-01-01

    This contribution describes recent efforts leading toward the successful application of particle image velocimetry (PIV) in highly luminescent flames avoiding saturation of the second frame of commonly available double shutter PIV cameras, which is usually inevitable when using their interline-transfer CCD sensors. Information on fuel placement, reaction zone and temperature field among other quantities can be provided by frequently used spectroscopic techniques. The velocity information is o...

  13. Lanthanide substitution by high pressure in the RuSr{sub 2}GdCu{sub 2}O{sub 8} magnetic superconductor

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz-Bustos, R.; Gallardo-Amores, J.M.; Saez-Puche, R.; Moran, E.; Alario-Franco, M.A

    2002-11-15

    A systematic study of the structural and magnetic properties of the family RuSr{sub 2}RECu{sub 2}O{sub 8} (RE=Er, Ho, Y, Dy, Tb, Gd and Eu) has been performed. All these materials appear to be tetragonal (P4/mmm) and the unit cell volume decreases along with the lanthanide ion dimension. Differences are observed in the magnetic behaviour of these compounds. High pressure and high temperature are needed to synthesize most of the members of this family.

  14. Non-leachable highly luminescent ordered mesoporous SiO2 spherical particles

    Science.gov (United States)

    Rocha, L. A.; Caiut, J. M. A.; Messaddeq, Y.; Ribeiro, S. J. L.; Martines, M. A. U.; Freiria, J. do C.; Dexpert-Ghys, J.; Verelst, M.

    2010-04-01

    Ordered mesoporous highly luminescent SiO2 particles have been synthesized by spray pyrolysis from solutions containing tetraethylorthosilicate (TEOS) and either cetyltrimethylammonium bromide (CTAB) or the block copolymer Pluronic F-68 as structure-directing agents. Rhodamine B (RhB)-containing samples were prepared by using a simple wet impregnation method followed by the growing of a second silica shell in order to prevent leaching of the dye. The obtained materials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder x-ray diffraction (XRD), ultraviolet-visible spectroscopy (UV-vis) and photoluminescence (PL). Powders with polydisperse spherical grains were obtained displaying an ordered hexagonal array of mesochannels. Luminescence results reveal that RhB molecules have been successfully encapsulated into the channels of mesoporous particles as monomeric species and that a well-defined silica coating hindered dye leaching.

  15. X-ray-induced radiophotodynamic therapy (RPDT) using lanthanide micelles: Beyond depth limitations

    Institute of Scientific and Technical Information of China (English)

    Slavka Kascakova[1,2; Alexandre Giuliani[1,3; Sara Lacerda[4; Agnes Pallier[4; Pascal Mercere[1; eva Toth[4; Matthieu Refregiers[1

    2015-01-01

    We report lanthanide-based micelles integrating hypericin (Hyp) for X-ray- triggered photodynamic therapy (PDT). The lanthanide luminescence induced by X-ray irradiation excites the photosensitizer, which leads to the generation of singlet oxygen. This versatile approach can be extended to other photosensitizers or other types of liponanoparticles and can allow for magnetic resonance imaging (MRI) guidance.

  16. Monitoring Delamination of Thermal Barrier Coatings During Interrupted High-Heat-Flux Laser Testing using Luminescence Imaging

    Science.gov (United States)

    Eldridge, Jeffrey I.; Zhu, Dongming; Wolfe, Douglas E.

    2011-01-01

    This presentation showed progress made in extending luminescence-base delamination monitoring to TBCs exposed to high heat fluxes, which is an environment that much better simulates actual turbine engine conditions. This was done by performing upconversion luminescence imaging during interruptions in laser testing, where a high-power CO2 laser was employed to create the desired heat flux. Upconverison luminescence refers to luminescence where the emission is at a higher energy (shorter wavelength) than the excitation. Since there will be negligible background emission at higher energies than the excitation, this methods produces superb contrast. Delamination contrast is produced because both the excitation and emission wavelengths are reflected at delamination cracks so that substantially higher luminescence intensity is observed in regions containing delamination cracks. Erbium was selected as the dopant for luminescence specifically because it exhibits upconversion luminescence. The high power CO2 10.6 micron wavelength laser facility at NASA GRC was used to produce the heat flux in combination with forced air backside cooling. Testing was performed at a lower (95 W/sq cm) and higher (125 W/sq cm) heat flux as well as furnace cycling at 1163C for comparison. The lower heat flux showed the same general behavior as furnace cycling, a gradual, "spotty" increase in luminescence associated with debond progression; however, a significant difference was a pronounced incubation period followed by acceleration delamination progression. These results indicate that extrapolating behavior from furnace cycling measurements will grossly overestimate remaining life under high heat flux conditions. The higher heat flux results were not only accelerated, but much different in character. Extreme bond coat rumpling occurred, and delamination propagation extended over much larger areas before precipitating macroscopic TBC failure. This indicates that under the higher heat flux (and

  17. Magnetic and fluorescent Gd2O3:Yb3+/Ln3+ nanoparticles for simultaneous upconversion luminescence/MR dual modal imaging and NIR-induced photodynamic therapy

    OpenAIRE

    LIU Jun; Huang, Long; Tian, Xiumei; Chen, Xiaoming; Shao, Yuanzhi; Xie, Fukang; Chen, Dihu; Li, Li

    2016-01-01

    The development of upconversion nanoparticles (UCNs) for theranostics application is a new strategy toward the accurate diagnosis and efficient treatment of cancer. Here, magnetic and fluorescent lanthanide-doped gadolinium oxide (Gd2O3) UCNs with bright upconversion luminescence (UCL) and high longitudinal relaxivity (r 1) are used for simultaneous magnetic resonance imaging (MRI)/UCL dual-modal imaging and photodynamic therapy (PDT). In vitro and in vivo MRI studies show that these products...

  18. A 5-kg time-resolved luminescence photometer with multiple excitation sources

    Science.gov (United States)

    A portable fluorometer was developed to detect food contaminants and environmental pollutants including, in particular, two classes of antibiotics: tetracyclines and fluoroquinolones. Time resolution was implemented to take advantage of lanthanide-sensitized luminescence. Excitation sources included...

  19. The Lanthanide Contraction Revisited

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, Michael; Oliver, Allen G.; Raymond, Kenneth N.

    2007-04-19

    A complete, isostructural series of lanthanide complexes (except Pm) with the ligand TREN-1,2-HOIQO has been synthesized and structurally characterized by means of single-crystal X-ray analysis. All complexes are 1D-polymeric species in the solid state, with the lanthanide being in an eight-coordinate, distorted trigonal-dodecahedral environment with a donor set of eight unique oxygen atoms. This series constitutes the first complete set of isostructural lanthanide complexes with a ligand of denticity greater than two. The geometric arrangement of the chelating moieties slightly deviates across the lanthanide series, as analyzed by a shape parameter metric based on the comparison of the dihedral angles along all edges of the coordination polyhedron. The apparent lanthanide contraction in the individual Ln-O bond lengths deviates considerably from the expected quadratic decrease that was found previously in a number of complexes with ligands of low denticity. The sum of all bond lengths around the trivalent metal cation, however, is more regular, showing an almost ideal quadratic behavior across the entire series. The quadratic nature of the lanthanide contraction is derived theoretically from Slater's model for the calculation of ionic radii. In addition, the sum of all distances along the edges of the coordination polyhedron show exactly the same quadratic dependency as the Ln-X bond lengths. The universal validity of this coordination sphere contraction, concomitant with the quadratic decrease in Ln-X bond lengths, was confirmed by reexamination of four other, previously published, almost complete series of lanthanide complexes. Due to the importance of multidentate ligands for the chelation of rare-earth metals, this result provides a significant advance for the prediction and rationalization of the geometric features of the corresponding lanthanide complexes, with great potential impact for all aspects of lanthanide coordination.

  20. Recent Progress on Spectroscopy of Lanthanide Ions Incorporated in Semiconductor Nanocrystals

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Doping luminescent lanthanide ions into semiconductor nanocrystals is an ideal approach for developing nano-devices for various applications. Quantum confinement effects are expected for lanthanide ions doped in small semiconductor nanocrystals. The most recent progress on the synthesis and spectroscopy of lanthanide ions in various semiconductor nanocrystals such as Ⅱ-Ⅵ, Ⅲ-Ⅴ and Ⅳ-Ⅵ families were systematically reviewed, focusing on our recent findings on the optical spectroscopy of Eu3+ doped in ZnO and TiO2 nanocrystals by wet chemical synthesis. The energy transfer from the band-gap excitation to lanthanides further confirmed that lanthanide ions could be successfully incorporated into the lattice sites in spite of the mismatch in ionic radii.

  1. Lanthanide complexes that respond to changes in cyanide concentration in water

    Energy Technology Data Exchange (ETDEWEB)

    Routledge, Jack D.; Zhang, Xuejian; Connolly, Michael; Tropiano, Manuel; Blackburn, Octavia A.; Beer, Paul D.; Aldridge, Simon; Faulkner, Stephen [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford (United Kingdom); Kenwright, Alan M. [Department of Chemistry, Durham University (United Kingdom)

    2017-06-26

    Cyanide ions are shown to interact with lanthanide complexes of phenacylDO3A derivatives in aqueous solution, giving rise to changes in the luminescence and NMR spectra. These changes are the consequence of cyanohydrin formation, which is favored by the coordination of the phenacyl carbonyl group to the lanthanide center. These complexes display minimal affinity for fluoride and can detect cyanide at concentrations less than 1 μm. By contrast, lanthanide complexes with DOTAM derivatives display no affinity for cyanide in water, but respond to changes in fluoride concentration. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Luminescence Instrumentation

    DEFF Research Database (Denmark)

    Jain, Mayank; Bøtter-Jensen, Lars

    2014-01-01

    This chapter gives an introduction to instrumentation for stimulated luminescence studies, with special focus on luminescence dating using the natural dosimeters, quartz and feldspars. The chapter covers basic concepts in luminescence detection, and thermal and optical stimulation, and reference...

  3. Experimental and first-principles studies of high-pressure effects on the structural, electronic, and optical properties of semiconductors and lanthanide doped solids

    Science.gov (United States)

    Brik, Mikhail G.; Mahlik, Sebastian; Jankowski, Dawid; Strak, Pawel; Korona, Krzysztof P.; Monroy, Eva; Krukowski, Stanislaw; Kaminska, Agata

    2017-05-01

    In this paper we present a broad overview of our recent experimental and theoretical results obtained for different types of materials: CdTe and CuGa1- x In x S2 chalcopyrite semiconductors, GaN/AlN wide band gap semiconductor quantum wells, and lanthanide-doped dielectric materials. The analysis of pressure-induced phase transitions, variations of the band gaps, refractive index and the pressure dependence of optical properties of these materials is discussed. The presented results show that the high pressure technique is a very useful tool for scientific research and development of of light-emitting technologies. It allows for identification of radiative recombination mechanisms in solid-state light emitters. In polar III-nitride semiconductors, ab initio calculations revealed that the pressure-induced change of the band gap plays minor role, whereas the built-in electric field in heterostructures increases with pressure thus affecting their basic physical properties, i.e., producing a large red-shift of the photoluminescence and lowering the quantum efficiency due to the quantum confined Stark effect. For wide (>4 nm) quantum wells, the reduction of the band-to-band emission efficiency leads to deep defect dominant emission which is almost pressure independent. The observed behavior proves that pressure investigations combined with ab initio calculations can identify the nature of the optical transitions and the main physical factors affecting the radiative efficiency in polar quantum well systems. Furthermore, high pressure studies of the emission and excitation spectra of Y2O2S doped with Tb3+ and Eu3+ allowed estimating the energies of the ground states of all divalent and trivalent lanthanide ions in respect to the valence and conduction band edges of the Y2O2S host. Band gap energy and difference between energies of the ground states of lanthanide ions and band edges have been calculated as a function of pressure. It is shown that pressure causes an

  4. Scintillation luminescence for high-pressure xenon gas

    Science.gov (United States)

    Kobayashi, S.; Hasebe, N.; Igarashi, T.; Kobayashi, M.-N.; Miyachi, T.; Miyajima, M.; Okada, H.; Okudaira, O.; Tezuka, C.; Yokoyama, E.; Doke, T.; Shibamura, E.; Dmitrenko, V. V.; Ulin, S. E.; Vlasik, K. F.

    2004-09-01

    Scintillation and ionization yields in xenon gas for 5.49MeV alpha-particles were measured in the range of pressure from 0.35 to 3.7MPa and the electric field strength (E) over the number density of xenon atoms (N), E/N from 0 to 5×10-18Vcm2. When our data are normalized at the data point measured by Saito et al., the number of scintillation photons is 2.3×105 while the number of ionization electrons is 2.0×105 at 2.6MPa and at 3.7×10-18Vcm2. The scintillation and ionization yields of xenon doped with 0.2% hydrogen, High-Pressure Xenon gas[H2-0.2%], at 2.6MPa was also measured. Scintillation yield of the Xe-H2 mixture gas is 80% as high as that of pure xenon. It is found that the scintillation yield is luminous enough to generate a trigger pulse of the high-pressure xenon time projection chamber, which is expected as a promising MeV Compton gamma-ray camera.

  5. High thermoelectric performance of reduced lanthanide molybdenum oxides densified by spark plasma sintering

    DEFF Research Database (Denmark)

    Xu, Jianxiao Jackie; Sonne, Monica; Yanangiya, Shun-ichi

    2010-01-01

    Four highly reduced molybdenum oxides LnMo8O14 (Ln = La, Ce, Nd and Sm) containing bicapped Mo8 clusters were synthesized via solid state reaction followed by spark plasma sintering. The thermoelectric properties were investigated, and NdMo8O14 exhibits the best performance with the maximum power...

  6. Theoretical description of the octupole phase transition in Lanthanide nuclei at high spin

    CERN Document Server

    Garrote, E; Robledo, L M

    1999-01-01

    The phase transition to reflection asymmetric intrinsic nuclear shapes at high angular momentum is analyzed in the framework of the cranked Hartree-Fock-Bogoliubov approximation, with the Gogny interaction, using approximate parity projection before variation. The N=88 isotones are studied and good agreement is found for the energy splitting and dipole moments before and after the transition.

  7. Lanthanide and actinide chemistry at high C/O ratios in the solar nebula

    Science.gov (United States)

    Lodders, Katharina; Fegley, Bruce, Jr.

    1993-01-01

    Chemical equilibrium calculations were performed to study the condensation chemistry of the REE and actinides under the highly reducing conditions which are necessary for the formation of the enstatite chondrites. Our calculations confirm that the REE and actinides condensed into oldhamite (CaS), the major REE and actinide host phase in enstatite chondrites, at a carbon-oxygen (C/O) ratio not less than 1 in an otherwise solar gas. Five basic types of REE abundance patterns, several of which are analogous to REE abundance patterns observed in the Ca, Al-rich inclusions in carbonaceous chondrites, are predicted to occur in meteoritic oldhamites. All of the reported REE patterns in oldhamites in enstatite chondrites can be interpreted in terms of our condensation calculations. The observed patterns fall into three of the five predicted categories. The reported Th and U enrichments and ratios in meteoritic oldhamites are also consistent with predictions of the condensation calculations. Pure REE sulfides are predicted to condense in the 10 exp -6 to 10 exp -9 bar range and may be found in enstatite chondrites if they formed in this pressure range.

  8. Highly luminescent, stable, transparent and flexible perovskite quantum dot gels towards light-emitting diodes

    Science.gov (United States)

    Sun, Chun; Shen, Xinyu; Zhang, Yu; Wang, Yu; Chen, Xingru; Ji, Changyin; Shen, Hongzhi; Shi, Hengchong; Wang, Yiding; Yu, William W.

    2017-09-01

    By controlling the hydrolysis of alkoxysilanes, highly luminescent, transparent and flexible perovskite quantum dot (QD) gels were synthesized. The gels could maintain the structure without shrinking and exhibited excellent stability comparing to the QDs in solution. This in situ fabrication can be easily scaled up for large-area/volume gels. The gels integrated the merits of the polymer matrices to avoid the non-uniformity of light output, making it convenient for practical LED applications. Monochrome and white LEDs were fabricated using these QD gels; the LEDs exhibited broader color gamut, demonstrating better property in the backlight display application.

  9. Development of highly luminescent and cytocompatible near-IR-emitting aqueous Ag2S quantum dots

    OpenAIRE

    Hocaoğlu, İbrahim; Sennaroğlu, Alphan ; Acar, Funda Havva Yağcı; Çizmeciyan, M. Natali; Erdem, Rengin ; Özen, Can ; Kurt, Adnan

    2012-01-01

    Colloidally stable and highly luminescent near-IR emitting Ag2S quantum dots (NIRQDs) were prepared by a very simple aqueous method using 2-mercaptopropionic acid (2MPA) as a coating. Emission of Ag2S-2MPA NIRQDs can be tuned between 780 and 950 nm. These NIRQDs have photoluminescence quantum yields (PLQY) around 7–39% and exhibit excellent cytocompatibility even at 600 mg mL 1 in NIH/3T3 cells. With such improved properties, Ag2S-2MPA NIRQDs have a great potential in practical...

  10. Liquid-crystalline lanthanide complexes

    OpenAIRE

    Binnemans, Koen

    1999-01-01

    The paper describes the recent developments in the field of liquid-crystalline lanthanide complexes. The role of trivalent lanthanide ions as the central metal ion in metallomesogens is considered. An outlook for the future is given.

  11. Three-Dimensional Energy Transport in Highly Luminescent Host-Guest Crystals: A Quantitative Experimental and Theoretical Study

    DEFF Research Database (Denmark)

    Poulsen, Lars; Jazdzyk, M; Communal, J.-E.

    2007-01-01

    We present a combined experimental and theoretical study on energy transfer processes in a well-defined three-dimensional host-guest system, which allows for high chromophore concentrations while maintaining the highly luminescent properties of the molecules in solution. The self-assembled, nanos......We present a combined experimental and theoretical study on energy transfer processes in a well-defined three-dimensional host-guest system, which allows for high chromophore concentrations while maintaining the highly luminescent properties of the molecules in solution. The self...

  12. Thermolysis of lanthanide dithiocarbamate complexes

    Science.gov (United States)

    Boncher, William L.; Regulacio, Michelle D.; Stoll, Sarah L.

    2010-01-01

    Polycrystalline lanthanide sulfide materials were formed at low temperatures using a single-source precursor based on the lanthanide dithiocarbamate complex. The synthesis temperatures are generally lower than standard solid state preparations, avoid toxic sulfurizing gases and provide a convenient route to prepare lanthanide chalcogenide nanoparticles. Depending on the reaction conditions and oxophilicity of the lanthanide, the sulfide material was formed with oxidized products including oxysulfides, oxysulfates and the oxide.

  13. Photoluminescence properties of lanthanide-organic frameworks (LnOFs) with thiophene-2,5-dicarboxylate and acetate

    Energy Technology Data Exchange (ETDEWEB)

    Han, Jing; Wei, Qing; Xie, Gang; Chen, Sanping [Key Lab. of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest Univ., Xi' an, Shaanxi (China); Zhang, Sheng [Key Lab. of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest Univ., Xi' an, Shaanxi (China); College of Chemistry and Chemical Engineering, Baoji Univ. of Arts and Science, Baoji, Shaanxi (China)

    2017-07-17

    S-heterocyclic dicarboxylic acid, thiophene-2,5-dicarboxylic acid (H{sub 2}TDC), was employed to construct a series of lanthanide-organic frameworks (LnOFs) with coligand acetate, formulated as [Ln(TDC)(OAc)(H{sub 2}O)]{sub n} [Ln = Eu (1), Tb (2), Gd (3), Dy (4), Sm (5)] under hydrothermal conditions. Structure analysis reveals that 1-5 have dinuclear 3D metal organic frameworks (MOFs), in which TDC{sup 2-} and OAc{sup -} display (κ{sup 1}-κ{sup 1})-(κ{sup 1}-κ{sup 1})-μ{sub 4} and (κ{sup 2}-κ{sup 1})-μ{sub 2} coordination fashions, respectively. The dehydrated products of all compounds show high thermal stability above 410 C. As for 1, 2, 4, and 5, the photoluminescence analyses exhibit characteristic luminescence emission bands of the corresponding lanthanide ions in the visible region. In particular, compound 2 displays bright green luminescence in the solid state with {sup 5}D{sub 4} lifetime of 0.510 ms and relative high overall quantum yield of 16 %, based on an ideal energy gap between the lowest triplet state energy level of H{sub 2}TDC ligand and the {sup 5}D{sub 4} state energy level of Tb{sup 3+}. The energy transfer mechanisms in compounds 1 and 2 were also discussed. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Synthesis of Luminescent Graphene Quantum Dots with High Quantum Yield and Their Toxicity Study.

    Directory of Open Access Journals (Sweden)

    Dan Jiang

    Full Text Available High fluorescence quantum yield graphene quantum dots (GQDs have showed up as a new generation for bioimaging. In this work, luminescent GQDs were prepared by an ameliorative photo-Fenton reaction and a subsequent hydrothermal process using graphene oxide sheets as the precursor. The as-prepared GQDs were nanomaterials with size ranging from 2.3 to 6.4 nm and emitted intense green luminescence in water. The fluorescence quantum yield was as high as 24.6% (excited at 340 nm and the fluorescence was strongest at pH 7. Moreover, the influences of low-concentration (12.5, 25 μg/mL GQDs on the morphology, viability, membrane integrity, internal cellular reactive oxygen species level and mortality of HeLa cells were relatively weak, and the in vitro imaging demonstrated GQDs were mainly in the cytoplasm region. More strikingly, zebrafish embryos were co-cultured with GQDs for in vivo imaging, and the results of heart rate test showed the intake of small amounts of GQDs brought little harm to the cardiovascular of zebrafish. GQDs with high quantum yield and strong photoluminescence show good biocompatibility, thus they show good promising for cell imaging, biolabeling and other biomedical applications.

  15. Microwave synthesis of homogeneous and highly luminescent BCNO nanoparticles for the light emitting polymer materials

    Energy Technology Data Exchange (ETDEWEB)

    Iwasaki, Hideharu [Battery Materials Laboratory, Kurashiki Research Center, Kuraray Co., Ltd., 2045-1, Sakazu, Kurashiki, Okayama 710-0801 (Japan); Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi Hiroshima 739 8527 (Japan); Ogi, Takashi, E-mail: ogit@hiroshima-u.ac.jp [Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi Hiroshima 739 8527 (Japan); Iskandar, Ferry [Department of Physics, Institute of Technology Bandung, Ganesha 10, Bandung 40132, West Java (Indonesia); Aishima, Kana; Okuyama, Kikuo [Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi Hiroshima 739 8527 (Japan)

    2015-10-15

    Nano-sized boron carbon oxynitride (BCNO) phosphors around 50 nm containing no rare earth metal and free from color heterogeneity were synthesized from mixtures of boric acid, urea, and citric acid by microwave heating with substantially shorter reaction times and lower temperatures than in the conventional BCNO preparation method such as electric-furnace heating. The emission wavelength of the phosphors varied with the mixing ratio of raw materials and it was found that lowering the proportion of urea to boric acid or citric acid tended to increase the internal quantum yield and shorten the emission wavelength under excitation at 365 nm. It was also found for the first time that a light-emitting polymer could be synthesized from a mixture of the prepared BCNO nanoparticles and a polyvinyl alcohol. This polymer composite exhibited uniform dispersion and stabilization of the luminescence and had a high internal quantum yield of 54%, which was higher than that of the phosphor alone. - Highlights: • Nano-sized BCNO phosphor was synthesized via microwave heating. • BCNO nanophosphor has homogeneous and high luminescence. • Emission wavelength was tunable by changing the ratio of precursor components. • BCNO nanophosphor can be easily dispersed in a polyvinyl alcohol. • BCNO–polymer composite exhibited uniform high internal quantum yield.

  16. 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.

  17. Lanthanide-based laser-induced phosphorescence for spray diagnostics

    Energy Technology Data Exchange (ETDEWEB)

    Voort, D. D. van der, E-mail: d.d.v.d.voort@tue.nl; Water, W. van de; Kunnen, R. P. J.; Clercx, H. J. H.; Heijst, G. J. F. van [Applied Physics Department, Eindhoven University of Technology, 5612 AZ Eindhoven (Netherlands); Maes, N. C. J.; Sweep, A. M.; Dam, N. J. [Mechanical Engineering Department, Eindhoven University of Technology, 5612 AZ Eindhoven (Netherlands); Lamberts, T. [Institute of Theoretical Chemistry, University of Stuttgart, D-70569 Stuttgart (Germany)

    2016-03-15

    Laser-induced phosphorescence (LIP) is a relatively recent and versatile development for studying flow dynamics. This work investigates certain lanthanide-based molecular complexes for their use in LIP for high-speed sprays. Lanthanide complexes in solutions have been shown to possess long phosphorescence lifetimes (∼1-2 ms) and to emit light in the visible wavelength range. In particular, europium and terbium complexes are investigated using fluorescence/phosphorescence spectrometry, showing that europium-thenoyltrifluoracetone-trioctylphosphineoxide (Eu-TTA-TOPO) can be easily and efficiently excited using a standard frequency-tripled Nd:YAG laser. The emitted spectrum, with maximum intensity at a wavelength of 614 nm, is shown not to vary strongly with temperature (293-383 K). The decay constant of the phosphorescence, while independent of ambient pressure, decreases by approximately 12 μs/K between 323 and 373 K, with the base level of the decay constant dependent on the used solvent. The complex does not luminesce in the gas or solid state, meaning only the liquid phase is visualized, even in an evaporating spray. By using an internally excited spray containing the phosphorescent complex, the effect of vaporization is shown through the decrease in measured intensity over the length of the spray, together with droplet size measurements using interferometric particle imaging. This study shows that LIP, using the Eu-TTA-TOPO complex, can be used with different solvents, including diesel surrogates. Furthermore, it can be easily handled and used in sprays to investigate spray breakup and evaporation.

  18. Highly luminescent polycaprolactone films doped with diaquatris(thenoyltrifluoroacetonate)europium(III) complex

    Energy Technology Data Exchange (ETDEWEB)

    Forster, Pedro L., E-mail: plforster@ipen.br [Nuclear and Energy Research Institute, National Nuclear Energy Commission, Avenida Professor Lineu Prestes 2242, Cidade Universitária, CEP 05508-000 São Paulo, SP (Brazil); Parra, Duclerc F., E-mail: dfparra@ipen.br [Nuclear and Energy Research Institute, National Nuclear Energy Commission, Avenida Professor Lineu Prestes 2242, Cidade Universitária, CEP 05508-000 São Paulo, SP (Brazil); Lugao, Ademar B. [Nuclear and Energy Research Institute, National Nuclear Energy Commission, Avenida Professor Lineu Prestes 2242, Cidade Universitária, CEP 05508-000 São Paulo, SP (Brazil); Kai, Jiang, E-mail: jkai@puc-rio.br [Department of Chemistry, Pontifical Catholic University of Rio de Janeiro, Rua Marquês de São Vicente 225, Gávea, CEP 22451-900 Rio de Janeiro, RJ (Brazil); Brito, Hermi F., E-mail: hefbrito@iq.usp.br [Institute of Chemistry, University of São Paulo, Avenida Professor Lineu Prestes 748, Cidade Universitária, CEP 05508-000 São Paulo, SP (Brazil)

    2015-11-15

    In this work we report the preparation, characterization, thermal and luminescence properties of highly luminescent polycaprolactone (PCL) polymer films incorporated with diaquatris(thenoyltrifluoroacetonate)europium(III) complex [Eu(tta){sub 3}(H{sub 2}O){sub 2}] (doping concentration at 1, 2, 5, 10 and 15 wt%). Thermogravimetry analysis (TGA) showed no weight loss in the range of 323–473 K for the polymeric systems, suggesting that the interaction between the polymer matrix and the Eu{sup 3+}-complex occurs when the carbonyl groups along the polymer backbone substitute the water molecules in the complex precursor. Differential scanning calorimetry (DSC) showed no significant changes in T{sub m} for the film samples, however crystallinity is affected by non combined complex in the polymer chains. The changes in the curve-fitted FTIR spectral areas for each component peak are gradually changed with the increase of doping concentration. The displacement of the C–O for the β-diketonate complex to new positions in PCLE systems provide good evidence that the metal ion is coordinated through the oxygen atoms deriving from PCL. The observation of characteristic emission bands arising from the {sup 5}D{sub 0}→{sup 7}F{sub J} transitions (J=0–4) dominated by the hypersensitive {sup 5}D{sub 0}→{sup 7}F{sub 2} transition at around 614 nm of Eu{sup 3+} ion indicates the incorporation of the Eu{sup 3+} ions in the system corroborating with the CHN and IR data. Luminescence quenching is observed, with the film of 5% doping concentration of the Eu{sup 3+} complexes showing the highest luminescence intensity among all samples. - Highlights: • Distribution of metal ion along polymer chains influences the fluorescence properties. • PCL acts as co-sensitizer to improve energy transfer from the tta{sup −} ligand to the Eu{sup 3+}. • PCL polymer films doped with Eu{sup 3+} enhance quantum yield and lifetimes. • PCL doping process restrains the polymeric

  19. Silica-modified monodisperse hexagonal lanthanide nanocrystals: synthesis and biological properties.

    Science.gov (United States)

    Kostiv, U; Janoušková, O; Šlouf, M; Kotov, N; Engstová, H; Smolková, K; Ježek, P; Horák, D

    2015-11-21

    Oleic acid-stabilized hexagonal NaYF4:Yb(3+)/Er(3+) nanocrystals, emitting green and red luminescence, were prepared by the high-temperature co-precipitation of lanthanide chlorides. By varying the reaction time and the Ln(3+)/Na(+) ratio, the nanocrystal size can be controlled within the range 16-270 nm. The maximum upconversion quantum yield is achieved under 970 nm excitation. The reverse microemulsion technique using hydrolysis and condensation of tetraethoxysilane is a suitable method to coat the nanocrystal surface with a silica shell to make the particles dispersible and colloidally stable in aqueous media. During the subsequent functionalization, (3-aminopropyl)trimethoxysilane introduced amino groups onto the silica to enable future bioconjugation with the target molecules. All specimens were characterized by TEM microscopy, electron and X-ray diffraction, ATR FT-IR spectroscopy, and upconversion luminescence. Finally, in vitro cytotoxicity and intracellular nanoparticle uptake (using confocal microscopy) were determined with human cervical carcinoma HeLa and mRoGFP HeLa cells, respectively. From the investigated particles, amino-functionalized NaYF4:Yb(3+)/Er(3+) nanocrystals internalized into the cells most efficiently. The nanoparticles proved to be nontoxic at moderate concentrations, which is important when considering their prospective application in biolabeling and luminescence imaging of various cell types.

  20. Syntheses, structures, molecular and cationic recognitions and catalytic properties of two lanthanide coordination polymers based on a flexible tricarboxylate

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Yu; Wang, Yan-Mei; Xu, Ji; Liu, Pan; Weththasinha, H.A.B.M.D.; Wu, Yun-Long; Lu, Xiao-Qing; Xie, Ji-Min, E-mail: xiejm391@sohu.com

    2014-11-15

    Two lanthanide coordination polymers, namely, ([La(TTTA)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (La-TTTA) and [Nd(TTTA)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (Nd-TTTA) have been hydrothermally synthesized through the reaction of lanthanide ions (La{sup 3+} and Nd{sup 3+}) with the flexible tripodal ligand 2,2′,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid (H{sub 3}TTTA). La-TTTA and Nd-TTTA are isostructural and both show three dimensional structures. La-TTTA and Nd-TTTA show good recognition of amine molecules via quenching the luminescent intensities in amines emulsions. They can also recognize Fe{sup 3+}, Cu{sup 2+}, Mg{sup 2+}, Cr{sup 3+} and Co{sup 2+} ions with the quenching the peak around 361 nm when the compounds immersed in ionic solutions. The two compounds act as efficient Lewis acid catalysts for the cyanosilylation of benzaldehyde and derivatives in high yields shortly due to the strong Lewis acidity and the possible open sites of the lanthanide ions. - Graphical abstract: We have synthesized two isostructural 3D compounds based on H{sub 3}TTTA. They are chemical sensor of amine solvents and cations. They have higher yields and TOFs to catalyze cyanosilylation reactions. - Highlights: • The compounds show recognition of amine molecules via quenching luminescent intensities. • The compounds recognize Fe{sup 3+}, Cu{sup 2+}, Mg{sup 2+}, Cr{sup 3+} and Co{sup 2+} ions via quenching the peak around 361 nm. • They act as efficient Lewis acid catalysts for the cyanosilylation reactions in high yields.

  1. Decreasing luminescence lifetime of evaporating phosphorescent droplets

    Science.gov (United States)

    van der Voort, D. D.; Dam, N. J.; Sweep, A. M.; Kunnen, R. P. J.; van Heijst, G. J. F.; Clercx, H. J. H.; van de Water, W.

    2016-12-01

    Laser-induced phosphorescence has been used extensively to study spray dynamics. It is important to understand the influence of droplet evaporation in the interpretation of such measurements, as it increases luminescence quenching. By suspending a single evaporating n-heptane droplet in an acoustic levitator, the properties of lanthanide-complex europium-thenoyltrifluoroacetone-trioctylphosphine oxide (Eu-TTA-TOPO) phosphorescence are determined through high-speed imaging. A decrease was found in the measured phosphorescence decay coefficient (780 → 200 μs) with decreasing droplet volumes (10-9 → 10-11 m3) corresponding to increasing concentrations (10-4 → 10-2 M). This decrease continues up to the point of shell-formation at supersaturated concentrations. The diminished luminescence is shown not to be attributable to triplet-triplet annihilation, quenching between excited triplet-state molecules. Instead, the pure exponential decays found in the measurements show that a non-phosphorescent quencher, such as free TTA/TOPO, can be attributable to this decay. The concentration dependence of the phosphorescence lifetime can therefore be used as a diagnostic of evaporation in sprays.

  2. High-Contrast Visualization of Upconversion Luminescence in Mice Using Time-Gating Approach.

    Science.gov (United States)

    Zheng, Xianlin; Zhu, Xingjun; Lu, Yiqing; Zhao, Jiangbo; Feng, Wei; Jia, Guohua; Wang, Fan; Li, Fuyou; Jin, Dayong

    2016-04-01

    Optical imaging through the near-infrared (NIR) window provides deep penetration of light up to several centimeters into biological tissues. Capable of emitting 800 nm luminescence under 980 nm illumination, the recently developed upconversion nanoparticles (UCNPs) suggest a promising optical contrast agent for in vivo bioimaging. However, presently they require high-power lasers to excite when applied to small animals, leading to significant scattering background that limits the detection sensitivity as well as a detrimental thermal effect. In this work, we show that the time-gating approach implementing pulsed illumination from a NIR diode laser and time-delayed imaging synchronized via an optical chopper offers detection sensitivity more than 1 order of magnitude higher than the conventional approach using optical band-pass filters (S/N, 47321/6353 vs 5339/58), when imaging UCNPs injected into Kunming mice. The pulsed laser illumination (70 μs ON in 200 μs period) also reduces the overall thermal accumulation to 35% of that under the continuous-wave mode. Technical details are given on setting up the time-gating unit comprising an optical chopper, a pinhole, and a microscopy eyepiece. Being generally compatible with any camera, this provides a convenient and low cost solution to NIR animal imaging using UCNPs as well as other luminescent probes.

  3. Use of a highly sensitive two-dimensional luminescence imaging system to monitor endogenous bioluminescence in plant leaves

    Directory of Open Access Journals (Sweden)

    Flor-Henry Michel

    2004-11-01

    Full Text Available Abstract Background All living organisms emit spontaneous low-level bioluminescence, which can be increased in response to stress. Methods for imaging this ultra-weak luminescence have previously been limited by the sensitivity of the detection systems used. Results We developed a novel configuration of a cooled charge-coupled device (CCD for 2-dimensional imaging of light emission from biological material. In this study, we imaged photon emission from plant leaves. The equipment allowed short integration times for image acquisition, providing high resolution spatial and temporal information on bioluminescence. We were able to carry out time course imaging of both delayed chlorophyll fluorescence from whole leaves, and of low level wound-induced luminescence that we showed to be localised to sites of tissue damage. We found that wound-induced luminescence was chlorophyll-dependent and was enhanced at higher temperatures. Conclusions The data gathered on plant bioluminescence illustrate that the equipment described here represents an improvement in 2-dimensional luminescence imaging technology. Using this system, we identify chlorophyll as the origin of wound-induced luminescence from leaves.

  4. Influence of charge transfer state on Eu3+ luminescence in LaAlO3, by high pressure spectroscopy

    Science.gov (United States)

    Behrendt, Mirosław; Mahlik, Sebastian; Grinberg, Marek; Stefańska, Dagmara; Dereń, Przemysław J.

    2017-01-01

    The contribution presents spectroscopic characterization of LaAlO3 doped with 0.5 mol %. Eu3+. We measured steady state luminescence, luminescence excitation spectra, as well as the time resolved spectra and luminescence kinetics. The experiments were performed at high hydrostatic pressure applied in diamond anvil cell (DAC) which was changed from ambient to 250 kbar. We found that for all pressures the emission from the 5D0 and 5D1 excited emitting state of Eu3+ was delayed in time after excitation pulse whilst emission from the 5D2 appear immediately after excitation. At pressure above 12 kbar the strong magnification of the luminescence lines related to the transitions from the 5D3 state which were very weak at ambient condition is observed. The emission decay of the 5D3 luminescence become slower when pressure is increased. All these effects are attributed to pressure-induced increase of the energy of the ground electronic configuration 4f6 of the Eu2+ with respect to the valence band edge which results in the charge transfer state, and 5D3 level crossing.

  5. Biocompatible and high-performance amino acids-capped MnWO4 nanocasting as a novel non-lanthanide contrast agent for X-ray computed tomography and T(1)-weighted magnetic resonance imaging.

    Science.gov (United States)

    Dong, Kai; Liu, Zhen; Liu, Jianhua; Huang, Sa; Li, Zhenhua; Yuan, Qinghai; Ren, Jinsong; Qu, Xiaogang

    2014-02-21

    In the present work, a novel non-lanthanide dual-modality contrast agent, manganese tungstate (MnWO4), has been successfully constructed by a facile and versatile hydrothermal route. With the merits of a high atomic number and a well-positioned K-edge energy of tungsten, our well-prepared non-lanthanide nanoprobes provide a higher contrast efficacy than routine iodine-based agents in clinics. Additionally, the presence of Mn in these nanoparticles endow them with excellent T1-weighted MR imaging capabilities. As an alternative to T2-weighted MRI and CT dual-modality contrast agents, the nanoprobes can provide a positive contrast signal, which prevents confusion with the dark signals from hemorrhage and blood clots. To the best of our knowledge, this is the first report that a non-lanthanide imaging nanoprobe is applied for CT and T1-weighted MRI simultaneously. Moreover, comparing with gadolinium-based T1-weighted MRI and CT dual-modality contrast agents that were associated with nephrogenic systemic fibrosis (NSF), our contrast agents have superior biocompatibility, which is proved by a detailed study of the pharmacokinetics, biodistribution, and in vivo toxicology. Together with excellent dispersibility, high biocompatibility and superior contrast efficacy, these nanoprobes provide detailed and complementary information from dual-modality imaging over traditional single-mode imaging and bring more opportunities to the new generation of non-lanthanide nanoparticulate-based contrast agents.

  6. 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.

  7. Nd3+,Yb3+ and Ho3+ Codoped Oxyfluoride Glass Ceramics with High Efficient Green Upconversion Luminescence

    Institute of Scientific and Technical Information of China (English)

    ZHANG Jun-Jie; KAWAMOTO Yoji; DAI Shi-Xun; ZHANG Li-Yan; HU Li-Li

    2004-01-01

    @@ New oxyfluoride glasses and glass ceramic codoped with Nd3+, Yb3+ and Ho3+ were prepared. The x-ray diffraction analysis revealed that the heat treatments of the oxyfluoride glasses could cause the precipitation of (Nd3+, Yb3+, Ho3+)-doped fluorite-type crystals. Very strong green up-conversion luminescence due to the Ho3+: (5F4, 5S2) → 5I8 transition under 800-nm excitation was observed in these transparent glass ceramics.The intensity of the green up-conversion luminescence in a 1-mo1% YbF3-containing glass ceramic was found to be about 120 times stronger than that in the precursor oxyfluoride glass. The reason for the highly efficient Ho3+up-conversion luminescence in the oxyfluoride glass ceramics is discussed.

  8. Liquid-Phase Epitaxy Effective Encapsulation of Lanthanide Coordination Compounds into MOF Film with Homogeneous and Tunable White-Light Emission.

    Science.gov (United States)

    Gu, Zhi-Gang; Chen, Zheng; Fu, Wen-Qiang; Wang, Fei; Zhang, Jian

    2015-12-30

    As a new family of hybrid inorganic-organic materials with large porosity, metal-organic frameworks (MOFs) have received attractive attention recently on encapsulating functional guest species. Although the encapsulation of luminescent guest into bulk MOFs can tune the luminescent property, the powder composite materials are limited to the application in optical sensors and devices. In the present work, we use a modified liquid-phase epitaxial (LPE) pump method for the fabrication of lanthanide coordination compounds (LCCs)-encapsulated MOF thin film on substrate with high encapsulation efficiency. The resultant composite film reveals an oriented and homogeneous composite film, in which a white light emission by tuning the LCCs of red, blue and green emission can be obtained. This strategy may open new perspectives for developing high-encapsulation-efficiency, oriented, and homogeneous solid-state lighting composite films in the application of optical sensors and devices.

  9. High energy sideband on the magnetic polaron related luminescence in EuTe

    Science.gov (United States)

    Heredia, E.; Motisuke, P.; de Oliveira Rappl, P. H.; Brasil, M. J. S. P.; Iikawa, F.

    2012-08-01

    We investigated the near band gap luminescence of EuTe thin films grown by molecular beam epitaxy, using excitation intensities up to 2 × 105 W/cm2. Besides the previously reported high energy emissions MX1 and MX2, we observed an additional emission band at higher energies. This higher-energy band is only detected when high excitation intensities, over 2 kW/cm2, are used. With increasing externally applied magnetic field, this additional emission band shifts to lower energies at a rate even higher than the MX1. The two bands, however, have different temperature dependences and decay times, suggesting that distinct electronic states are involved in their emission.

  10. Relationship between lanthanide contents in aquatic turtles and environmental exposures.

    Science.gov (United States)

    Censi, P; Randazzo, L A; D'Angelo, S; Saiano, F; Zuddas, P; Mazzola, S; Cuttitta, A

    2013-05-01

    Trace elements released in the environment during agricultural practices can be incorporated and accumulated in biological fluids and tissues of living organisms. The assessment of these exposures were carried out investigating lanthanide distributions in blood and exoskeleton samples collected from Emys trinacris turtle specimens coming from sites with anthropogenic discharge in western and south Sicily, along migration paths of many bird species from Africa to Europe. The data show a significant (Rxy=0.72; Rxy>0.67; α=0.025) linear relationship between the size of turtle specimens and the lanthanide contents in blood lower than 0.4 μg L(-1) whereas this relationship disappears in blood with higher lanthanide contents. Comparative evaluations of normalised concentrations show that lanthanides fractionate between blood and exoskeleton inducing antithetical lanthanide patterns therein. These features are more evident in specimens with high lanthanide contents in blood, suggesting that lanthanide accumulations in the exoskeleton can represent the physiological response of E. trinacris to environmental and the further confirmation of relationship occurring between the environmental and the biological fluids.

  11. Three-photon luminescence of gold nanorods and its applications for high contrast tissue and deep in vivo brain imaging.

    Science.gov (United States)

    Wang, Shaowei; Xi, Wang; Cai, Fuhong; Zhao, Xinyuan; Xu, Zhengping; Qian, Jun; He, Sailing

    2015-01-01

    Gold nanoparticles can be used as contrast agents for bio-imaging applications. Here we studied multi-photon luminescence (MPL) of gold nanorods (GNRs), under the excitation of femtosecond (fs) lasers. GNRs functionalized with polyethylene glycol (PEG) molecules have high chemical and optical stability, and can be used as multi-photon luminescent nanoprobes for deep in vivo imaging of live animals. We have found that the depth of in vivo imaging is dependent upon the transmission and focal capability of the excitation light interacting with the GNRs. Our study focused on the comparison of MPL from GNRs with two different aspect ratios, as well as their ex vivo and in vivo imaging effects under 760 nm and 1000 nm excitation, respectively. Both of these wavelengths were located at an optically transparent window of biological tissue (700-1000 nm). PEGylated GNRs, which were intravenously injected into mice via the tail vein and accumulated in major organs and tumor tissue, showed high image contrast due to distinct three-photon luminescence (3PL) signals upon irradiation of a 1000 nm fs laser. Concerning in vivo mouse brain imaging, the 3PL imaging depth of GNRs under 1000 nm fs excitation could reach 600 μm, which was approximately 170 μm deeper than the two-photon luminescence (2PL) imaging depth of GNRs with a fs excitation of 760 nm.

  12. Luminescence detection of cysteine based on Ag{sup +}-mediated conformational change of terbium ion-promoted G-quadruplex

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Hongliang, E-mail: hltan@jxnu.edu.cn; Tang, Gonge; Ma, Chanjiao; Li, Qian

    2016-02-18

    In this work, we developed a simple and sensitive method for the detection of cysteine (Cys) by employing terbium ion (Tb{sup 3+})-promoted G-qudraplex (G4/Tb) as a luminescent probe, which is based on Ag{sup +}-mediated conformational change of G4/Tb. Due to Ag{sup +} is able to compete with Tb{sup 3+} to bind guanine at G4, the presence of Ag{sup +} can lead to the formation of G4/Tb–Ag{sup +} complex and disrupt the structure of G4/Tb. Meanwhile, the binding of Ag{sup +} with G4/Tb will also cause the alteration of the excited state of G4 and more efficient energy transfer from G4 to Tb{sup 3+}, enhancing the luminescence of G4/Tb. However, upon the addition of Cys, Ag{sup +} will be released from G4/Tb–Ag{sup +} complex because of the high affinity of Cys to Ag{sup +}. This results in the re-formation of the conformation of G4/Tb and the decrease of the luminescence of G4/Tb. So, Ag{sup +}-enhanced luminescence of G4/Tb is associated with its conformational transformation. As a luminescent probe for Cys, G4/Tb not only shows excellent selectivity and sensitivity with a detection limit of 20 nM, but also possesses the features of simple preparation, easy reproducibility, and eliminating the interferences from background fluorescence. We envision that the presented strategy might provide new insight into the biosensing applications of lanthanide complex. - Highlights: • A G4/Tb-based luminescent probe for Cys detection was developed for the first time. • The binding and remove of Ag{sup +} mediate the luminescence of G4/Tb. • The luminescent ​sensor showed excellent selectivity and high sensitivity to Cys.

  13. Circularly Polarized Luminescence in Enantiopure Europium and Terbium Complexes with Modular, All-Oxygen Donor Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, Michael; Do, King; Ingram, Andrew; Moore, Evan; Muller, Gilles; Raymond, Kenneth

    2009-06-04

    The modular syntheses of three new octadentate, enantiopure ligands are reported, one with the bidentate chelating unit 2-hydroxyisophthalamide (IAM) and two with bidentate 1-hydroxy-2-pyridinone (1,2-HOPO) units. A new design principle is introduced for the chiral, non-racemic hexamines which constitute the central backbones for the presented class of ligands. The terbium(III) complex of the IAM ligand, as well as the europium(III) complexes of the 1,2-HOPO ligands, are synthesized and characterized by various techniques (NMR, UV, CD, luminescence spectroscopy). All species exhibit excellent stability and moderate to high luminescence efficiency (quantum yields {phi}{sub Eu} = 0.05-0.08 and {phi}{sub Tb} = 0.30-0.57) in aqueous solution at physiological pH. Special focus is put onto the properties of the complexes in regard to circularly polarized luminescence (CPL). The maximum luminescence dissymmetry factors (glum) in aqueous solution are high with |glum|max = 0.08-0.40. Together with the very favorable general properties (good stability, high quantum yields, long lifetimes), the presented lanthanide complexes can be considered as good candidates for analytical probes based on CPL in biologically relevant environments.

  14. Investigating quartz optically stimulated luminescence dose-response curves at high doses

    Energy Technology Data Exchange (ETDEWEB)

    Lowick, Sally E., E-mail: lowick@geo.unibe.c [Institut fuer Geologie, Universitaet Bern, Baltzerstrasse 1-3, 3012 Bern (Switzerland); Preusser, Frank [Institut fuer Geologie, Universitaet Bern, Baltzerstrasse 1-3, 3012 Bern (Switzerland); Wintle, Ann G. [Institute of Geography and Earth Sciences, Aberystwyth University, AberystwythSY23 3DB (United Kingdom)

    2010-10-15

    Despite the general expectation that optically stimulated luminescence (OSL) growth should be described by a simple saturating exponential function, an additional high dose component is often reported in the dose response of quartz. Although often reported as linear, it appears that this response is the early expression of a second saturating exponential. While some studies using equivalent doses that fall in this high dose region have produced ages that correlate well with independent dating, others report that it results in unreliable age determinations. Two fine grain sedimentary quartz samples that display such a response were used to investigate the origin of this additional high dose component: three experiments were conducted to examine their dose-response up to >1000 Gy. The high dose rates provided by laboratory irradiation were found not to induce a sensitivity change in the response to a subsequent test dose, with the latter not being significantly different from those generated following naturally acquired doses. The relative percentage contributions of the fast and medium OSL components remained fixed throughout the dose-response curve, suggesting that the electron traps that give rise to the initial OSL do not change with dose. An attempt was made to investigate a change in luminescence centre recombination probability by monitoring the depletion of the '325 {sup o}C' thermoluminescence (TL) during the optical stimulation that would result in depletion of the OSL signal. The emissions measured through both the conventional ultraviolet (UV), and a longer wavelength violet/blue (VB) window, displayed similar relative growth with dose, although it was not possible to resolve the origin of the VB emissions. No evidence was found to indicate whether the additional component at high doses occurs naturally or is a product of laboratory treatment. However, it appears that these samples display an increased sensitivity of quartz OSL to high doses

  15. A low-cost smartphone-based platform for highly sensitive point-of-care testing with persistent luminescent phosphors.

    Science.gov (United States)

    Paterson, Andrew S; Raja, Balakrishnan; Mandadi, Vinay; Townsend, Blane; Lee, Miles; Buell, Alex; Vu, Binh; Brgoch, Jakoah; Willson, Richard C

    2017-03-14

    Through their computational power and connectivity, smartphones are poised to rapidly expand telemedicine and transform healthcare by enabling better personal health monitoring and rapid diagnostics. Recently, a variety of platforms have been developed to enable smartphone-based point-of-care testing using imaging-based readout with the smartphone camera as the detector. Fluorescent reporters have been shown to improve the sensitivity of assays over colorimetric labels, but fluorescence readout necessitates incorporating optical hardware into the detection system, adding to the cost and complexity of the device. Here we present a simple, low-cost smartphone-based detection platform for highly sensitive luminescence imaging readout of point-of-care tests run with persistent luminescent phosphors as reporters. The extremely bright and long-lived emission of persistent phosphors allows sensitive analyte detection with a smartphone by a facile time-gated imaging strategy. Phosphors are first briefly excited with the phone's camera flash, followed by switching off the flash, and subsequent imaging of phosphor luminescence with the camera. Using this approach, we demonstrate detection of human chorionic gonadotropin using a lateral flow assay and the smartphone platform with strontium aluminate nanoparticles as reporters, giving a detection limit of ≈45 pg mL(-1) (1.2 pM) in buffer. Time-gated imaging on a smartphone can be readily adapted for sensitive and potentially quantitative testing using other point-of-care formats, and is workable with a variety of persistent luminescent materials.

  16. Highly efficient large-area colourless luminescent solar concentrators using heavy-metal-free colloidal quantum dots.

    Science.gov (United States)

    Meinardi, Francesco; McDaniel, Hunter; Carulli, Francesco; Colombo, Annalisa; Velizhanin, Kirill A; Makarov, Nikolay S; Simonutti, Roberto; Klimov, Victor I; Brovelli, Sergio

    2015-10-01

    Luminescent solar concentrators serving as semitransparent photovoltaic windows could become an important element in net zero energy consumption buildings of the future. Colloidal quantum dots are promising materials for luminescent solar concentrators as they can be engineered to provide the large Stokes shift necessary for suppressing reabsorption losses in large-area devices. Existing Stokes-shift-engineered quantum dots allow for only partial coverage of the solar spectrum, which limits their light-harvesting ability and leads to colouring of the luminescent solar concentrators, complicating their use in architecture. Here, we use quantum dots of ternary I-III-VI2 semiconductors to realize the first large-area quantum dot-luminescent solar concentrators free of toxic elements, with reduced reabsorption and extended coverage of the solar spectrum. By incorporating CuInSexS2-x quantum dots into photo-polymerized poly(lauryl methacrylate), we obtain freestanding, colourless slabs that introduce no distortion to perceived colours and are thus well suited for the realization of photovoltaic windows. Thanks to the suppressed reabsorption and high emission efficiencies of the quantum dots, we achieve an optical power efficiency of 3.2%. Ultrafast spectroscopy studies suggest that the Stokes-shifted emission involves a conduction-band electron and a hole residing in an intragap state associated with a native defect.

  17. Highly efficient large-area colourless luminescent solar concentrators using heavy-metal-free colloidal quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Meinardi, Francesco; McDaniel, Hunter; Carulli, Francesco; Colombo, Annalisa; Velizhanin, Kirill A.; Makarov, Nikolay S.; Simonutti, Roberto; Klimov, Victor I.; Brovelli, Sergio

    2015-08-24

    Luminescent solar concentrators serving as semitransparent photovoltaic windows could become an important element in net zero energy consumption buildings of the future. Colloidal quantum dots are promising materials for luminescent solar concentrators as they can be engineered to provide the large Stokes shift necessary for suppressing reabsorption losses in large-area devices. Existing Stokes-shift-engineered quantum dots allow for only partial coverage of the solar spectrum, which limits their light-harvesting ability and leads to colouring of the luminescent solar concentrators, complicating their use in architecture. Here, we use quantum dots of ternary I–III–VI2 semiconductors to realize the first large-area quantum dot–luminescent solar concentrators free of toxic elements, with reduced reabsorption and extended coverage of the solar spectrum. By incorporating CuInSexS2–x quantum dots into photo-polymerized poly(lauryl methacrylate), we obtain freestanding, colourless slabs that introduce no distortion to perceived colours and are thus well suited for the realization of photovoltaic windows. Thanks to the suppressed reabsorption and high emission efficiencies of the quantum dots, we achieve an optical power efficiency of 3.2%. Ultrafast spectroscopy studies suggest that the Stokes-shifted emission involves a conduction-band electron and a hole residing in an intragap state associated with a native defect.

  18. A Highly Stable 3D Luminescent Indium-Polycarboxylic Framework for the Turn-off Detection of UO2(2+), Ru(3+), and Biomolecule Thiamines.

    Science.gov (United States)

    Du, Ning; Song, Jian; Li, Shuang; Chi, Yu-Xian; Bai, Feng-Ying; Xing, Yong-Heng

    2016-10-17

    Hydrothermal reaction of the multidentate organic ligand (H6TTHA) with indium chloride (InCl3) produced a highly stable 3D luminescent indium-organic framework [In2(OH)2(H2TTHA)(H2O)2]n (1). Complex 1 exhibits remarkable luminescent properties, especially the multifunction sensitivity and selectivity for detecting Ru(3+), UO2(2+); as well as small biomolecules thiamines (TPP, TMP, and TCl) based on a "turn-off" manner. In particular, the pyrophosphate groups of TPP and the phosphate groups of TMP could further affect the quenching rate, leading to different luminescent responds. In addition, we also discussed and proved the luminescence quenching mechanism in detail through comparative test and PXRD characterization. Therefore, complex 1 could be used as a kind of excellent luminescence sensor to detect Ru(3+), UO2(2+), and thiamines (TPP, TMP, and TCl).

  19. Lanthanides caged by the organic chelates; structural properties.

    Science.gov (United States)

    Smentek, Lidia

    2011-04-13

    The structure, in particular symmetry, geometry and morphology of organic chelates coordinated with the lanthanide ions are analyzed in the present review. This is the first part of a complete presentation of a theoretical description of the properties of systems, which are widely used in technology, but most of all, in molecular biology and medicine. The discussion is focused on the symmetry and geometry of the cages, since these features play a dominant role in the spectroscopic activity of the lanthanides caged by organic chelates. At the same time, the spectroscopic properties require more formal presentation in the language of Racah algebra, and deserve a separate analysis. In addition to the parent systems of DOTA, DOTP, EDTMP and CDTMP presented here, their modifications by various antennas are analyzed. The conclusions that have a strong impact upon the theory of the energy transfer and the sensitized luminescence of these systems are based on the results of numerical density functional theory calculations.

  20. The synthesis, design and applications of lanthanide cored complexes

    Science.gov (United States)

    Phelan, Gregory David

    Novel luminescent materials based on lanthanide cored complexes have been designed and synthesized. The complexes consist of a beta-diketone ligand chelated to a lanthanide metal such as europium or gadolinium. A series of beta-diketone ligands were designed and synthesized. The ligands consist of a polycyclic aromatic sensitizer, phenanthrene, and a second functional group. The second groups consisted of another unit of phenanthrene, a dendritic structure, or a fluorinated alkyl chain. The europium complexes have been incorporated into organic light emitting devices that have a major emission at 615 nm and a maximum brightness of 300 cd/m2. The gadolinium complexes were used to dope into the resulting organic light emitting devices to help improve the efficiency of the device. The use of the gadolinium complexes results in a 25 fold increase in efficiency.

  1. 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.

  2. Improvement of electroluminescent property of blue LED coated with highly luminescent yellow-emitting phosphors

    Science.gov (United States)

    Jang, H. S.; Won, Y.-H.; Jeon, D. Y.

    2009-06-01

    White light-emitting diodes (WLEDs) were fabricated by combining InGaN-based blue light-emitting diodes (LEDs) with highly luminescent Tb3Al5O12:Ce3+ (TAG:Ce), Y3Al5O12:Ce3+ (YAG:Ce), and Sr3SiO5:Eu2+ (SS:Eu). The TAG:Ce-based WLED showed a color rendering index ( R a ) of 79 and a luminous efficiency ( η L ) of 34.1 lm/W at 20 mA. The YAG:Ce-based WLED and the SS:Eu-based WLED showed low R a values of 75 and 57 but high luminous efficiency values of 38.9 and 41.3 lm/W at 20 mA, respectively. When a mixture of YAG:Ce and SS:Eu was coated on a blue LED and the resultant WLED operated at 20 mA, the WLED showed a highly bright white light similar to daylight ( η L =40.9 lm/W, color temperature T c =5,716 K, and R a =76). Moreover, the WLED showed stable color coordinates against a considerable variation of applied current.

  3. A Terbium Metal-Organic Framework for Highly Selective and Sensitive Luminescence Sensing of Hg(2+) Ions in Aqueous Solution.

    Science.gov (United States)

    Xia, Tifeng; Song, Tao; Zhang, Gege; Cui, Yuanjing; Yang, Yu; Wang, Zhiyu; Qian, Guodong

    2016-12-19

    A series of isomorphic lanthanide metal-organic frameworks (MOFs) Ln(TATAB)⋅(DMF)4 (H2 O)(MeOH)0.5 (LnTATAB, Ln=Eu, Tb, Sm, Dy, Gd; H3 TATAB=4,4',4''-s-triazine-1,3,5-triyltri-p-aminobenzoic acid) have been solvothermally synthesized and structurally characterized. Among these MOFs, TbTATAB exhibits good water stability and a high fluorescence quantum yield. Because mercury ions (Hg(2+) ) have a high affinity to nitrogen atoms, and the space between multiple nitrogen atoms from triazine and imino groups is suitable for interacting with Hg(2+) ions, TbTATAB shows highly selective and sensitive detection of Hg(2+) in aqueous solution with a detection limit of 4.4 nm. Furthermore, it was successfully applied to detect Hg(2+) ions in natural water samples. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Synthesis of highly luminescent Mn:ZnSe/ZnS nanocrystals in aqueous media.

    Science.gov (United States)

    Fang, Zheng; Wu, Ping; Zhong, Xinhua; Yang, Yong-Ji

    2010-07-30

    High-quality water-dispersible Mn(2+)-doped ZnSe core/ZnS shell (Mn:ZnSe/ZnS) nanocrystals have been synthesized directly in aqueous media. Overcoating a high bandgap ZnS shell around the Mn:ZnSe cores can bring forward an efficient energy transfer from the ZnSe host nanocrystals to the dopant Mn. The quantum yields of the dopant Mn photoluminescence in the as-prepared water-soluble Mn:ZnSe/ZnS core/shell nanocrystals can be up to 35 +/- 5%. The optical features and structure of the obtained Mn:ZnSe/ZnS core/shell nanocrystals have been characterized by UV-vis, PL spectroscopy, TEM, XRD and ICP elementary analysis. The influences of various experimental variables, including the Mn concentration, the Se/Zn molar ratio as well as the kind and amount of capping ligand used in the core production and shell deposition process, on the luminescent properties of the obtained Mn:ZnSe/ZnS nanocrystals have been systematically investigated.

  5. Biocompatible and high-performance amino acids-capped MnWO4 nanocasting as a novel non-lanthanide contrast agent for X-ray computed tomography and T1-weighted magnetic resonance imaging

    Science.gov (United States)

    Dong, Kai; Liu, Zhen; Liu, Jianhua; Huang, Sa; Li, Zhenhua; Yuan, Qinghai; Ren, Jinsong; Qu, Xiaogang

    2014-01-01

    In the present work, a novel non-lanthanide dual-modality contrast agent, manganese tungstate (MnWO4), has been successfully constructed by a facile and versatile hydrothermal route. With the merits of a high atomic number and a well-positioned K-edge energy of tungsten, our well-prepared non-lanthanide nanoprobes provide a higher contrast efficacy than routine iodine-based agents in clinics. Additionally, the presence of Mn in these nanoparticles endow them with excellent T1-weighted MR imaging capabilities. As an alternative to T2-weighted MRI and CT dual-modality contrast agents, the nanoprobes can provide a positive contrast signal, which prevents confusion with the dark signals from hemorrhage and blood clots. To the best of our knowledge, this is the first report that a non-lanthanide imaging nanoprobe is applied for CT and T1-weighted MRI simultaneously. Moreover, comparing with gadolinium-based T1-weighted MRI and CT dual-modality contrast agents that were associated with nephrogenic systemic fibrosis (NSF), our contrast agents have superior biocompatibility, which is proved by a detailed study of the pharmacokinetics, biodistribution, and in vivo toxicology. Together with excellent dispersibility, high biocompatibility and superior contrast efficacy, these nanoprobes provide detailed and complementary information from dual-modality imaging over traditional single-mode imaging and bring more opportunities to the new generation of non-lanthanide nanoparticulate-based contrast agents.In the present work, a novel non-lanthanide dual-modality contrast agent, manganese tungstate (MnWO4), has been successfully constructed by a facile and versatile hydrothermal route. With the merits of a high atomic number and a well-positioned K-edge energy of tungsten, our well-prepared non-lanthanide nanoprobes provide a higher contrast efficacy than routine iodine-based agents in clinics. Additionally, the presence of Mn in these nanoparticles endow them with excellent T1

  6. Lanthanide extraction with 2,5-dimethyl-2-hydroxyhexanoic acid

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J. H.

    1977-12-01

    This research is concerned with the solvent extraction into chloroform of the lanthanides, using 2,5-dimethyl-2-hydroxyhexanoic acid (DMHHA). This acid is the first ..cap alpha..-hydroxy aliphatic acid to be studied as an extracting agent for the lanthanides. The chloroform-water DMHHA partition constant was determined to be 1.0 (at 0.1 M ionic strength and 25/sup 0/C). The acid dimerizes in chloroform with a constant of 56. The light lanthanides can be extracted into chloroform by forming complexes with the DMHHA anions. The extracted metal species is highly aggregated. This extraction has a solubility limit which increases with the addition of unionized acid. The resultant extract is also highly aggregated. At unionized acid-to-metal ratios greater than one, extractions first occur followed by the slow precipitation of the lanthanide. At the tracer level, neodymium is extracted primarily as NdA/sub 3/(HA)/sub 5/ and (NdA/sub 3/)/sub 2/(HA)/sub q/. Very small amounts of (NdA/sub 3/)/sub 2/ and other metal aggregates are also present. The heavy lanthanides do not extract from solutions of DMHHA and its potassium salt, but form aqueous emulsions and precipitates. In the presence of the organic soluble tetrabutylammonium ion the heavy lanthanides can be extracted, presumably as ion pairs. The stability constants of the light lanthanides and DMHHA were determined. The separation factors obtained from DMHHA extractions of the light lanthanides were also investigated and found to be comparable to those obtained employing normal aliphatic carboxylic acid.

  7. Monitoring Delamination of Thermal Barrier Coating During Interrupted High-Heat Flux Laser Testing Using Upconversion Luminescence Imaging

    Science.gov (United States)

    Eldridge, Jeffrey I.; Zhu, Dongming; Wolfe, Douglas E.

    2011-01-01

    Upconversion luminescence imaging of thermal barrier coatings (TBCs) has been shown to successfully monitor TBC delamination progression during interrupted furnace cycling. However, furnace cycling does not adequately model engine conditions where TBC-coated components are subjected to significant heat fluxes that produce through-thickness temperature gradients that may alter both the rate and path of delamination progression. Therefore, new measurements are presented based on luminescence imaging of TBC-coated specimens subjected to interrupted high-heat-flux laser cycling exposures that much better simulate the thermal gradients present in engine conditions. The TBCs tested were deposited by electron-beam physical vapor deposition (EB-PVD) and were composed of 7wt% yttria-stabilized zirconia (7YSZ) with an integrated delamination sensing layer composed of 7YSZ co-doped with erbium and ytterbium (7YSZ:Er,Yb). The high-heat-flux exposures that produce the desired through-thickness thermal gradients were performed using a high power CO2 laser operating at a wavelength of 10.6 microns. Upconversion luminescence images revealed the debond progression produced by the cyclic high-heat-flux exposures and these results were compared to that observed for furnace cycling.

  8. Real-Time Detection of Traces of Benzaldehyde in Benzyl Alcohol as a Solvent by a Flexible Lanthanide Microporous Metal-Organic Framework.

    Science.gov (United States)

    Zhang, Huan; Chen, Diming; Ma, Huili; Cheng, Peng

    2015-10-26

    Luminescent 3D lanthanide metal-organic framework (Ln-MOF) {[Tb2 (TATAB)2 ]⋅4 H2 O⋅6 DMF}n (1) was synthesized under solvothermal conditions by using flexible ligand 4,4',4''-s-triazine-1,3,5-triyltri-p-aminobenzoate (TATAB). A phase transition was observed between low temperature and room temperature. The luminescence of 1 could be enhanced by formaldehyde and quenched efficiently by trace amounts of benzaldehyde in solvents such as benzyl alcohol (0.01-2.0 vol %) and ethanol (0.01-2.5 vol %). This is the first use of a Ln-MOF as chemical sensor for both formaldehyde and benzaldehyde. The high sensitivity and selectivity of the luminescence response of 1 to benzaldehyde allows it to be used as an excellent sensor for identifying benzaldehyde and provides a simple and convenient method for detecting traces of benzaldehyde in benzyl alcohol based injections. This work establishes a new strategy for detection of benzaldehyde in benzyl alcohol by luminescent MOFs.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-04-15

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

  10. Influence of high magnetic field on the luminescence of Eu{sup 3+}-doped glass ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Wei; Chen, Weibo; Chen, Ping; Xu, Beibei; Zheng, Shuhong; Guo, Qiangbing; Liu, Xiaofeng, E-mail: xfliu@zju.edu.cn, E-mail: qjr@zju.edu.cn [State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou, Zhejiang 310027 (China); Zhang, Junpei; Han, Junbo [Wuhan National High Magnetic field Center, Huazhong University of Science and Technology, Wuhan, Hubei 430074 (China); Qiu, Jianrong, E-mail: xfliu@zju.edu.cn, E-mail: qjr@zju.edu.cn [State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou, Zhejiang 310027 (China); State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, Guangdong 510640 (China)

    2014-09-28

    Rare earth (RE) doped materials have been widely exploited as the intriguing electronic configuration of RE ions offers diverse functionalities from optics to magnetism. However, the coupling of magnetism with photoluminescence (PL) in such materials has been rarely reported in spite of its fundamental significance. In the present paper, the effect of high pulsed magnetic field on the photoluminescence intensity of Eu{sup 3+}-doped nano-glass-ceramics has been investigated. In our experiment, Eu-doped oxyfluoride glass and glass ceramic were prepared by the conventional melt-quenching process and controlled heat treatment. The results demonstrate that the integrated PL intensity of Eu{sup 3+} decreases with the enhancement of magnetic field, which can be interpreted in terms of cooperation effect of Zeeman splitting and magnetic field induced change in site symmetry. Furthermore, as a result of Zeeman splitting, both blue and red shift in the emission peaks of Eu{sup 3+} can be observed, and this effect becomes more prominent with the increase of magnetic field. Possible mechanisms associated with the observed magneto-optical behaviors are suggested. The results of the present paper may open a new gate for modulation of luminescence by magnetic field and remote optical detection of magnetic field.

  11. Influence of high magnetic field on the luminescence of Eu3+-doped glass ceramics

    Science.gov (United States)

    Jiang, Wei; Zhang, Junpei; Chen, Weibo; Chen, Ping; Han, Junbo; Xu, Beibei; Zheng, Shuhong; Guo, Qiangbing; Liu, Xiaofeng; Qiu, Jianrong

    2014-09-01

    Rare earth (RE) doped materials have been widely exploited as the intriguing electronic configuration of RE ions offers diverse functionalities from optics to magnetism. However, the coupling of magnetism with photoluminescence (PL) in such materials has been rarely reported in spite of its fundamental significance. In the present paper, the effect of high pulsed magnetic field on the photoluminescence intensity of Eu3+-doped nano-glass-ceramics has been investigated. In our experiment, Eu-doped oxyfluoride glass and glass ceramic were prepared by the conventional melt-quenching process and controlled heat treatment. The results demonstrate that the integrated PL intensity of Eu3+ decreases with the enhancement of magnetic field, which can be interpreted in terms of cooperation effect of Zeeman splitting and magnetic field induced change in site symmetry. Furthermore, as a result of Zeeman splitting, both blue and red shift in the emission peaks of Eu3+ can be observed, and this effect becomes more prominent with the increase of magnetic field. Possible mechanisms associated with the observed magneto-optical behaviors are suggested. The results of the present paper may open a new gate for modulation of luminescence by magnetic field and remote optical detection of magnetic field.

  12. Highly efficient luminescent solar concentrators based on earth-abundant indirect-bandgap silicon quantum dots

    Science.gov (United States)

    Meinardi, Francesco; Ehrenberg, Samantha; Dhamo, Lorena; Carulli, Francesco; Mauri, Michele; Bruni, Francesco; Simonutti, Roberto; Kortshagen, Uwe; Brovelli, Sergio

    2017-02-01

    Building-integrated photovoltaics is gaining consensus as a renewable energy technology for producing electricity at the point of use. Luminescent solar concentrators (LSCs) could extend architectural integration to the urban environment by realizing electrode-less photovoltaic windows. Crucial for large-area LSCs is the suppression of reabsorption losses, which requires emitters with negligible overlap between their absorption and emission spectra. Here, we demonstrate the use of indirect-bandgap semiconductor nanostructures such as highly emissive silicon quantum dots. Silicon is non-toxic, low-cost and ultra-earth-abundant, which avoids the limitations to the industrial scaling of quantum dots composed of low-abundance elements. Suppressed reabsorption and scattering losses lead to nearly ideal LSCs with an optical efficiency of η = 2.85%, matching state-of-the-art semi-transparent LSCs. Monte Carlo simulations indicate that optimized silicon quantum dot LSCs have a clear path to η > 5% for 1 m2 devices. We are finally able to realize flexible LSCs with performances comparable to those of flat concentrators, which opens the way to a new design freedom for building-integrated photovoltaics elements.

  13. Doped zirconia phase and luminescence dependence on the nature of charge compensation

    Science.gov (United States)

    Smits, Krisjanis; Olsteins, Dags; Zolotarjovs, Aleksejs; Laganovska, Katrina; Millers, Donats; Ignatans, Reinis; Grabis, Janis

    2017-01-01

    Zirconia is a relatively new material with many promising practical applications in medical imaging, biolabeling, sensors, and other fields. In this study we have investigated lanthanide and niobium doped zirconia by luminescence and XRD methods. It was proven that charge compensation in different zirconia phases determines the incorporation of intrinsic defects and activators. Thus, the structure of zirconia does not affect the Er luminescence directly; however, it strongly affects the defect distribution around lanthanide ions and the way in which activator ions are incorporated in the lattice. Our results demonstrate the correlation between the crystalline phase of zirconia and charge compensation, as well as the contribution of different nanocrystal grain sizes. In addition, our experimental results verify the theoretical studies of metastable (tetragonal, cubic) phase stabilization determined using only oxygen vacancies. Moreover, it was found that adding niobium drastically increases activator luminescence intensity, which makes Ln3+ doped zirconia even more attractive for various practical applications. Although this study was based on the luminescence of the Er ion, the phase stabilization, charge compensation, and luminescence properties described in our results are expected to be similar for other lanthanide elements. Our results suggest that the luminescence intensity of other oxide matrices where lanthanides incorporate in place of tetravalent cations could be increased by addition of Nb ions. PMID:28287623

  14. Doped zirconia phase and luminescence dependence on the nature of charge compensation

    Science.gov (United States)

    Smits, Krisjanis; Olsteins, Dags; Zolotarjovs, Aleksejs; Laganovska, Katrina; Millers, Donats; Ignatans, Reinis; Grabis, Janis

    2017-03-01

    Zirconia is a relatively new material with many promising practical applications in medical imaging, biolabeling, sensors, and other fields. In this study we have investigated lanthanide and niobium doped zirconia by luminescence and XRD methods. It was proven that charge compensation in different zirconia phases determines the incorporation of intrinsic defects and activators. Thus, the structure of zirconia does not affect the Er luminescence directly; however, it strongly affects the defect distribution around lanthanide ions and the way in which activator ions are incorporated in the lattice. Our results demonstrate the correlation between the crystalline phase of zirconia and charge compensation, as well as the contribution of different nanocrystal grain sizes. In addition, our experimental results verify the theoretical studies of metastable (tetragonal, cubic) phase stabilization determined using only oxygen vacancies. Moreover, it was found that adding niobium drastically increases activator luminescence intensity, which makes Ln3+ doped zirconia even more attractive for various practical applications. Although this study was based on the luminescence of the Er ion, the phase stabilization, charge compensation, and luminescence properties described in our results are expected to be similar for other lanthanide elements. Our results suggest that the luminescence intensity of other oxide matrices where lanthanides incorporate in place of tetravalent cations could be increased by addition of Nb ions.

  15. Hydrothermal synthesis of highly luminescent blue-emitting ZnSe(S) quantum dots exhibiting low toxicity

    Energy Technology Data Exchange (ETDEWEB)

    Mirnajafizadeh, Fatemeh; Ramsey, Deborah; McAlpine, Shelli [School of Chemistry, University of New South Wales, Sydney, NSW 2052 (Australia); Wang, Fan; Reece, Peter [School of Physics, University of New South Wales, Sydney, NSW 2052 (Australia); Stride, John Arron, E-mail: j.stride@unsw.edu.au [School of Chemistry, University of New South Wales, Sydney, NSW 2052 (Australia); Bragg Institute, Australian Nuclear Science and Technology Organisation, PMB 1, Menai, NSW 2234 (Australia)

    2016-07-01

    Highly luminescent quantum dots (QDs) that emit in the visible spectrum are of interest to a number of imaging technologies, not least that of biological samples. One issue that hinders the application of luminescent markers in biology is the potential toxicity of the fluorophore. Here we show that hydrothermally synthesized ZnSe(S) QDs have low cytotoxicity to both human colorectal carcinoma cells (HCT-116) and human skin fibroblast cells (WS1). The QDs exhibited a high degree of crystallinity, with a strong blue photoluminescence at up to 29% quantum yield relative to 4′,6-diamidino-2-phenylindole (DAPI) without post-synthetic UV-irradiation. Confocal microscopy images obtained of HCT-116 cells after incubation with the QDs highlighted the stability of the particles in cell media. Cytotoxicity studies showed that both HCT-116 and WS1 cells retain 100% viability after treatment with the QDs at concentrations up to 0.5 g/L, which makes them of potential use in biological imaging applications. - Highlights: • Highly luminescent ZnSe(S) QDs were synthesized using a simple, one-step hydrothermal method. • The as-synthesized QDs were found to be nontoxic in the presence of biological cells. • The QDs were stable in biological media with identical emission profile to that in water.

  16. Evidence of a green luminescence band related to surface flaws in high purity silica glass

    Energy Technology Data Exchange (ETDEWEB)

    Fournier, J.; Neauport, J.; Grua, P. [CEA, CESTA, F-33114 Le Barp (France); Fournier, J.; Fargin, E.; Jubera, V. [Univ Bordeaux, CNRS, ICMCB, F-33608 Pessac (France); Talaga, D. [Univ Bordeaux, CNRS, ISM, F-33405 Talence (France); Jouannigot, S. [Univ Bordeaux 1, LCTS, SAFRAN, CNRS, CEA, UMR 5801, Pessac (France)

    2010-07-01

    Using luminescence con-focal microscopy under 325 nm laser excitation, we explore the populations of defects existing in or at the vicinity of macroscopic surface flaws in fused silica. We report our luminescence results on two types of surface flaws: laser damage and indentation on fused silica polished surfaces. Luminescence cartographies are made to show the spatial distribution of each kind of defect. Three bands, centered at 1.89 eV, 2.75 eV and 2.25 eV are evidenced on laser damage and indentations. The band centered at 2.25 eV was not previously reported in photo luminescence experiments on indentations and pristine silica, for excitation wavelengths of 325 nm or larger. The luminescent objects, expected to be trapped in sub-surface micro-cracks, are possibly involved in the first step of the laser damage mechanism when fused silica is enlightened at 351 nm laser in nanosecond regime. (authors)

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

    Science.gov (United States)

    Ahmed, Zubair; Iftikhar, K

    2013-11-07

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

  18. New AIE-active pyrimidine-based boronfluoride complexes with high solid-state emission and reversible mechanochromism luminescence behavior.

    Science.gov (United States)

    Qi, Fen; Lin, Jianjian; Wang, Xiaoqing; Cui, Peng; Yan, Hui; Gong, Shuwen; Ma, Chunlin; Liu, Zhipeng; Huang, Wei

    2016-04-25

    A new family of pyrimidine-based BF2 complexes () with aggregation-induced emission (AIE) and mechanochromic luminescence properties were developed. These compounds exhibit intense fluorescence in their aggregation/solid-state resulting from their large Stokes shift and AIE. X-ray crystallographic analysis shows that the weak intermolecular interactions by fixing the molecular conformations of are responsible for the intense fluorescence in solid-state. In addition to their pronounced AIE behaviour, also exhibits a reversible chromic response to grinding, and a distinct red-shift of emission is observed. The high solid-state luminescence and grinding-stimuli response properties of these compounds make them potential candidates for smart materials.

  19. Revealing and tuning the core, structure, properties and function of polymer micelles with lanthanide-coordination complexes

    NARCIS (Netherlands)

    Wang, J.; Groeneveld, A.; Oikonomou, M.E.; Prusova, A.; As, van H.; Lent, van J.W.M.; Velders, A.H.

    2016-01-01

    Controlling self-assembly processes is of great interest in various fields where multifunctional and tunable materials are designed. We here present the versatility of lanthanide-complex-based micelles (Ln-C3Ms) with tunable coordination structures and corresponding functions (e.g. luminescence and

  20. The effect of lanthanides on photosynthesis, growth, and chlorophyll profile of the green alga Desmodesmus quadricauda.

    Science.gov (United States)

    Řezanka, Tomáš; Kaineder, Katrin; Mezricky, Dana; Řezanka, Michal; Bišová, Kateřina; Zachleder, Vilém; Vítová, Milada

    2016-12-01

    Lanthanides (La, Gd, Nd, Ce) accumulated in the green alga Desmodesmus quadricauda but their intracellular localizations were distinctly different: lanthanum and gadolinium were localized in cytoplasm, while neodymium and cerium were in the chloroplast. The effect of lanthanum and neodymium, as representatives of these two groups, on growth, chlorophyll content and photosynthetic rate at different light intensities was studied. At the lowest light intensity used (50 µmol photons m(-2) s(-1)), in the presence of lanthanides (Nd), growth was enhanced by as much as 36 % over lanthanide free control, and the photosynthetic rate increased by up to 300 %. At high light intensities (238, 460, and 750 µmol photons m(-2) s(-1)), photosynthetic rate increased markedly, but there was no significant difference between rates in the presence or absence of lanthanides. However, growth, measured as a percentage of dry weight, if compared with lanthanide free control, increased at all light intensities (31, 39, and 20 %, respectively). The total amount of chlorophyll after lanthanide treatment increased by up to 21 % relative to the control culture, mainly due to an increase in the level of chlorophyll b. Addition of lanthanides caused a change in the chlorophyll a/b ratio from 4.583 in control cultivation, to 1.05. Possible mechanisms of lanthanide-induced photosynthetic change, alterations in photosynthetic structures, and increases in growth are discussed and compared with findings in higher plants. The hypothesis that the lanthanide effect could be due to formation of lanthanide-pheophytins was not confirmed as lanthanide pheophytins were not found in D. quadricauda. Furthermore, we have shown that the preferential incorporation of heavy isotopes of magnesium, namely (25)Mg and (26)Mg, into chlorophyll during photosynthesis that occurred in controls was diminished in the presence of lanthanides.

  1. Constructing Interfacial Energy Transfer for Photon Up- and Down-Conversion from Lanthanides in a Core-Shell Nanostructure.

    Science.gov (United States)

    Zhou, Bo; Tao, Lili; Chai, Yang; Lau, Shu Ping; Zhang, Qinyuan; Tsang, Yuen Hong

    2016-09-26

    We report a new mechanistic strategy for controlling and modifying the photon emission of lanthanides in a core-shell nanostructure by using interfacial energy transfer. By taking advantage of this mechanism with Gd(3+) as the energy donor, we have realized efficient up- and down-converted emissions from a series of lanthanide emitters (Eu(3+) , Tb(3+) , Dy(3+) , and Sm(3+) ) in these core-shell nanoparticles, which do not need a migratory host sublattice. Moreover, we have demonstrated that the Gd(3+) -mediated interfacial energy transfer, in contrast to energy migration, is the leading process contributing to the photon emission of lanthanide dopants for the NaGdF4 @NaGdF4 core-shell system. Our finding suggests a new direction for research into better control of energy transfer at the nanometer length scale, which would help to stimulate new concepts for designing and improving photon emission of the lanthanide-based luminescent materials.

  2. Lanthanide-doped NaScF4 nanoprobes: crystal structure, optical spectroscopy and biodetection

    Science.gov (United States)

    Ai, Yu; Tu, Datao; Zheng, Wei; Liu, Yongsheng; Kong, Jintao; Hu, Ping; Chen, Zhuo; Huang, Mingdong; Chen, Xueyuan

    2013-06-01

    Trivalent lanthanide ions (Ln3+)-doped inorganic nanoparticles (NPs) as potential luminescent bioprobes have been attracting tremendous interest because of their unique upconversion (UC) and downconversion (DC) luminescence properties. NaScF4, as an important host material, has been rarely reported and its crystal structure remains unclear. Herein, based on the single crystal X-ray diffraction, the space group of NaScF4 crystals was determined to be P31 containing multiple sites of Sc3+ with crystallographic site symmetry of C1, which was verified by high-resolution photoluminescence spectroscopy of Eu3+ at low temperature (10 K). Furthermore, monodisperse and size-controllable NaScF4:Ln3+ NPs were synthesized via a facile thermal decomposition method. The biotinylated NaScF4:Er3+/Yb3+ NPs were demonstrated for their applications as a heterogeneous UC luminescence bioprobe to detect avidin with a detection limit of 180 pM. After bioconjugation with amino-terminal fragment (ATF) of urokinase plasminogen activator (uPA), NaScF4:Ln3+ NPs also exhibited specific recognition of cancer cells overexpressed with uPA receptor (uPAR, an important marker of tumor biology and metastasis), showing great potentials in tumor-targeted bioimaging.Trivalent lanthanide ions (Ln3+)-doped inorganic nanoparticles (NPs) as potential luminescent bioprobes have been attracting tremendous interest because of their unique upconversion (UC) and downconversion (DC) luminescence properties. NaScF4, as an important host material, has been rarely reported and its crystal structure remains unclear. Herein, based on the single crystal X-ray diffraction, the space group of NaScF4 crystals was determined to be P31 containing multiple sites of Sc3+ with crystallographic site symmetry of C1, which was verified by high-resolution photoluminescence spectroscopy of Eu3+ at low temperature (10 K). Furthermore, monodisperse and size-controllable NaScF4:Ln3+ NPs were synthesized via a facile thermal

  3. The Crystal Structure of Lanthanide Zirconates

    Science.gov (United States)

    Clements, Richard; Kennedy, Brendan; Ling, Christopher; Stampfl, Anton P. J.

    2010-03-01

    The lanthanide zirconates of composition Ln2Zr2O7 (Ln = La-Gd) are of interest for use in inert matrix fuels and nuclear wasteforms. The series undergoes a pyrochlore to fluorite phase transition as a function of the Ln atomic radii. The phase transition has been attributed to disordering of both the cation and the anion [1]. We have undertaken a synthesis of the lanthanide zirconate series Ln2Zr2O7 (Ln = La-Gd), Ln0.2Zr0.8O1.9 (Ln = Tb-Yb) and NdxHo2-xZr2O7 (0ANSTO's new high resolution powder diffractometer Echidna, in order to obtain accurate data on atomic displacement parameters and O 48f position across the series. These results will be presented, along with details of the analysis and synthetic techniques used.

  4. Magnetic and fluorescent Gd2O3:Yb(3+)/Ln(3+) nanoparticles for simultaneous upconversion luminescence/MR dual modal imaging and NIR-induced photodynamic therapy.

    Science.gov (United States)

    Liu, Jun; Huang, Long; Tian, Xiumei; Chen, Xiaoming; Shao, Yuanzhi; Xie, Fukang; Chen, Dihu; Li, Li

    The development of upconversion nanoparticles (UCNs) for theranostics application is a new strategy toward the accurate diagnosis and efficient treatment of cancer. Here, magnetic and fluorescent lanthanide-doped gadolinium oxide (Gd2O3) UCNs with bright upconversion luminescence (UCL) and high longitudinal relaxivity (r1) are used for simultaneous magnetic resonance imaging (MRI)/UCL dual-modal imaging and photodynamic therapy (PDT). In vitro and in vivo MRI studies show that these products can serve as good MRI contrast agents. The bright upconversion luminescence of the products allows their use as fluorescence nanoprobes for live cells imaging. We also utilized the luminescence-emission capability of the UCNs for the activation of a photosensitizer to achieve significant PDT results. To the best of our knowledge, this study is the first use of lanthanide-doped Gd2O3 UCNs in a theranostics application. This investigation provides a useful platform for the development of Gd2O3-based UCNs for clinical diagnosis, treatment, and imaging-guided therapy of cancer.

  5. Magnetic and fluorescent Gd2O3:Yb3+/Ln3+ nanoparticles for simultaneous upconversion luminescence/MR dual modal imaging and NIR-induced photodynamic therapy

    Science.gov (United States)

    Liu, Jun; Huang, Long; Tian, Xiumei; Chen, Xiaoming; Shao, Yuanzhi; Xie, Fukang; Chen, Dihu; Li, Li

    2017-01-01

    The development of upconversion nanoparticles (UCNs) for theranostics application is a new strategy toward the accurate diagnosis and efficient treatment of cancer. Here, magnetic and fluorescent lanthanide-doped gadolinium oxide (Gd2O3) UCNs with bright upconversion luminescence (UCL) and high longitudinal relaxivity (r1) are used for simultaneous magnetic resonance imaging (MRI)/UCL dual-modal imaging and photodynamic therapy (PDT). In vitro and in vivo MRI studies show that these products can serve as good MRI contrast agents. The bright upconversion luminescence of the products allows their use as fluorescence nanoprobes for live cells imaging. We also utilized the luminescence-emission capability of the UCNs for the activation of a photosensitizer to achieve significant PDT results. To the best of our knowledge, this study is the first use of lanthanide-doped Gd2O3 UCNs in a theranostics application. This investigation provides a useful platform for the development of Gd2O3-based UCNs for clinical diagnosis, treatment, and imaging-guided therapy of cancer. PMID:28031709

  6. Isoquinoline-based lanthanide complexes: bright NIR optical probes and efficient MRI agents.

    Science.gov (United States)

    Caillé, Fabien; Bonnet, Célia S; Buron, Frédéric; Villette, Sandrine; Helm, Lothar; Petoud, Stéphane; Suzenet, Franck; Tóth, Eva

    2012-02-20

    In the objective of developing ligands that simultaneously satisfy the requirements for MRI contrast agents and near-infrared emitting optical probes that are suitable for imaging, three isoquinoline-based polyaminocarboxylate ligands, L1, L2 and L3, have been synthesized and the corresponding Gd(3+), Nd(3+) and Yb(3+) complexes investigated. The specific challenge of the present work was to create NIR emitting agents which (i) have excitation wavelengths compatible with biological applications and (ii) are able to emit a sufficient number of photons to ensure sensitive NIR detection for microscopic imaging. Here we report the first observation of a NIR signal arising from a Ln(3+) complex in aqueous solution in a microscopy setup. The lanthanide complexes have high thermodynamic stability (log K(LnL) =17.7-18.7) and good selectivity for lanthanide ions versus the endogenous cations Zn(2+), Cu(2+), and Ca(2+) thus preventing transmetalation. A variable temperature and pressure (17)O NMR study combined with nuclear magnetic relaxation dispersion measurements yielded the microscopic parameters characterizing water exchange and rotation. Bishydration of the lanthanide cation in the complexes, an important advantage to obtain high relaxivity for the Gd(3+) chelates, has been demonstrated by (17)O chemical shifts for the Gd(3+) complexes and by luminescence lifetime measurements for the Yb(3+) analogues. The water exchange on the three Gd(3+) complexes is considerably faster (k(ex)(298) = (13.9-15.4) × 10(6) s(-1)) than on commercial Gd(3+)-based contrast agents and proceeds via a dissociative mechanism, as evidenced by the large positive activation volumes for GdL1 and GdL2 (+10.3 ± 0.9 and +10.6 ± 0.9 cm(3) mol(-1), respectively). The relaxivity of GdL1 is doubled at 40 MHz and 298 K in fetal bovine serum (r(1) = 16.1 vs 8.5 mM(-1) s(-1) in HEPES buffer), due to hydrophobic interactions between the chelate and serum proteins. The isoquinoline core allows for the

  7. Lanthanide complexes as luminogenic probes to measure sulfide levels in industrial samples.

    Science.gov (United States)

    Thorson, Megan K; Ung, Phuc; Leaver, Franklin M; Corbin, Teresa S; Tuck, Kellie L; Graham, Bim; Barrios, Amy M

    2015-10-08

    A series of lanthanide-based, azide-appended complexes were investigated as hydrogen sulfide-sensitive probes. Europium complex 1 and Tb complex 3 both displayed a sulfide-dependent increase in luminescence, while Tb complex 2 displayed a decrease in luminescence upon exposure to NaHS. The utility of the complexes for monitoring sulfide levels in industrial oil and water samples was investigated. Complex 3 provided a sensitive measure of sulfide levels in petrochemical water samples (detection limit ∼ 250 nM), while complex 1 was capable of monitoring μM levels of sulfide in partially refined crude oil.

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

    Science.gov (United States)

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

    2015-04-20

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

  9. New luminescent materials and filters for Luminescent Solar Concentrators

    NARCIS (Netherlands)

    De Boer, D.K.G.; Ronda, C.R.; Keur, W.C.; Meijerink, A.

    2012-01-01

    In a Luminescent Solar Concentrator (LSC), short-wavelength light isconverted by a luminescent material into long-wavelength light, which is guided towards a photovoltaic cell. In principle, an LSC allows for high concentration, but in practice this is prevented by lossmechanisms like limited sunlig

  10. High coating of Ru(II) complexes on gold nanoparticles for single particle luminescence imaging in cells.

    Science.gov (United States)

    Rogers, Nicola J; Claire, Sunil; Harris, Robert M; Farabi, Shiva; Zikeli, Gerald; Styles, Iain B; Hodges, Nikolas J; Pikramenou, Zoe

    2014-01-18

    Gold nanoparticles are efficiently labelled with a luminescent ruthenium complex, producing 13 and 100 nm diameter, monodisperse red-emissive imaging probes with luminescence lifetimes prolonged over the molecular unit. Single, 100 nm particles are observed in whole cell luminescence imaging which reveals their biomolecular association with chromatin in the nucleus of cancer cells.

  11. Synthèse par voie hydrothermale des orthophosphates de lanthanides pour des applications optiques

    OpenAIRE

    Garrido-Hernandez, Aristeo

    2015-01-01

    Rare earth (Re) doped lanthanide orthophosphates (LnPO4) are considered like promising phosphors for optical applications. Phosphors are luminescent materials which convert certain types of energy (X-ray, ultraviolet, visible, infrared) mainly into visible light. In this research Eu3+ (europium), Ce3+ (cerium), Tb3+ (terbium), Er3+ (erbium), Tm3+ (thulium) and/or Yb3+ (ytterbium) doped LuPO4 (lutetium orthophosphate), YPO4 (yttrium orthophosphate), GdPO4 (gadolinium orthophosphate) and/or Gdx...

  12. Synthèse par voie hydrothermale des orthophosphates de lanthanides pour des applications optiques

    OpenAIRE

    Garrido-Hernandez, Aristeo

    2015-01-01

    Rare earth (Re) doped lanthanide orthophosphates (LnPO4) are considered like promising phosphors for optical applications. Phosphors are luminescent materials which convert certain types of energy (X-ray, ultraviolet, visible, infrared) mainly into visible light. In this research Eu3+ (europium), Ce3+ (cerium), Tb3+ (terbium), Er3+ (erbium), Tm3+ (thulium) and/or Yb3+ (ytterbium) doped LuPO4 (lutetium orthophosphate), YPO4 (yttrium orthophosphate), GdPO4 (gadolinium orthophosphate) and/or Gdx...

  13. Partial least-squares analysis of time decay data for Eu(III)-tetracycline complexes: simultaneous luminescent determination of tetracycline and oxytetracycline in bovine serum.

    Science.gov (United States)

    Ibañez, Gabriela A

    2008-05-30

    A simple and sensitive methodology to simultaneously quantify tetracycline and oxytetracycline in bovine serum samples is described. The method combines the advantages of the lanthanide-sensitized luminescence (i.e., sensitivity and selectivity) with partial least-squares (PLS) analysis, and requires no previous separation steps. Due to the strong overlapping of emission and excitation spectra of the analytes and their europium complexes, the luminescence decay curve (intensity of luminescence vs. time) of analyte-Eu complex was selected to resolve mixtures of tetracycline and oxytetracycline. Partial least-squares uses the luminescence decay as discriminatory parameter and regresses the luminescence versus time onto the concentrations of standards. Using a 16-sample aqueous calibration set, 10 validation samples, 11 spiked serum bovine samples and a blank of serum were studied. The analyte recoveries from serum samples ranged from 87 to 104% for tetracycline and from 94 to 106% for oxytetracycline. The results obtained by the developed method were statistically comparable to those obtained with high performance liquid chromatography.

  14. Luminescent properties of aluminum hydride

    Energy Technology Data Exchange (ETDEWEB)

    Baraban, A.P.; Gabis, I.E.; Dmitriev, V.A. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Dobrotvorskii, M.A., E-mail: mstislavd@gmail.com [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Kuznetsov, V.G. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Matveeva, O.P. [National Mineral Resources University, Saint Petersburg 199106 (Russian Federation); Titov, S.A. [Petersburg State University of Railway Transport, Saint-Petersburg 190031 (Russian Federation); Voyt, A.P.; Elets, D.I. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation)

    2015-10-15

    We studied cathodoluminescence and photoluminescence of α-AlH{sub 3}– a likely candidate for use as possible hydrogen carrier in hydrogen-fueled vehicles. Luminescence properties of original α-AlH{sub 3} and α-AlH{sub 3} irradiated with ultraviolet were compared. The latter procedure leads to activation of thermal decomposition of α-AlH{sub 3} and thus has a practical implementation. We showed that the original and UV-modified aluminum hydride contain luminescence centers ‐ structural defects of the same type, presumably hydrogen vacancies, characterized by a single set of characteristic bands of radiation. The observed luminescence is the result of radiative intracenter relaxation of the luminescence center (hydrogen vacancy) excited by electrons or photons, and its intensity is defined by the concentration of vacancies, and the area of their possible excitation. UV-activation of the dehydrogenation process of aluminum hydride leads to changes in the spatial distribution of the luminescence centers. For short times of exposure their concentration increases mainly in the surface regions of the crystals. At high exposures, this process extends to the bulk of the aluminum hydride and ends with a decrease in concentration of luminescence centers in the surface region. - Highlights: • Aluminum hydride contains hydrogen vacancies which serve as luminescence centers. • The luminescence is the result of radiative relaxation of excited centers. • Hydride UV-irradiation alters distribution and concentration of luminescence centers.

  15. Modulating the near-infrared luminescence of neodymium and ytterbium complexes with tridentate ligands based on benzoxazole-substituted 8-hydroxyquinolines.

    Science.gov (United States)

    Shavaleev, Nail M; Scopelliti, Rosario; Gumy, Frédéric; Bünzli, Jean-Claude G

    2009-04-01

    An improved synthesis of 2-(2'-benzothiazole)- and 2-(2'-benzoxazole)-8-hydroxyquinoline ligands that combine a tridentate N,N,O-chelating unit for metal binding and extended chromophore for light harvesting is developed. The 2-(2'-benzoxazole)-8-hydroxyquinoline ligands form mononuclear nine-coordinate complexes with neodymium, [Nd(kappa(3)-ligand)(3)], and an eight-coordinate complex with ytterbium, [Yb(kappa(3)-ligand)(2) x (kappa(1)-ligand) x H(2)O], as verified by crystallographic characterization of five complexes with four different ligands. The chemical stability of the complexes increases when the ligand contains 5,7-dihalo-8-hydroxyquinoline versus an 8-hydroxyquinoline group. The complexes feature a ligand-centered visible absorption band with a maximum at 508-527 nm and an intensity of (7.5-9.6) x 10(3) M(-1) x cm(-1). Upon excitation with UV and visible light within ligand absorption transitions, the complexes display characteristic lanthanide luminescence in the near-infrared at 850-1450 nm with quantum yields and lifetimes in the solid state at room temperature as high as 0.33% and 1.88 micros, respectively. The lanthanide luminescence in the complexes is enhanced upon halogenation of the 5,7-positions in the 8-hydroxyquinoline group and upon the addition of electron-donating substituents to the benzoxazole ring. Facile modification of chromophore units in 2-(2'-benzoxazole)-8-hydroxyquinoline ligands provides means for controlling the luminescence properties of their lanthanide complexes.

  16. A high sensitivity optically stimulated luminescence scanning system for measurement of single sand-sized grains

    DEFF Research Database (Denmark)

    Duller, G.A.T.; Bøtter-Jensen, L.; Kohsiek, P.;

    1999-01-01

    An instrument has been designed for the routine analysis of the optically stimulated luminescence signal from single grains of sand. The system is capable of analysing over 3000 individual grains in a single measurement sequence, and the OSL signal from each grain can be read in less than 3 s....... The design principles are described, along with preliminary measurements that illustrate the operation of the system and its capabilities....

  17. 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

  18. Highly luminescent and cytocompatible cationic Ag2S NIR-emitting quantum dots for optical imaging and gene transfection

    OpenAIRE

    Duman, Fatma Demir; Hocaoğlu, İbrahim; Hocaoglu, Ibrahim; Öztürk, Deniz Gülfem; Ozturk, Deniz Gulfem; Gözüaçık, Devrim; Gozuacik, Devrim; Kiraz, Alper; Yağcı Acar, Havva; Yagci Acar, Havva

    2015-01-01

    Nanoscale PAPER Cite this: Nanoscale, 2015, 7, 11352 Received 12th January 2015, Accepted 23rd May 2015 DOI: 10.1039/c5nr00189g www.rsc.org/nanoscale Highly luminescent and cytocompatible cationic Ag2S NIR-emitting quantum dots for optical imaging and gene transfection† Fatma Demir Duman,a Ibrahim Hocaoglu,a Deniz Gulfem Ozturk,b Devrim Gozuacik,b Alper Kiraza,c and Havva Yagci Acar*a,d,e The development of non-toxic theranostic nanoparticles capable of del...

  19. Future prospects of luminescent nanomaterial based security inks: from synthesis to anti-counterfeiting applications

    Science.gov (United States)

    Kumar, Pawan; Singh, Satbir; Gupta, Bipin Kumar

    2016-07-01

    Counterfeiting of valuable documents, currency and branded products is a challenging problem that has serious economic, security and health ramifications for governments, businesses and consumers all over the world. It is estimated that counterfeiting represents a multi-billion dollar underground economy with counterfeit products being produced on a large scale every year. Counterfeiting is an increasingly high-tech crime and calls for high-tech solutions to prevent and deter the acts of counterfeiting. The present review briefly outlines and addresses the key challenges in this area, including the above mentioned concerns for anti-counterfeiting applications. This article describes a unique combination of all possible kinds of security ink formulations based on lanthanide doped luminescent nanomaterials, quantum dots (semiconductor and carbon based), metal organic frameworks as well as plasmonic nanomaterials for their possible use in anti-counterfeiting applications. Moreover, in this review, we have briefly discussed and described the historical background of luminescent nanomaterials, basic concepts and detailed synthesis methods along with their characterization. Furthermore, we have also discussed the methods adopted for the fabrication and design of luminescent security inks, various security printing techniques and their anti-counterfeiting applications.

  20. Effect of indium addition in U-Zr metallic fuel on lanthanide migration

    Science.gov (United States)

    Kim, Yeon Soo; Wiencek, T.; O'Hare, E.; Fortner, J.; Wright, A.; Cheon, J. S.; Lee, B. O.

    2017-02-01

    Advanced fast reactor concepts to achieve ultra-high burnup (∼50%) require prevention of fuel-cladding chemical interaction (FCCI). Fission product lanthanide accumulation at high burnup is substantial and significantly contributes to FCCI upon migration to the cladding interface. Diffusion barriers are typically used to prevent interaction of the lanthanides with the cladding. A more active method has been proposed which immobilizes the lanthanides through formation of stable compounds with an additive. Theoretical analysis showed that indium, thallium, and antimony are good candidates. Indium was the strongest candidate because of its low reactivity with iron-based cladding alloys. Characterization of the as-fabricated alloys was performed to determine the effectiveness of the indium addition in forming compounds with lanthanides, represented by cerium. Tests to examine how effectively the dopant prevents lanthanide migration under a thermal gradient were also performed. The results showed that indium effectively prevented cerium migration.

  1. Synthesis and bio-imaging application of highly luminescent mercaptosuccinic acid-coated CdTe nanocrystals.

    Directory of Open Access Journals (Sweden)

    Erbo Ying

    Full Text Available Here we present a facile one-pot method to prepare high-quality CdTe nanocrystals in aqueous phase. In contrast to the use of oxygen-sensitive NaHTe or H(2Te as Te source in the current synthetic methods, we employ more stable sodium tellurite as the Te source for preparing highly luminescent CdTe nanocrystals in aqueous solution. By selecting mercaptosuccinic acid (MSA as capping agent and providing the borate-citrate acid buffering solution, CdTe nanocrystals with high quantum yield (QY >70% at pH range 5.0-8.0 can be conveniently prepared by this method. The influence of parameters such as the pH value of the precursor solution and the molar ratio of Cd(2+ to Na(2TeO(3 on the QY of CdTe nanocrystals was systematically investigated in our experiments. Under optimal conditions, the QY of CdTe nanocrystals is even high up to 83%. The biological application of luminescent MSA-CdTe to HEK 293 cell imaging was also illustrated.

  2. Synthesis of highly luminescent water stable ZnO quantum dots as photoluminescent sensor for picric acid

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Kulvinder; Chaudhary, G.R.; Singh, Sukhjinder; Mehta, S.K., E-mail: skmehta@pu.ac.in

    2014-10-15

    Highly luminescent, water stable (3-aminopropyl) triethoxysilane capped ZnO quantum dots (QDs) have been synthesized using a simple solution route. The synthesized ZnO QDs have been characterized using X-ray diffraction (XRD), Transmission electron microscopy (TEM), Particle size analyzer (PSA), UV–visible (UV–vis), Photoluminescence (PL) and Fourier transform infrared (FTIR) spectroscopy. The PL studies demonstrate that the particles synthesized are highly luminescent in nature emitting yellow color on exposure to UV radiation. Further, PL emission of ZnO QDs in the presence of picric acid (PA) shows their high sensitivity and selectivity for PA. The superior response of ZnO QDs in the presence of PA makes them very effective PL sensors. The limit of detection comes out to be 2.86 µM. - Highlights: • ZnO QDs act as photoluminiscent sensor for picric acid in aqueous medium. • Sensor shows high selectivity and sensitivity with a detection limit of 2.86 μM. • More the number of nitro groups, more is the quenching in PL emission of ZnO QDs.

  3. The Lanthanide Contraction beyond Coordination Chemistry.

    Science.gov (United States)

    Ferru, Geoffroy; Reinhart, Benjamin; Bera, Mrinal K; Olvera de la Cruz, Monica; Qiao, Baofu; Ellis, Ross J

    2016-05-10

    The lanthanide contraction is conceptualized traditionally through coordination chemistry. Here we break this mold in a structural study of lanthanide ions dissolved in an amphiphilic liquid. The lanthanide contraction perturbs the weak interactions between molecular aggregates that drive mesoscale assembly and emergent behavior. The weak interactions correlate with lanthanide ion transport properties, suggesting new strategies for rare-earth separation that exploit forces outside of the coordination sphere.

  4. Fungus-promoted transformation of lanthanides during the biooxidation of divalent manganese

    Science.gov (United States)

    Yu, Qianqian; Ohnuki, Toshihiko; Tanaka, Kazuya; Kozai, Naofumi; Yamasaki, Shinya; Sakamoto, Fuminori; Tani, Yukinori

    2016-02-01

    Although microorganisms possess high sorption capability for lanthanides, the effect of their biological response on lanthanides migration is unclear. Using active fungus Acremonium strictum KR21-2, supplied with nutrients, this study compared the transformation of lanthanides during the biooxidation of Mn(II) in the absence and presence of trisodium citrate. In the absence of trisodium citrate, lanthanides were rapidly sorbed on fungal cells within 24 h, followed by the preferential desorption of Ce over other lanthanides as Mn oxide formed. Most of the desorbed Ce was in the colloidal phase and associated with a biomolecule produced by the active fungus. In contrast, neither desorption of Ce nor release of this biomolecule occurred in the presence of trisodium citrate. Most importantly, the Ce-binding biomolecule was not found to associate with any other trivalent lanthanides tested or with Fe. The biomolecule was characterized as c.a. 4700 Da in size, and it contains saccharides that differed from those non-nuclide-specific organic substances released from resting cells, as reported previously. This study highlights the importance of biotic reactions between lanthanides and microbial cells, which may affect the migration of lanthanides at the water-Mn oxide interface.

  5. New Lanthanide Alkynylamidinates and Diiminophosphinates

    Directory of Open Access Journals (Sweden)

    Farid M. Sroor

    2015-11-01

    Full Text Available This contribution reports the synthesis and structural characterization of several new lithium and lanthanide alkynylamidinate complexes. Treatment of PhC≡CLi with N,N′-diorganocarbodiimides, R–N=C=N–R (R = iPr, Cy (cyclohexyl, in THF or diethyl ether solution afforded the lithium-propiolamidinates Li[Ph–C≡C–C(NCy2] S (1: R = iPr, S = THF; 2: R = Cy, S = THF; 3: R = Cy, S = Et2O. Single-crystal X-ray diffraction studies of 1 and 2 showed the presence of typical ladder-type dimeric structures in the solid state. Reactions of anhydrous LnCl3 (Ln = Ce, Nd, Sm or Ho with 2 in a 1:3 molar ratio in THF afforded a series of new homoleptic lanthanide tris(propiolamidinate complexes, [Ph–C≡C–C(NCy2]3Ln (4: Ln = Ce; 5: Ln = Nd; 6: Ln = Sm; 7: Ln = Ho. The products were isolated in moderate to high yields (61%–89% as brightly colored, crystalline solids. The chloro-functional neodymium(III bis(cyclopropylethynylamidinate complex [{c-C3H5–C≡C–C(NiPr2}2Ln(µ-Cl(THF]2 (8 was prepared from NdCl3 and two equiv. of Li[c-C3H5–C≡C–C(NiPr2] in THF and structurally characterized. A new monomeric Ce(III-diiminophosphinate complex, [Ph2P(NSiMe32]2Ce(µ-Cl2Li(THF2 (9, has also been synthesized in a similar manner from CeCl3 and two equiv. of Li[Ph2P(NSiMe32]. Structurally, this complex resembles the well-known “ate” complexes (C5Me52Ln(µ-Cl2Li(THF2. Attempts to oxidize compound 9 using trityl chloride or phenyliodine(III dichloride did not lead to an isolable cerium(IV species.

  6. Temperature dependent NIR emitting lanthanide-PMO/silica hybrid materials.

    Science.gov (United States)

    Kaczmarek, Anna M; Esquivel, Dolores; Ouwehand, Judith; Van Der Voort, Pascal; Romero-Salguero, Francisco J; Van Deun, Rik

    2017-06-28

    Two materials - a mesoporous silica (MS) and a periodic mesoporous organosilica (PMO) functionalized with dipyridyl-pyridazine (dppz) units were grafted with near-infrared (NIR) emitting lanthanide (Nd(3+), Er(3+), Yb(3+)) complexes in an attempt to obtain hybrid NIR emitting materials. The parent materials: dppz-vSilica and dppz-ePMO were prepared by a hetero Diels-Alder reaction between 3,6-di(2-pyridyl)-1,2,4,5-tetrazine (dptz) and the double bonds of either ethenylene-bridged PMO (ePMO) or vinyl-silica (vSilica) and subsequent oxidation. The dppz-vSilica is reported here for the first time. The prepared lanthanide-PMO/silica hybrid materials were studied in depth for their luminescence properties at room temperature and chosen Nd(3+) and Yb(3+) samples also at low temperature (as low as 10 K). We show that both the dppz-vSilica and dppz-ePMO materials can be used as "platforms" for obtaining porous materials showing NIR luminescence. To obtain NIR emission these materials can be excited either in the UV or Vis region (into the π→π* transitions of the ligands or directly into the f-f transitions of the Ln(3+) ions). More interestingly, when functionalized with Nd(3+) or Yb(3+)β-diketonate complexes these materials showed interesting luminescence properties over a wide temperature range (10-360 K). The Yb(3+) materials were investigated for their potential use as ratiometric temperature sensors.

  7. Hydrothermal synthesis of highly luminescent blue-emitting ZnSe(S) quantum dots exhibiting low toxicity.

    Science.gov (United States)

    Mirnajafizadeh, Fatemeh; Ramsey, Deborah; McAlpine, Shelli; Wang, Fan; Reece, Peter; Stride, John Arron

    2016-07-01

    Highly luminescent quantum dots (QDs) that emit in the visible spectrum are of interest to a number of imaging technologies, not least that of biological samples. One issue that hinders the application of luminescent markers in biology is the potential toxicity of the fluorophore. Here we show that hydrothermally synthesized ZnSe(S) QDs have low cytotoxicity to both human colorectal carcinoma cells (HCT-116) and human skin fibroblast cells (WS1). The QDs exhibited a high degree of crystallinity, with a strong blue photoluminescence at up to 29% quantum yield relative to 4',6-diamidino-2-phenylindole (DAPI) without post-synthetic UV-irradiation. Confocal microscopy images obtained of HCT-116 cells after incubation with the QDs highlighted the stability of the particles in cell media. Cytotoxicity studies showed that both HCT-116 and WS1 cells retain 100% viability after treatment with the QDs at concentrations up to 0.5g/L, which makes them of potential use in biological imaging applications.

  8. Lanthanide tris(β-diketonates) as useful probes for chirality determination of biological amino alcohols in vibrational circular dichroism: ligand to ligand chirality transfer in lanthanide coordination sphere.

    Science.gov (United States)

    Miyake, Hiroyuki; Terada, Keiko; Tsukube, Hiroshi

    2014-06-01

    A series of lanthanide tris(β-diketonates) functioned as useful chirality probes in the vibrational circular dichroism (VCD) characterization of biological amino alcohols. Various chiral amino alcohols induced intense VCD signals upon ternary complexation with racemic lanthanide tris(β-diketonates). The VCD signals observed around 1500 cm(-1) (β-diketonate IR absorption region) correlated well with the stereochemistry and enantiomeric purity of the targeted amino alcohol, while the corresponding monoalcohol, monoamine, and diol substrates induced very weak VCD signals. The high-coordination number and dynamic property of the lanthanide complex offer an effective chirality VCD probing of biological substrates.

  9. Highly luminescent nanostructures of CdS and ZnS prepared by microwaves heating: effect of sulphide concentration

    Energy Technology Data Exchange (ETDEWEB)

    Ortiz, Samuel; Gomez, Idalia; Elizondo, Perla [Facultad de Ciencias Quimicas, Universidad Autonoma de Nuevo Leon, Av. Universidad s/n, C.P. 66450 San Nicolas de los Garza (Mexico); Cavazos, Jose [Facultad de Ingenieria Mecanica y Electrica, Universidad Autonoma de Nuevo Leon, Av. Universidad s/n, C.P. 66450 San Nicolas de los Garza (Mexico)

    2010-11-15

    Nearly monodisperse and highly luminescent ZnS and CdS NPs were obtained by microwave irradiation. The ZnS and CdS NPs solutions were prepared by adding freshly prepared ZnSO{sub 4} or CdSO{sub 4} solution to a thioacetamide solution at pH 8 in the presence of sodium citrate in solution used as stabilizer. The precursors concentration were such that the sulphide ion concentrations were 3 x 10{sup -2} M, 6 x 10{sup -2} M and 8 x 10{sup -2} M, for each of these [S] concentrations the [Zn] or [Cd] content were fixed at 3 x 10{sup -2} M. NPs were prepared under microwave irradiation for 1 min at 905 W of power. The NPs samples were taken when the temperature descended to ambient temperature for further analysis. Effect of concentration of Cd and Zn ions were studied in the luminescence property. RXD, AFM, TEM and UV-Vis were used too as analytical equipment for characterization. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  10. Fabrication and characterization of highly luminescent Er3+:Al2O3 thin films with optimized growth parameters

    Science.gov (United States)

    Nayar, Priyanka; Zhu, Xue-Yi; Yang, Fuyi; Lu, Minghui; Lakshminarayana, G.; Liu, Xiao Ping; Chen, Yan-Feng; Kityk, I. V.

    2016-10-01

    Erbium doped amorphous alumina thin films were fabricated using Co-sputtering technique in various depositions runs with varying parameters for optimizing the deposition parameters to obtain the films with best optical performance. The main subject of investigation includes the effects of change in various deposition parameters such as substrate heating, radio frequency (RF) power and oxygen pressure inside the chamber while deposition. High quality as-deposited films with various Er concentrations and low carbon content have been confirmed by XPS. Substrate heating ∼500 °C was found to be very effective in getting highly dense films with high refractive index of 1.70 at 1530-1570 nm emission band. The Er3+-doped films showed very intense near-infrared luminescence peak at 1550 nm even without any post-deposition annealing treatment.

  11. Fracture-resistant lanthanide scintillators

    Science.gov (United States)

    Doty, F. Patrick

    2011-01-04

    Lanthanide halide alloys have recently enabled scintillating gamma ray spectrometers comparable to room temperature semiconductors (lanthanide alloy substitution, while preserving scintillation, have been demonstrated. Isovalent alloys having nominal compositions of comprising Al, Ga, Sc, Y, and In dopants as well as aliovalent alloys comprising Ca, Sr, Zr, Hf, Zn, and Pb dopants were prepared. All of these alloys exhibit bright fluorescence under UV excitation, with varying shifts in the spectral peaks and intensities relative to pure CeBr.sub.3. Further, these alloys scintillate when coupled to a photomultiplier tube (PMT) and exposed to .sup.137Cs gamma rays.

  12. Synthesis and Thermal Behaviour of Lanthanide Complexes of 4′-[(Cholesterylox y)Carbonyl]-Benzo-15-Crown-5

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Lanthanide complexes of a steroid-substituted benzocrown ether were synthesised . The metal-to-ligand ratio of all the metal complexes is 1∶1. The ligand 4′ -[(cholesteryloxy)carbonyl]-benzo-15-crown-5 is a monotropic liquid cryst al, displaying a cholesteric mesophase. The lanthanide complexes with nitrate co unter-ions form a highly viscous mesophase, decomposing at the clearing point. The transition temperatures change as a function of the lanthanide ion. The corr esponding lanthanide complexes with dodecylsulphate (DOS) counter-ions do not f orm a mesophase. In both cases, the metal complexes have a much lower melting po int than the parent ligand.

  13. Lanthanide upconversion luminescence at the nanoscale: fundamentals and optical properties.

    Science.gov (United States)

    Nadort, Annemarie; Zhao, Jiangbo; Goldys, Ewa M

    2016-07-01

    Upconversion photoluminescence is a nonlinear effect where multiple lower energy excitation photons produce higher energy emission photons. This fundamentally interesting process has many applications in biomedical imaging, light source and display technology, and solar energy harvesting. In this review we discuss the underlying physical principles and their modelling using rate equations. We discuss how the understanding of photophysical processes enabled a strategic influence over the optical properties of upconversion especially in rationally designed materials. We subsequently present an overview of recent experimental strategies to control and optimize the optical properties of upconversion nanoparticles, focussing on their emission spectral properties and brightness.

  14. Lanthanide upconversion luminescence at the nanoscale: fundamentals and optical properties

    Science.gov (United States)

    Nadort, Annemarie; Zhao, Jiangbo; Goldys, Ewa M.

    2016-07-01

    Upconversion photoluminescence is a nonlinear effect where multiple lower energy excitation photons produce higher energy emission photons. This fundamentally interesting process has many applications in biomedical imaging, light source and display technology, and solar energy harvesting. In this review we discuss the underlying physical principles and their modelling using rate equations. We discuss how the understanding of photophysical processes enabled a strategic influence over the optical properties of upconversion especially in rationally designed materials. We subsequently present an overview of recent experimental strategies to control and optimize the optical properties of upconversion nanoparticles, focussing on their emission spectral properties and brightness.

  15. Sensing temperature via downshifting emissions of lanthanide-doped metal oxides and salts. A review

    Science.gov (United States)

    Dramićanin, Miroslav D.

    2016-12-01

    Temperature is important because it has an effect on even the tiniest elements of daily life and is involved in a broad spectrum of human activities. That is why it is the most commonly measured physical quantity. Traditional temperature measurements encounter difficulties when used in some emerging technologies and environments, such as nanotechnology and biomedicine. The problem may be alleviated using optical techniques, one of which is luminescence thermometry. This paper reviews the state of luminescence thermometry and presents different temperature read-out schemes with an emphasis on those utilizing the downshifting emission of lanthanide-doped metal oxides and salts. The read-out schemes for temperature include those based on measurements of spectral characteristics of luminescence (band positions and shapes, emission intensity and ratio of emission intensities), and those based on measurements of the temporal behavior of luminescence (lifetimes and rise times). This review (with 140 references) gives the basics of the fundamental principles and theory that underlie the methods presented, and describes the methodology for the estimation of their performance. The major part of the text is devoted to those lanthanide-doped metal oxides and salts that are used as temperature probes, and to the comparison of their performance and characteristics.

  16. Highly potent extranuclear-targeted luminescent iridium(iii) antitumor agents containing benzimidazole-based ligands with a handle for functionalization.

    Science.gov (United States)

    Yellol, Jyoti; Pérez, Sergio A; Yellol, Gorakh; Zajac, Juraj; Donaire, Antonio; Vigueras, Gloria; Novohradsky, Vojtech; Janiak, Christoph; Brabec, Viktor; Ruiz, José

    2016-12-01

    A series of 6 substitutionally inert and luminescent iridium(iii) antitumor agents of the type [Ir(C(∧)N)2(N(∧)N)][PF6] containing a benzimidazole N(∧)N ligand with an ester group as a handle for further functionalization has been prepared. They exhibit IC50 values in the high nanomolar range in some ovarian and breast cancer cell lines (approximately 100× more cytotoxic than cisplatin (CDDP) in MDA-MB-231) and are located in the actin cortex predominantly as shown by confocal luminescence microscopy. This discovery could open the door to a new large family of drug bioconjugates with diverse and simultaneous functions.

  17. Highly luminescent water-soluble quaternary Zn-Ag-In-S quantum dots for tumor cell-targeted imaging.

    Science.gov (United States)

    Deng, Dawei; Cao, Jie; Qu, Lingzhi; Achilefu, Samuel; Gu, Yueqing

    2013-04-14

    Exploring the synthesis and biomedical applications of biocompatible quantum dots (QDs) is currently one of the fastest growing fields of nanotechnology. Hence, in this work, we present a facile approach to produce water-soluble (cadmium-free) quaternary Zn-Ag-In-S (ZAIS) QDs. Their efficient photoluminescence (PL) emissions can be tuned widely in the range of 525-625 nm by controlling the size and composition of the QDs with the PL quantum yields (QYs) of 15-30%. These highly luminescent ZAIS QDs are less toxic due to the absence of highly toxic cadmium, and can be versatilely modified by a DHLA-PEG-based ligand. Importantly, after being modified by tumor cell-specific targeting ligands (e.g., folate and RGD peptide), the PEGylated quaternary QDs show potential applications in tumor cell imaging as a promising alternative for Cd-based QDs.

  18. Separation of lanthanides through hydroxyapatite; Separacion de lantanidos mediante hidroxiapatita

    Energy Technology Data Exchange (ETDEWEB)

    Garcia M, F.G

    2006-07-01

    With the objective of obtaining from an independent way to each one of the lanthanides {sup 151} Pm, {sup 161} Tb, {sup 166} Ho and {sup 177} Lu free of carrier and with high specific activities starting from the indirect irradiation via, it intends in this work to determine the viability of separation of the couples Nd/Pm, Dy/Ho, Gd/Tb and Yb/Lu, by means of ion exchange column chromatography, using hydroxyapatite (HAp) and fluorite like absorbent material in complexing media. It is important to mention that have registered separation studies among lanthanides of the heavy group with those of the slight group, using the same mass and, in comparison with this work, quantities different from the father were used and of the son, also, that the separation studies were carried out among neighboring lanthanides. In this investigation, it was determined the effect that its have the complexing media: KSCN, sodium tartrate, sodium citrate, EDTA and aluminon, their pH and concentration, in the adsorption of the lanthanides in both minerals, in order to determine the chromatographic conditions for separation of the couples Nd/Pm, Dy/Ho, Gd/Tb and Yb/Lu. The work consists of five chapters, in the first one they are presented a theoretical introduction of the characteristics more important of the lanthanides, the hydroxyapatite and the fluorite; in the second, it is deepened in the ion exchange, as well as the two techniques (XRD and High Vacuum Electron Microscopy) to make the characterization of LnCI{sub 3} (Ln = Nd, Gd, Dy or Yb) synthesized. The third chapter, it describes the methodology continued in our experimental work; in the room, its are presented the obtained results of the static and dynamic method to determine the viability of separation of neighboring lanthanides; and finally, the five chapter shows the conclusions. In this study, it is concludes that the separation among neighboring lanthanides cannot be carried out in the minerals and used media; because

  19. Beryl-II, a high-pressure phase of beryl: Raman and luminescence spectroscopy to 16.4 GPa

    Science.gov (United States)

    O'Bannon, Earl; Williams, Quentin

    2016-10-01

    The Raman and Cr3+ and V2+ luminescence spectra of beryl and emerald have been characterized up to 15.0 and 16.4 GPa, respectively. The Raman spectra show that an E 1g symmetry mode at 138 cm-1 shifts negatively by -4.57 (±0.55) cm-1/GPa, and an extrapolation of the pressure dependence of this mode indicates that a soft-mode transition should occur near 12 GPa. Such a transition is in accord with prior theoretical results. Dramatic changes in Raman mode intensities and positions occur between 11.2 and 15.0 GPa. These changes are indicative of a phase transition that primarily involves tilting and mild distortion of the Si6O18 rings. New Raman modes are not observed in the high-pressure phase, which indicates that the local bonding environment is not altered dramatically across the transition (e.g., changes in coordination do not occur). Both sharp line and broadband luminescence are observed for both Cr3+ and V2+ in emerald under compression to 16.4 GPa. The R-lines of both Cr3+ and V2+ shift to lower energy (longer wavelength) under compression. Both R-lines of Cr3+ split at ~13.7 GPa, and the V2+ R1 slope changes at this pressure and shifts more rapidly up to ~16.4 GPa. The Cr3+ R-line splitting and FWHM show more complex behavior, but also shift in behavior at ~13.7 GPa. These changes in the pressure dependency of the Cr3+ and V2+ R-lines and the changes in R-line splitting and FWHM at ~13.7 GPa further demonstrate that a phase transition occurs at this pressure, in good agreement with our Raman results. The high-pressure phase of beryl appears to have two Al sites that become more regular under compression. Hysteresis is not observed in our Raman or luminescence spectra on decompression, suggesting that this transition is second order in nature: The occurrence of a second-order transition near this pressure is also in accord with prior theoretical results. We speculate that the high-pressure phase (beryl-II) might be a mildly modulated structure, and/or that

  20. Luminescent and Non-Luminescent Solar Concentrators: Challenges andd Progress

    NARCIS (Netherlands)

    De Boer, D.K.G.

    2012-01-01

    Luminescent concentrators would allow for high concentration if losses by reabsorption and escape could be minimized. We present new phosphors and filters that facilitate this. Another type of lightguide-based concentrators, diffraction-based, is discussed as well.

  1. Luminescent and Non-Luminescent Solar Concentrators: Challenges andd Progress

    NARCIS (Netherlands)

    De Boer, D.K.G.

    2012-01-01

    Luminescent concentrators would allow for high concentration if losses by reabsorption and escape could be minimized. We present new phosphors and filters that facilitate this. Another type of lightguide-based concentrators, diffraction-based, is discussed as well.

  2. Core–shell Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses: Preparation and their effects on photoluminescence of lanthanide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Jie; Li, Yuan; Chen, Yingnan; Wang, Ailing; Yue, Bin; Qu, Yanrong; Zhao, Yongliang; Chu, Haibin, E-mail: chuhb@imu.edu.cn

    2015-11-15

    Highlights: • Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses were prepared via the Stöber process. • Sm and Dy complexes with benzoate, 1,10-phenanthroline and 2,2′-bipyridine were synthesized. • The complex-doped Ag@SiO{sub 2} composites show stronger luminescent intensities than pure complexes. • The luminescent intensities of the composites strongly depend on the SiO{sub 2} shell thickness. - Abstract: Three kinds of almost spherical core–shell Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses (10, 25 and 80 nm) were prepared via the Stöber process. The Ag core nanoparticles were prepared by reducing silver nitrate with sodium citrate. The size, morphology and structure of core–shell Ag@SiO{sub 2} nanoparticles were characterized by transmission electron microscopy. Subsequently, eight kinds of lanthanide complexes with benzoate, 1,10-phenanthroline and 2,2′-bipyridine were synthesized. The composition of the lanthanide complexes was characterized by elemental analysis, IR and UV spectra. Finally, lanthanide complexes were attached to the surface of Ag@SiO{sub 2} nanoparticles to form lanthanide-complex-doped Ag@SiO{sub 2} nanocomposites. The results show that the complex-doped Ag@SiO{sub 2} nanocomposites display much stronger luminescence intensities than the lanthanide complexes. Furthermore, the luminescence intensities of the lanthanide-complex-doped Ag@SiO{sub 2} nanocomposites with SiO{sub 2} shell thickness of 25 nm are stronger than those of the nanocomposites with SiO{sub 2} shell thickness of 10 and 80 nm.

  3. Bright CuInS2/CdS nanocrystal phosphors for high-gain full-spectrum luminescent solar concentrators.

    Science.gov (United States)

    Knowles, Kathryn E; Kilburn, Troy B; Alzate, Dane G; McDowall, Stephen; Gamelin, Daniel R

    2015-06-04

    The performance of colloidal CuInS2/CdS nanocrystals as phosphors for full-spectrum luminescent solar concentrators has been examined. Their combination of large solar absorption, high photoluminescence quantum yields, and only moderate reabsorption produces the highest projected flux gains of any nanocrystal luminophore to date.

  4. Structure-Triggered High Quantum Yield Luminescence and Switchable Dielectric Properties in Manganese(II) Based Hybrid Compounds.

    Science.gov (United States)

    Wang, Zhong-Xia; Li, Peng-Fei; Liao, Wei-Qiang; Tang, Yuanyuan; Ye, Heng-Yun; Zhang, Yi

    2016-04-01

    Two new manganese(II) based organic-inorganic hybrid compounds, C11H21Cl3MnN2 (1) and C11H22Cl4MnN2 (2), with prominent photoluminescence and dielectric properties were synthesized by solvent modulation. Compound 1 with novel trigonal bipyramidal geometry exhibits bright red luminescence with a lifetime of 2.47 ms and high quantum yield of 35.8 %. Compound 2 with tetrahedral geometry displays intense long-lived (1.54 ms) green light emission with higher quantum yield of 92.3 %, accompanied by reversible solid-state phase transition at 170 K and a distinct switchable dielectric property. The better performance of 2 results from the structure, including a discrete organic cation moiety and inorganic metal anion framework, which gives the cations large freedom of motion.

  5. Thermodynamic and Spectroscopic Studies of Lanthanides(III) Complexation with Polyamines in Dimethyl Sulfoxide

    Energy Technology Data Exchange (ETDEWEB)

    Di Bernardo, Plinio [Univ. of Padova (Italy); Zanonato, Pier Luigi [Univ. of Padova (Italy); Melchior, Andrea [Univ. of Udine (Italy); Portanova, Roberto [Univ. of Udine (Italy); Tolazzi, Marilena [Univ. of Udine (Italy); Choppin, Gregory R. [Florida State Univ., Tallahassee, FL (United States); Wang, Zheming [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2008-01-01

    The thermodynamic parameters of complexation of Ln(III) cations with tris(2-aminoethyl)amine (tren) and tetraethylenepentamine (tetren) were determined in dimethyl sulfoxide (DMSO) by potentiometry and calorimetry. The excitation and emission spectra and luminescence decay constants of Eu3+ and Tb3+ complexed by tren and tetren, as well as those of the same lanthanides(III) complexed with diethylenetriamine (dien) and triethylenetetramine (trien), were also obtained in the same solvent. The combination of thermodynamic and spectroscopic data showed that, in the 1:1 complexes, all nitrogens of the ligands bound to the lanthanides except in the case of tren, in which only pendant N bound. For the larger ligands (trien, tren, tetren) in the higher complexes (ML2), there was less complete binding by available donors, presumably due to steric crowding. FT-IR studies were carried out in an acetonitrile/DMSO mixture, suitably chosen in order to follow the changes in the primary solvation sphere of lanthanide(III) due to complexation of amine ligands. Results show that the mean number of molecules of DMSO removed from the inner coordination sphere of lanthanides(III) is lower than ligand denticity and that the coordination number of the metal ions increases with amine complexation from ~8 to ~10. Independently of the number and structure of the amines, linear trends, similar for all lanthanides, were obtained by plotting the values of ΔGj°, ΔHj° and TΔSj° for the complexation of ethylenediamine (en), dien, trien, tren and tetren as a function of the number of amine metal-coordinated nitrogen atoms. The main factors on which the thermodynamic functions of lanthanide(III) complexation reactions in DMSO depend are discussed.

  6. Preparation, characterization and luminescence of nanocrystalline Y{sub 2}O{sub 3}:Ho

    Energy Technology Data Exchange (ETDEWEB)

    Biljan, Tomislav [Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb (Croatia)]. E-mail: tomislav.biljan@chem.pmf.hr; Gajovic, Andreja [Ruder Boskovic Institute, POB 180, HR-10002 Zagreb (Croatia); Meic, Zlatko [Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb (Croatia); Mestrovic, Ernest [PLIVA, Research and Development Ltd., Prilaz baruna Filipovica 29, 10000 Zagreb (Croatia)

    2007-04-04

    Nanocrystalline Y{sub 2}O{sub 3}:Ho was synthesized by solution combustion method with ethylene glycol as fuel. Material was characterized using powder X-ray diffraction and transmission electron microscopy (TEM). X-ray diffraction and TEM showed that the material is nanostructured. Luminescence properties were studied using Raman spectrometers with excitation in near infrared (NIR) and visible regions. The visible and NIR luminescence spectra of nanocrystalline Y{sub 2}O{sub 3}:Ho show some important differences from those of bulk material. The convenience of using Raman instruments for studying luminescence of lanthanide ions is demonstrated.

  7. Optical Properties of Heavily Fluorinated Lanthanide Tris β-Diketonate Phosphine Oxide Adducts

    Directory of Open Access Journals (Sweden)

    Adam N. Swinburne

    2016-09-01

    Full Text Available The construction of lanthanide(III chelates that exhibit superior photophysical properties holds great importance in biological and materials science. One strategy to increase the luminescence properties of lanthanide(III chelates is to hinder competitive non-radiative decay processes through perfluorination of the chelating ligands. Here, the synthesis of two families of heavily fluorinated lanthanide(III β-diketonate complexes bearing monodentate perfluorinated tris phenyl phosphine oxide ligands have been prepared through a facile one pot reaction [Ln(hfac3{(ArF3PO}(H2O] and [Ln(F7-acac3{(ArF3PO}2] (where Ln = Sm3+, Eu3+, Tb3+, Er3+ and Yb3+. Single crystal X-ray diffraction analysis in combination with photophysical studies have been performed to investigate the factors responsible for the differences in the luminescence lifetimes and intrinsic quantum yields of the complexes. Replacement of both bound H2O and C–H oscillators in the ligand backbone has a dramatic effect on the photophysical properties of the complexes, particularly for the near infra-red emitting ion Yb3+, where a five fold increase in luminescence lifetime and quantum yield is observed. The complexes [Sm(hfac3{(ArF3PO}(H2O] (1, [Yb(hfac3{(ArF3PO}(H2O] (5, [Sm(F7-acac3{(ArF3PO}2] (6 and [Yb(F7-acac3{(ArF3PO}2] (10 exhibit unusually long luminescence lifetimes and attractive intrinsic quantum yields of emission in fluid solution (ΦLn = 3.4% (1; 1.4% (10 and in the solid state (ΦLn = 8.5% (1; 2.0% (5; 26% (6; 11% (10, which are amongst the largest values for this class of compounds to date.

  8. Structural and spectroscopic investigation of new luminescent hybrid materials based on calix[4]arene-tetracarboxylate and Ln3+ ions (Ln = Gd, Tb or Eu)

    Science.gov (United States)

    Viana, R. S.; Oliveira, C. A. F.; Chojnacki, J.; Barros, B. S.; Alves-Jr, S.; Kulesza, J.

    2017-07-01

    Lanthanide-calixarene hybrid materials are of particular interest due to the combination of the interesting properties of the ligand cavity-like structure and the luminescent features of lanthanides. The aim of this study was to synthesize and investigate the photophysical properties of Eu3+, Tb3+ and Gd3+ hybrids based on calix[4]arene-tetracarboxylate. The preparation of two structurally different Tb3+ compounds (calix-TA-SC-Tb and calix-TA-Tb) was dictated by the ligand to metal molar ratio and the synthesis time. Analysis of calix-TA-SC-Tb monocrystals revealed the formation of a mononuclear complex of C2 symmetry containing Tb3+ coordinated by four calixarene ionized groups and formate anion encapsulated within the upper cavity. Syntheses of other hybrids failed in producing high-quality crystals and the structures could not be solved. The solid-state luminescent properties of hybrids were evaluated, and the structure/property relationship was investigated. Based on the emission and excitation spectra, the energy diagrams for calix-TA-Eu, calix-TA-Tb and calix-TA-Gd were proposed.

  9. Optimizing the Readout of Lanthanide-DOTA Complexes for the Detection of Ligand-Bound Copper(I

    Directory of Open Access Journals (Sweden)

    Jill R. Hanna

    2017-05-01

    Full Text Available The CuAAC ‘click’ reaction was used to couple alkyne-functionalized lanthanide-DOTA complexes to a range of fluorescent antennae. Screening of the antenna components was aided by comparison of the luminescent output of the resultant sensors using data normalized to account for reaction conversion as assessed by IR. A maximum 82-fold enhanced signal:background luminescence output was achieved using a Eu(III-DOTA complex coupled to a coumarin-azide, in a reaction which is specific to the presence of copper(I. This optimized complex provides a new lead design for lanthanide-DOTA complexes which can act as irreversible ‘turn-on’ catalytic sensors for the detection of ligand-bound copper(I.

  10. Investigation into scanning tunnelling luminescence microscopy

    CERN Document Server

    Manson-Smith, S K

    2001-01-01

    This work reports on the development of a scanning tunnelling luminescence (STL) microscope and its application to the study of Ill-nitride semiconductor materials used in the production of light emitting devices. STL microscopy is a technique which uses the high resolution topographic imaging capabilities of the scanning tunnelling microscope (STM) to generate high resolution luminescence images. The STM tunnelling current acts as a highly localised source of electrons (or holes) which generates luminescence in certain materials. Light generated at the STM tunnelling junction is collected concurrently with the height variation of the tunnelling probe as it is scanned across a sample surface, producing simultaneous topographic and luminescence images. Due to the very localised excitation source, high resolution luminescence images can be obtained. Spectroscopic resolution can be obtained by using filters. Additionally, the variation of luminescence intensity with tunnel current and with bias voltage can provi...

  11. Characteristics of Trivalent Lanthanides in Coordination Chemistry

    Institute of Scientific and Technical Information of China (English)

    Xue Dongfeng(薛冬峰); Zuo Sen(左森); Henryk Ratajczak

    2004-01-01

    Some basic characteristics of lanthanide-oxygen bonds in various trivalent lanthanide metal-organic complexes are quantitatively studied by the bond valence model. Some important relationships among the electronegativity, bond valence parameter, bond length and lanthanide coordination number in these complexes are generally found , which show that for each trivalent lanthanide cation all calculated parameters may well be correlated with its coordination number in their coordination complexes. Specifically,32 new data for the bond valence parameter are first calculated in this work.An approximate linear relationship between the Ln-O bond valence parameter and the coordination number of Ln3+ is obtained.The Ln-O bond length increases with the increase in the lanthanide coordination number.The difference of electronegative values decreases with the increase in the lanthanide coordination number.

  12. Luminescence detection of cysteine based on Ag⁺-mediated conformational change of terbium ion-promoted G-quadruplex.

    Science.gov (United States)

    Tan, Hongliang; Tang, Gonge; Ma, Chanjiao; Li, Qian

    2016-02-18

    In this work, we developed a simple and sensitive method for the detection of cysteine (Cys) by employing terbium ion (Tb(3+))-promoted G-qudraplex (G4/Tb) as a luminescent probe, which is based on Ag(+)-mediated conformational change of G4/Tb. Due to Ag(+) is able to compete with Tb(3+) to bind guanine at G4, the presence of Ag(+) can lead to the formation of G4/Tb-Ag(+) complex and disrupt the structure of G4/Tb. Meanwhile, the binding of Ag(+) with G4/Tb will also cause the alteration of the excited state of G4 and more efficient energy transfer from G4 to Tb(3+), enhancing the luminescence of G4/Tb. However, upon the addition of Cys, Ag(+) will be released from G4/Tb-Ag(+) complex because of the high affinity of Cys to Ag(+). This results in the re-formation of the conformation of G4/Tb and the decrease of the luminescence of G4/Tb. So, Ag(+)-enhanced luminescence of G4/Tb is associated with its conformational transformation. As a luminescent probe for Cys, G4/Tb not only shows excellent selectivity and sensitivity with a detection limit of 20 nM, but also possesses the features of simple preparation, easy reproducibility, and eliminating the interferences from background fluorescence. We envision that the presented strategy might provide new insight into the biosensing applications of lanthanide complex. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Visualization of exhaled hydrogen sulphide on test paper with an ultrasensitive and time-gated luminescent probe.

    Science.gov (United States)

    Zhang, Ruilong; Liu, Shijiang; Wang, Jianping; Han, Guangmei; Yang, Linlin; Liu, Bianhua; Guan, Guijian; Zhang, Zhongping

    2016-08-01

    Luminescent chemosensors for hydrogen sulphide (H2S) are of great interest because of the close association of H2S with our health. However, current probes for H2S detection have problems such as low sensitivity/selectivity, poor aqueous-solubility or interference from background fluorescence. This study reports an ultrasensitive and time-gated "switch on" probe for detection of H2S, and its application in test paper for visualization of exhaled H2S. The complex probe is synthesized with a luminescent Tb(3+) centre and three ligands of azido (-N3) substituted pyridine-2,6-dicarboxylic acid, giving the probe high hydrophilicity and relatively fast reaction dynamics with H2S because there are three -N3 groups in each molecule. The introduced -N3 group as a strong electron-withdrawing moiety effectively changes the energy level of ligand via intramolecular charge transfer (ICT), and thus breaks the energy transferring from ligand to lanthanide ion, resulting in quenching of Tb(3+) luminescence. On addition of H2S, the -N3 group can be reduced to an amine group to break the process of ICT, and the luminescence of Tb(3+) is recovered at a nanomolar sensitivity level. With a long lifetime of luminescence of Tb(3+) centre (1.9 ms), use of a time-gated technique effectively eliminates the background fluorescence by delaying fluorescence collection for 0.1 ms. The test paper imprinted by the complex probe ink can visualize clearly the trace H2S gas exhaled by mice.

  14. Pure zinc sulfide quantum dot as highly selective luminescent probe for determination of hazardous cyanide ion.

    Science.gov (United States)

    Shamsipur, Mojtaba; Rajabi, Hamid Reza

    2014-03-01

    A rapid and simple fluorescence method is presented for selective and sensitive determination of hazardous cyanide ion in aqueous solution based on functionalized zinc sulfide (ZnS) quantum dot (QD) as luminescent prob. The ultra-small ZnS QDs were synthesized using a chemical co-precipitation method in the presence of 2-mercaptoethanol (ME) as an efficient capping agent. The prepared pure ZnS QDs was applied as an optical sensor for determination of cyanide ions in aqueous solutions. ZnS nanoparticles have exhibited a strong fluorescent emission at about 424 nm. The fluorescence intensity of QDs is linearly proportional to the cyanide ion concentration in the range 2.44×10(-6) to 2.59×10(-5)M with a detection limit of 1.70×10(-7)M at pH11. The designed fluorescent sensor possesses remarkable selectivity for cyanide ion over other anions such as Cl(-), Br(-), F(-), I(-), IO3(-), ClO4(-), BrO3(-), CO3(2-), NO2(-), NO3(-), SO4(2-), S2O4(2-), C2O4(2-), SCN(-), N3(-), citrate and tartarate with negligible influences on the cyanide detection by fluorescence spectroscopy. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Nonstoichiometry and luminescent properties of ZnSe crystals grown from the melt at high pressures

    Science.gov (United States)

    Khanh, Tran; Mozhevitina, Elena; Khomyakov, Andrew; Avetisov, Roman; Davydov, Albert; Chegnov, Vladimir; Antonov, Vladimir; Kobeleva, Svetlana; Zhavoronkov, Nikolai; Avetissov, Igor

    2017-01-01

    50 mm diameter ZnSe crystals have been grown from the melt by a vertical Bridgman technique at 100 atm argon pressure in a graphite crucible. 3D impurities concentration and nonstoichiometry mappings of the grown crystals have been defined by ICP-MS and a direct physic-chemical method, correspondingly. Photoluminescence mapping of the analyzed crystal has been done. It was found out that along the crystal height the nonstoichiometry changed from Se excess over stoichiometrical composition in the cone (bottom) part to Zn excess in the tail (upper) part passing through the stoichiometrical composition in the cylindrical part of the crystal. Metal impurities concentrated in the upper part of the crystal. The gas-forming impurities (H, C, O, N, F) had stochastic distribution but Cl impurity concentrated in the crystal peripheral part (near the crucible walls). It was found out that the as-grown crystal had a single wide PL peal with maximum of 583 nm. A proposal about complex structure luminescent center based on Cl dopant an overstoichiometric Se has been made.

  16. Dating loess with high temperature IRSL signals from polymineral fine grains: luminescence characteristics and comparison with conventional techniques

    Science.gov (United States)

    Thiel, C.; Buylaert, J.-P.; Murray, A. S.; Tsukamoto, S.; Jain, M.; Frechen, M.

    2009-04-01

    % of the given dose). This high temperature signal is also bleachable by daylight, as confirmed by the values of De observed in young samples and by performing controlled laboratory bleaching experiments. The enhanced post-IR IR dating protocol was applied to loess samples from Austria and Japan and compared with standard IRSL at 50°C and quartz OSL measurements. First results suggest that there is good agreement for the younger samples of Weichselian age but that the ages begin to deviate for the older samples. Final results, including a comparison with independent age control provided by known age tephra layers for the Japan samples (Watanuki et al., 2005), will be presented. Buylaert, J. P., Murray, A. S., Thomsen, K. J., Jain, M., accepted. Testing the potential of an elevated temperature IRSL signal from K-feldspar. Radiation Measurements, Special Issue, LED08. Murray, A. S., Buylaert, J. P., Thomsen, K. J., Jain, M., accepted. The Effect of Preheating on the IRSL Signal from Feldspar. Radiation Measurements, Special Issue, LED08. Thomsen, K. J., Murray, A. S., Jain, M., Bøtter-Jensen, L., 2008. Laboratory fading rates of various luminescence signals from feldspar-rich sediment extracts. Radiation Measurements, 43, 1474-1486. Watanuki, T., Murray, A. S., Tsukamoto, S., 2005. Quartz and polymineral luminescence dating of Japanese loess over the last 0.6 Ma: Comparison with an independent chronology. Earth and Planetary Science Letters, 240, 774-789.

  17. A Supramolecular Sensor Array Using Lanthanide-Doped Nanoparticles for Sensitive Detection of Glyphosate and Proteins.

    Science.gov (United States)

    Wang, Meng; Ye, Hebo; You, Lei; Chen, Xueyuan

    2016-01-13

    Lanthanide (Ln(3+))-doped nanoparticles (NPs) are an intensive area of research in chemical and materials sciences. Herein a sensor array of Ln(3+)-doped NPs was developed for the first time toward sensitive molecular sensing based on a novel strategy of the hybridized time-resolved Förster resonance energy transfer (TR-FRET) with the indicator displacement assay (IDA) concept (TR-FRET-IDA). The sensor platform was generated in situ by binding a series of negatively charged indicators on the surface of ligand-free LiYF4:Ce/Tb NPs. The TR-FRET between NPs and dyes resulted in indicator emission and was employed as a means of removing undesired short-lived background luminescence from the indicator effectively. Displacement of indicators from the NP/indicator ensembles by glyphosate, a common herbicide, led to turn-off of the indicator emission. The sensor array was able to successfully discriminate 11 biologically relevant anions with high accuracy and sensitivity in pure aqueous buffer both qualitatively and quantitatively. Furthermore, the differentiation of six model proteins in the nM range was achieved with 100% accuracy for the classification, thereby demonstrating the versatility of this simple sensor platform. The study of the mechanism of binding and signal modulation further verified TR-FRET-IDA as a reliable sensing paradigm.

  18. Progress on Study of Luminescence of Rare Earth Organic Chelates

    Institute of Scientific and Technical Information of China (English)

    杨燕生; 安保礼; 龚孟濂; 史华红; 雷衡毅; 孟建新

    2002-01-01

    Based on the investigation of the luminescence of a series of rare earth organic chelates, some relationships between luminescence and the structure of the chelates were proposed: the intensity of sensitized luminescence of central lanthanide ions(Ln3+) in a rare earth organic chelate depends on (1)the suitability of the energy gap between the excited triplet energy level of the ligands and the lowest excited energy level of Ln3+ ions; (2)the rigidity and planarity of the structure of the chelate molecule; (3)the existence of a suitable secondary ligand which may increase rigidity and the stability of the chelate molecule; and (4) the existence of a suitable π-conjugated system in the chelate molecule. According to the above relationships, 25 novel organic ligands were designed and synthesized, and their lanthanide chelates were prepared. Investigation of the photoluminescence for the new chelates shows that some of the chelates are strongly luminescent, and are applied to fluoroimmunoassay for determination of human immunoglobulin(IgG), to preparation of fluorescent plastics, and to determination of growth hormone for plants. Two novel spectroscopy-probe techniques for structure of coordination compounds and biological molecules were proposed and developed based on vibronic spectroscopy of Tb3+ complexes and fluorescence of Ce3+.

  19. Lanthanide-activated Na{sub 5}Gd{sub 9}F{sub 32} nanocrystals precipitated from a borosilicate glass: Phase-separation-controlled crystallization and optical property

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Daqin, E-mail: dqchen@hdu.edu.cn [College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Institute of Research on the Structure of Matter, CAS, Fuzhou 350002 (China); Wan, Zhongyi; Zhou, Yang [College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Chen, Yan, E-mail: chenyan@hdu.edu.cn [College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Yu, Hua; Lu, Hongwei; Ji, Zhenguo [College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Huang, Ping, E-mail: phuang@fjirsm.ac.cn [Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Institute of Research on the Structure of Matter, CAS, Fuzhou 350002 (China)

    2015-03-15

    Highlights: • Na{sub 5}Gd{sub 9}F{sub 32} nanocrystals embedded glass ceramics were fabricated for the first time. • Such glass ceramics were achieved by phase-separation-controlled crystallization. • Elemental mapping evidenced the segregation of activators into the Na{sub 5}Gd{sub 9}F{sub 32} lattice. • Luminescent color could be tuned by controlling glass crystallization temperature. - Abstract: Lanthanide-activated cubic Na{sub 5}Gd{sub 9}F{sub 32} nanocrystals were precipitated from a borosilicate glass with a specifically designed composition. The precursor glass is already phase-separated after melt-quenching, which is beneficial to the realization of the controllable glass crystallization for affording desirable size, morphology and activator partition. Elemental mapping in the scanning transmission electron microscopy evidenced that the segregation of lanthanide ions into the Na{sub 5}Gd{sub 9}F{sub 32} lattice was in situ formed without the requirement of long-range ionic diffusion. Impressively, such fabricated glass ceramic co-doped with Yb{sup 3+}/Er{sup 3+} ions exhibited intense upconversion luminescence, which was about 500 times higher than that of the precursor glass, and its luminescent color could be easily tuned from red to green by controlling glass crystallization temperature. It is anticipated that such phase-separation synthesis strategy with precise control over nanostructure of glass ceramics offer a great opportunity to design other highly transparent nanocomposites with a wide range of tunable optical properties.

  20. Lanthanide Complexes for Oligomerization of Phenyl Isocyanate

    Institute of Scientific and Technical Information of China (English)

    DENG,Ming-Yu; YAO,Ying-Ming; ZHOU,Yu-Fang; ZHANG,Li-Fen; SHEN,Qi

    2003-01-01

    A series of lanthanide complexes including (Ind)3Sm(THF)(1),[(MeCp)2Sm(μ-SPh)(THF)]2(2),[(MeCp)2Y(μ-O-i-Pr)]2(3),(MeCp)3Sm·THF(4),Sm(SPh)3(hmpa)3(5),[(MeCp)2Y-(μ-OCH2CF3)2(6)and (CF3CH2O)3Y(THF)3(7) were synthesized and they have good activity for the oligomerization of phenylisocyanate.Among them 5 shows the highest activity.The conversion is as high as 96.2%,with 1/2500 of the molar ratio of cat./PhNCO.The main components in oligomer were characterized to be a cycdlodimer and a cyclotrimer.The ratio of cyclodimer to cyclotrimer depends on the lanthanide complexes used.7 gave 85.2%cyclotrimer with 1/300 of the molar ratio of cat./PhNCO at 40℃ for 0.5h,while 5 gave 77.6% cyclodimer with 1/300 of the molar ratio of cat./PhNCO at 40℃ for 4h.

  1. Magnetic molecular materials with paramagnetic lanthanide ions

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The diverse magnetic properties of lanthanide-based magnetic molecular materials are introduced in the following organization.First,the general aspects of magnetic molecular materials and electronic states of lanthanide ions are introduced.Then the structures and magnetic properties are described and analyzed for molecules with one lanthanide ion,4f-4f,4f-3d and 4f-p magnetic coupling interactions.In each section,magnetic coupling,magnetic ordering and magnetic relaxation phenomenon are briefly reviewed using some examples.Finally,some possibilities of developing magnetic molecular materials containing lanthanide ions are discussed in the outlook part.

  2. 3d-4f Metal-Organic Framework with Dual Luminescent Centers That Efficiently Discriminates the Isomer and Homologues of Small Organic Molecules.

    Science.gov (United States)

    Zeng, Guang; Xing, Shanghua; Wang, Xiuru; Yang, Yulin; Ma, Dingxuan; Liang, Hongwei; Gao, Lu; Hua, Jia; Li, Guanghua; Shi, Zhan; Feng, Shouhua

    2016-02-01

    A 3d-4f luminescent metal-organic framework (MOF), [Tb2(Cu8I8)(C12H8NO2)6(H2O)4]·5C4H8O2 (4), and three analogues {[La2(Cu8I8)(C12H8NO2)6(C4H8O2)2(H2O)2]·3C4H8O2·2H2O (1), [Ce2(Cu8I8)(C12H8NO2)6(H2O)4]·5C4H8O2 (2), and [Eu2(Cu8I8)(C12H8NO2)6(H2O)4]·5C4H8O2 (3)}, were self-assembled from copper(I) halide clusters and lanthanide metal ions with an organic linker [3-(pyridin-4-yl)benzoic acid] under solvothermal conditions. Compound 4 with high quantum yield (Φ = 68%) exhibits reversible luminescence behavior, accompanying the removal and recovery of guest molecules (1,4-dioxane). Because of the unique porous structure and dual luminescent centers of compound 4, it can efficiently differentiate benzene series with different sizes and provide readouts in corresponding optical signals. Furthermore, it also can unambiguously discriminate the isomers, homologues, and other small molecules with similar structural motifs from one another. The luminescent color of the MOF sensor in different guest solvents has obvious changes that can be clearly distinguished by the naked eye. This multicolor luminescence originates from emissions of the dual luminescent centers, and the emissions have shifted, enhanced, weakened, or quenched to different degrees.

  3. Using the Antenna Effect as a Spectroscopic Tool; Photophysics and Solution Thermodynamics of the Model Luminescent Hydroxypyridonate Complex [EuIII(3,4,3-LI(1,2-HOPO))]-

    Energy Technology Data Exchange (ETDEWEB)

    Abergel, Rebecca J.; D' Aleo, Anthony; Ng Pak Leung, Clara; Shuh, David; Raymond, Kenneth

    2009-11-20

    While widely used in bioassays, the spectrofluorimetric method described here uses the antenna effect as a tool to probe the thermodynamic parameters of ligands that sensitize lanthanide luminescence. The Eu3+ coordination chemistry, solution thermodynamic stability and photophysical properties of the spermine-based hydroxypyridonate octadentate chelator 3,4,3-LI(1,2-HOPO) are reported. The complex [EuIII(3,4,3-LI(1,2-HOPO))]- luminesces with a long lifetime (805 mu s) and a quantum yield of 7.0percent in aqueous solution, at pH 7.4. These remarkable optical properties were exploited to determine the high (and proton-independent) stability of the complex (log beta 110 = 20.2(2)) and to define the influence of the ligand scaffold on the stability and photophysical properties.

  4. Design and Synthesis of an MOF Thermometer with High Sensitivity in the Physiological Temperature Range.

    Science.gov (United States)

    Zhao, Dian; Rao, Xingtang; Yu, Jiancan; Cui, Yuanjing; Yang, Yu; Qian, Guodong

    2015-12-07

    An important result of research on mixed-lanthanide metal-organic frameworks (M'LnMOFs) is the realization of highly sensitive ratiometric luminescent thermometers. Here, we report the design and synthesis of the new M'LnMOF Tb0.80Eu0.20BPDA with high relative sensitivity in the physiological temperature regime (298-318 K). The emission intensity and luminescence lifetime were investigated and compared to those of existing materials. It was found that the temperature-dependent luminescence properties of Tb0.80Eu0.20BPDA are strongly associated with the distribution of the energy levels of the ligand. Such a property can be useful in the design of highly sensitive M'LnMOF thermometers.

  5. Revealing and tuning the core, structure, properties and function of polymer micelles with lanthanide-coordination complexes.

    Science.gov (United States)

    Wang, Junyou; Groeneveld, Andrea; Oikonomou, Maria; Prusova, Alena; Van As, Henk; van Lent, Jan W M; Velders, Aldrik H

    2016-01-07

    Controlling self-assembly processes is of great interest in various fields where multifunctional and tunable materials are designed. We here present the versatility of lanthanide-complex-based micelles (Ln-C3Ms) with tunable coordination structures and corresponding functions (e.g. luminescence and magnetic relaxation enhancement). Micelles are prepared by charge-driven self-assembly of a polycationic-neutral diblock copolymer and anionic coordination complexes formed by Ln(III) ions and the bis-ligand L2EO4, which contains two dipicolinic acid (DPA) ligand groups (L) connected by a tetra-ethylene oxide spacer (EO4). By varying the DPA/Ln ratio, micelles are obtained with similar size but with different stability, different aggregation numbers and different oligomeric and polymeric lanthanide(III) coordination structures in the core. Electron microscopy, light scattering, luminescence spectroscopy and magnetic resonance relaxation experiments provide an unprecedented detailed insight into the core structures of such micelles. Concomitantly, the self-assembly is controlled such that tunable luminescence or magnetic relaxation with Eu-C3Ms, respectively, Gd-C3Ms is achieved, showing potential for applications, e.g. as contrast agents in (pre)clinical imaging. Considering the various lanthanide(III) ions have unique electron configurations with specific physical chemical properties, yet very similar coordination chemistry, the generality of the current coordination-structure based micellar design shows great promise for development of new materials such as, e.g., hypermodal agents.

  6. Highly Efficient and Excitation Tunable Two-Photon Luminescence Platform For Targeted Multi-Color MDRB Imaging Using Graphene Oxide

    Science.gov (United States)

    Pramanik, Avijit; Fan, Zhen; Chavva, Suhash Reddy; Sinha, Sudarson Sekhar; Ray, Paresh Chandra

    2014-08-01

    Multiple drug-resistance bacteria (MDRB) infection is one of the top three threats to human health according to the World Health Organization (WHO). Due to the large penetration depth and reduced photodamage, two-photon imaging is an highly promising technique for clinical MDRB diagnostics. Since most commercially available water-soluble organic dyes have low two-photon absorption cross-section and rapid photobleaching tendency, their applications in two-photon imaging is highly limited. Driven by the need, in this article we report extremely high two-photon absorption from aptamer conjugated graphene oxide (σ2PA = 50800 GM) which can be used for highly efficient two-photon fluorescent probe for MDRB imaging. Reported experimental data show that two-photon photoluminescence imaging color, as well as luminescence peak position can be tuned from deep blue to red, just by varying the excitation wavelength without changing its chemical composition and size. We have demonstrated that graphene oxide (GO) based two-photon fluorescence probe is capable of imaging of multiple antibiotics resistance MRSA in the first and second biological transparency windows using 760-1120 nm wavelength range.

  7. Enrichment of lanthanides in aragonite

    Institute of Scientific and Technical Information of China (English)

    瞿成利; 路波; 刘刚

    2009-01-01

    Using the constant addition technique,the coprecipitation of lanthanum,gadolinium,and lutetium with aragonite in seawater was experimentally investigated at 25 ℃.Their concentrations in aragonite overgrowths were determined by inductive coupled plasma mass spectrometer.All these lanthanides were strongly enriched in aragonite overgrowths.The amount of lanthanum,gadolinium,and lutetium incorporated into aragonite accounted for 57%-99%,50%-89%,and 40%-91% of their initial total amount,respectively.With the in...

  8. Luminescent metal-organic framework-functionalized graphene oxide nanocomposites and the reversible detection of high explosives

    Science.gov (United States)

    Lee, Ji Ha; Jaworski, Justyn; Jung, Jong Hwa

    2013-08-01

    Achieving both high specificity and sensitivity are essential for gas phase chemical detection systems. Recent implementation of Metal-Organic Frameworks (MOFs) have shown great success in separation and storage systems for specific gas molecules. By implementing a MOF structure comprised of Zn2+ coordinated trans-stilbene derivatives, a gas responsive material has been created which exhibits a high photoluminescence quantum yield, offering new opportunities for chemical sensors. Here, we reveal a nanocomposite material, assembled from azobenzene functionalized graphene oxide and stilbene-MOF, that is capable of luminescent quenching by explosive gases. This unique system displays selectivity to dinitrotoluene (71% quenching) over trinitrotoluene (20% quenching) with sub ppm sensitivity and response times of less than a minute. We show that this implementation of a graphene-based MOF composite provides a unique strategy in the development of molecularly well-defined materials having rapid, reversible, and gas selective fluorescent quenching capabilities. This opens the way for new advances in the assembly of low density frameworks using isomerization suppressed materials.Achieving both high specificity and sensitivity are essential for gas phase chemical detection systems. Recent implementation of Metal-Organic Frameworks (MOFs) have shown great success in separation and storage systems for specific gas molecules. By implementing a MOF structure comprised of Zn2+ coordinated trans-stilbene derivatives, a gas responsive material has been created which exhibits a high photoluminescence quantum yield, offering new opportunities for chemical sensors. Here, we reveal a nanocomposite material, assembled from azobenzene functionalized graphene oxide and stilbene-MOF, that is capable of luminescent quenching by explosive gases. This unique system displays selectivity to dinitrotoluene (71% quenching) over trinitrotoluene (20% quenching) with sub ppm sensitivity and

  9. Applications of quantum dots with upconverting luminescence in bioimaging.

    Science.gov (United States)

    Chen, Yunyun; Liang, Hong

    2014-06-05

    Quantum dots (QDs) have attracted great attention in recent years due to their promising applications in bioimaging. Compared with traditional ultraviolet excitation of QDs, near-infrared laser (NIR) excitation has many advantages, such as being less harmful, little blinking effects, zero autofluorescence and deep penetration in tissue. Composing QDs with upconverting properties is promising to enable NIR excitation. This article provides a review of QDs with upconverting luminescence and their applications in bioimaging. Based on the mechanisms of luminescence, discussion will be divided into four groups: nanoheterostructures/mixtures of QDs and upconverting nanoparticles, graphene quantum dots, lanthanide-doped QDs, and double QDs. The content includes synthetic routes, upconverting luminescence properties, and their applications in bioimaging.

  10. Lanthanide salts solutions: representation of osmotic coefficients within the binding mean spherical approximation.

    Science.gov (United States)

    Ruas, Alexandre; Moisy, Philippe; Simonin, Jean-Pierre; Bernard, Olivier; Dufrêche, Jean-François; Turq, Pierre

    2005-03-24

    Osmotic coefficients of aqueous solutions of lanthanide salts are described using the binding mean spherical approximation (BIMSA) model based on the Wertheim formalism for association. The lanthanide(III) cation and the co-ion are allowed to form a 1-1 ion pair. Hydration is taken into account by introducing concentration-dependent cation size and solution permittivity. An expression for the osmotic coefficient, derived within the BIMSA, is used to fit data for a wide variety of lanthanide pure salt aqueous solutions at 25 degrees C. A total of 38 lanthanide salts have been treated, including perchlorates, nitrates, and chlorides. For most solutions, good fits could be obtained up to high ionic strengths. The relevance of the fitted parameters has been discussed, and a comparison with literature values has been made (especially the association constants) when available.

  11. The luminescence of doped and undoped BaLn2(MoO4)4 (Ln = La,Gd)

    NARCIS (Netherlands)

    Keller, R.C.A.; Blasse, G.; Lindholm, T.; Leskela, M.

    1988-01-01

    The luminescence of nominally pure BaLn2(MoO4)4 (Ln = La,Gd) is reported. Below 300 K molybdate emission is observed. The following activators were investigated: Eu3+, Tb3+, Pb2+ and Bi3+. The two lanthanide ions show their characteristic emission, the two s2 configuration ions give an emission in w

  12. Exploring the ability of the nalidixate to sensitize visible and near-infrared emitting lanthanide(III) cations

    Science.gov (United States)

    Eliseeva, Svetlana V.; Liasotkyi, Valerii S.; Golovach, Iurii P.; Doga, Pavel G.; Antonovich, Valery P.; Petoud, Stéphane; Meshkova, Svetlana B.

    2017-03-01

    Recently, a strong interest has been directed towards near-infrared (NIR) emitting lanthanide(III) compounds as they do possess complementary advantages in respect to organic molecules and semi-conductor nanocrystals, especially in the fields of biological analysis and imaging. To benefit from their emission, a key requirement to fulfill is the sensitization of lanthanide(III) cations with an appropriate chromophore. This condition is especially challenging to address for the lanthanide(III) cations emitting in the NIR. The quest for new chromophores well adapted to the NIR-emitting lanthanide(III) ions is an important direction of research in order to broaden the rationalization of the parameters that control the sensitization process. In this work, we have investigated the ability of a readily available chromophoric ligand, the nalidixic acid, to sensitize lanthanide(III) cations with a specific interest for those emitting in the NIR. We have therefore performed an extensive study of the luminescence properties of lanthanide(III) complexes emitting in the visible and in the NIR ranges formed in situ upon mixing the corresponding Ln(III) nitrates (Ln(III)  =  Pr, Nd, Sm, Eu, Tb, Dy, Ho, Tm, Yb) with nalidixic acid (HNA) in a 1:3 molar ratio in the presence of a base. Luminescence spectra, quantum yields and luminescence lifetimes have been measured and discussed. The red emission of Eu with a quantum yield value of 5.90(3)%, red and NIR of Pr (7(1) · 10-4 and 5.6(1) · 10-4%) and Ho (9.3(2) · 10-4 and 2.8(1) · 10-4%), green of Tb (5.21(5)%), yellow and NIR of Dy (0.51(2) and 0.065(4)%), orange and NIR of Sm (0.147(5) and 0.037(2)%), as well as NIR of Nd (0.0321(2)%) and Yb (0.021(1)%) were observed. These results and analysis show that the nalidixate is a versatile chromophoric ligand that is suitable for the sensitization of nine different lanthanide(III) cations, five of them emitting in the NIR.

  13. Simple efficient synthesis of strongly luminescent polypyrene with intrinsic conductivity and high carbon yield by chemical oxidative polymerization of pyrene.

    Science.gov (United States)

    Li, Xin-Gui; Liu, You-Wei; Huang, Mei-Rong; Peng, Sai; Gong, Ling-Zhi; Moloney, Mark G

    2010-04-26

    A wholly aromatic polypyrene was synthesized by direct chemical oxidative polymerization of pyrene with ferric chloride as oxidant in hexane/nitromethane. Successful synthesis of polypyrene was thoroughly confirmed by IR, UV/Vis, 1D (1)H NMR, 2D (1)H-(1)H COSY, 2D (1)H-(13)C HSQC, MALDI-TOF MS, elemental analysis, and X-ray diffraction methods. The results indicated that the polypyrene was formed mainly through dehydro coupling between 2- or 1- and 2'- or 1'-positions on pyrene rings having a degree of polymerization of around 24. The polypyrene was purified and then separated into THF-soluble (ca. 10 %) and THF-insoluble (ca. 90 %) fractions. Compared with insulating pyrene monomer, the polypyrene is a controllably conducting polymer that has low conductivity of 3.4x10(-8) S cm(-1) in its virgin state, moderate conductivity of 2.28x10(-4) S cm(-1) upon iodine doping, but much higher conductivity of up to 81.2 S cm(-1) after the insoluble polypyrene was heated up to 1300 degrees C in nitrogen with a high char yield of 70.6 %. In particular, the soluble polypyrene demonstrates much stronger visible color fluorescence and much lower toxicity than pyrene. The soluble polypyrene would be advantageous for detecting Fe(3+) with almost no interference of other metal ions. The soluble and insoluble polypyrene fractions have potential applications as intrinsically luminescent and highly conducting carbon materials, respectively.

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

    Science.gov (United States)

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

    2013-11-01

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

  15. Electrochemistry and Spectroelectrochemistry of Luminescent Europium Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Lines, Amanda M. [Department of Chemistry, Washington State University, Pullman WA 99163; Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99352; Wang, Zheming [E Directorate, Pacific Northwest National Laboratory, Richland WA 99352; Clark, Sue B. [Department of Chemistry, Washington State University, Pullman WA 99163; Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99352; Bryan, Samuel A. [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99352

    2016-05-04

    Fast, cost effective, and robust means of detecting and quantifying lanthanides are needed for supporting more efficient tracking within the nuclear, medicinal, and industrial fields. Spectroelectrochemistry (SEC) is a powerful technique combining electrochemistry and spectroscopy that can meet those needs. The primary limitation of SEC as a detection method for lanthanides is their low molar absorptivity in absorbance based measurements and low emission intensities in fluorescence based measurements; both lead to high limits of detection. These limitations can be circumvented by complexing the lanthanides with sensitizing ligands that enhance fluorescence, thereby dropping the limits of detection. Complexation may also stabilize the metal ions in solution and improve the electrochemical reversibility, or Nernstian behavior, of the redox couples. To demonstrate this concept, studies were completed using europium in complexes with four different sensitizing ligands. Initial work indicates Eu in the four complexes studied does display the necessary characteristics for SEC analysis, which was successfully and reproducibly applied to all Eu complexes.

  16. Photo-reactive charge trapping memory based on lanthanide complex.

    Science.gov (United States)

    Zhuang, Jiaqing; Lo, Wai-Sum; Zhou, Li; Sun, Qi-Jun; Chan, Chi-Fai; Zhou, Ye; Han, Su-Ting; Yan, Yan; Wong, Wing-Tak; Wong, Ka-Leung; Roy, V A L

    2015-10-09

    Traditional utilization of photo-induced excitons is popularly but restricted in the fields of photovoltaic devices as well as photodetectors, and efforts on broadening its function have always been attempted. However, rare reports are available on organic field effect transistor (OFET) memory employing photo-induced charges. Here, we demonstrate an OFET memory containing a novel organic lanthanide complex Eu(tta)3ppta (Eu(tta)3 = Europium(III) thenoyltrifluoroacetonate, ppta = 2-phenyl-4,6-bis(pyrazol-1-yl)-1,3,5-triazine), in which the photo-induced charges can be successfully trapped and detrapped. The luminescent complex emits intense red emission upon ultraviolet (UV) light excitation and serves as a trapping element of holes injected from the pentacene semiconductor layer. Memory window can be significantly enlarged by light-assisted programming and erasing procedures, during which the photo-induced excitons in the semiconductor layer are separated by voltage bias. The enhancement of memory window is attributed to the increasing number of photo-induced excitons by the UV light. The charges are stored in this luminescent complex for at least 10(4) s after withdrawing voltage bias. The present study on photo-assisted novel memory may motivate the research on a new type of light tunable charge trapping photo-reactive memory devices.

  17. Detrimental nonlocality in luminescence measurements

    Science.gov (United States)

    Pluska, Mariusz; Czerwinski, Andrzej

    2017-08-01

    Luminescence studies are used to investigate the local properties of various light-emitting materials. A critical issue of these studies is presented that the signals often lack all advantages of luminescence-studies of high locality, and may originate from an extended spatial region of even a few millimeters in size or the whole sample, i.e., places other than intended for investigation. This is a key problem for research and development in photonics. Due to this nonlocality, information indicating defects, irregularities, nonuniformities and inhomogeneities is lost. The issue refers to typical structures with a strong built-in electric field. Such fields exist intentionally in most photonic structures and occur unintentionally in many other materials investigated by applied physics. We reveal [using test samples prepared with focused ion beam (FIB) on an AlGaAs/GaAs laser heterostructure with an InGaAs quantum well (QW)] that nonlocality increases at low temperatures. This is contrary to the widely expected outcome, as low-temperature luminescence measurements are usually assumed to be free from disturbances. We explain many effects observed due to nonlocality in luminescence studies and prove that separation of the investigated area by focused ion beam milling is a practical solution enabling truly local luminescence measurements. All conclusions drawn using the example of cathodoluminescence are useful for other luminescence techniques.

  18. Microwave-assisted hydrothermal synthesis of highly luminescent ZnSe-based quantum dots with a quantum yield higher than 90%

    Science.gov (United States)

    Lee, Yong-Shin; Nakano, Kaoru; Bu, Hang-Beom; Gwi Kim, Dae

    2017-06-01

    Highly luminescent ZnSe-based quantum dots (QDs) were synthesized by a microwave-assisted hydrothermal method. The characteristics of the ZnSe precursor solution strongly influenced the photoluminescence (PL) quantum yields (QYs) of the QDs. The PL QY of ZnSe-core QDs synthesized under the optimum conditions reached 60%. Furthermore, the PL QY further increased to higher than 90% when a ZnS shell was applied to prepare ZnSe/ZnS-core/shell QDs.

  19. Highly Luminescent Carbon Dots Synthesized by Microwave-Assisted Pyrolysis and Evaluation of Their Toxicity to Physa acuta.

    Science.gov (United States)

    Sun, Xiaobo; Jin, Xiaozhe; Pan, Wei; Guo, Enmian; Liu, Weijian; Li, Denghui; Lu, Kunchao; Si, Shuxin; Zhang, Nianxing; Jia, Zhenzhen; Shi, Yanping; Li, Qianqian; Wang, Jinping

    2016-01-01

    As a newly emerging class of nanomaterials, carbon dots have increasingly attracted researchers' attention. However, their potentially adverse environmental effects are yet largely unknown. In this work, the highly luminescent carbon dots were synthesized by microwave-assisted pyrolysis of tris(hydroxymethyl)aminomethane (Tris) and citric acid. Then acute and chronic toxicities of carbon dots to Physa acuta (P. acuta), as well as their effect on reproduction, were evaluated using the as-synthesized dots as an example. The quantum yield of the as-synthesized carbon dots was up to 53.5% excited at 360 nm with the most fluorescent fraction of 82.6% after simple purification by gel column. The results showed that no acute but chronic toxicities to P. acuta exposed to different treatment concentrations of the as-synthesized carbon dots were observed with dose- dependence. In addition, the fecundity of P. acuta was promoted significantly by the carbon dots at the concentrations of 0.5 and 1.0 mg/mL, yet inhibited at the concentration of 3.0 mg/mL after 12-day exposure. Mainly distributing in the visceral mass might be responsible for the effects of the carbon dots on the survival and fecundity of P. acuta. And there was no further evidence to confirm that the carbon dots can cause malformation in developing embryos.

  20. High Luminescence White LEDs Prepared with 2D Island-Pattern of Quantum Dots Dispersed Photopolymer Films

    Directory of Open Access Journals (Sweden)

    Hyun-Guk Hong

    2015-01-01

    Full Text Available Since the reabsorption loss among different size quantum dots (QDs is a critical issue in the QD based white LEDs, we proposed and fabricated new film structure of 2D island-patterns consisting of separate green and red QDs dispersed photopolymer patterns in a zigzag form. A small air-gap such as 60 μm between QD islands helps to control the optical path at the interface to reduce the lateral reabsorption loss to enhance the optical efficiency of white LED. The 2D island-patterns of QD phosphor film were fabricated using a UV imprinting process and compared the optical efficiency with the other QD film structure prepared with same QD concentrations and thicknesses such as a mixed and separately layered QD structure. Experimental and simulation analysis were performed to confirm the better optical efficiency from the 2D island-patterns of QD films due to the reduced reabsorption loss. High luminescence white LED was finally realized with 2D island-patterns of QD film, resulting in a luminous efficiency of 62.2 lm/W and CRI of 83 with CCT of 4537 K at the operation current of 60 mA.

  1. Enhancing solar cell efficiency: the search for luminescent materials as spectral converters.

    Science.gov (United States)

    Huang, Xiaoyong; Han, Sanyang; Huang, Wei; Liu, Xiaogang

    2013-01-07

    Photovoltaic (PV) technologies for solar energy conversion represent promising routes to green and renewable energy generation. Despite relevant PV technologies being available for more than half a century, the production of solar energy remains costly, largely owing to low power conversion efficiencies of solar cells. The main difficulty in improving the efficiency of PV energy conversion lies in the spectral mismatch between the energy distribution of photons in the incident solar spectrum and the bandgap of a semiconductor material. In recent years, luminescent materials, which are capable of converting a broad spectrum of light into photons of a particular wavelength, have been synthesized and used to minimize the losses in the solar-cell-based energy conversion process. In this review, we will survey recent progress in the development of spectral converters, with a particular emphasis on lanthanide-based upconversion, quantum-cutting and down-shifting materials, for PV applications. In addition, we will also present technical challenges that arise in developing cost-effective high-performance solar cells based on these luminescent materials.

  2. Hybrid luminescence materials assembled by [Ln(DPA)3]3- and mesoporous host through ion-pairing interactions with high quantum efficiencies and long lifetimes

    Science.gov (United States)

    Li, Qing-Feng; Yue, Dan; Lu, Wei; Zhang, Xinlei; Li, Chunyang; Wang, Zhenling

    2015-02-01

    A kind of mesoporous hybrid luminescence material was assembled through the ion exchange method between [Ln(DPA)3]3- and ionic liquid functionalized SBA-15. [Ln(DPA)3]3- was successfully anchored onto positive-charge modified SBA-15 by the strong electrostatic interaction. In [Ln(DPA)3]3-, Ln3+ ions are in 9-fold coordination through six oxygen atoms of carboxyl groups and three nitrogen atoms of pyridine units, leaving no coordination site for water molecules. Therefore the hybrids possess prominent luminescent properties, SBA-15-IMI-Tb(DPA)3 and SBA-15-IMI-Eu(DPA)3 exhibit high quantum yield values of 63% and 79%, and long lifetimes values of 2.38 ms and 2.34 ms, respectively. Especially, SBA-15-IMI-Eu(DPA)3 presents a high color purity, and the red/orange intensity ratio is as high as 7.6. The excellent luminescence properties and ordered mesoporous structures give rise to many potential applications in optical and electronic areas.

  3. Tough photoluminescent hydrogels doped with lanthanide.

    Science.gov (United States)

    Wang, Mei Xiang; Yang, Can Hui; Liu, Zhen Qi; Zhou, Jinxiong; Xu, Feng; Suo, Zhigang; Yang, Jian Hai; Chen, Yong Mei

    2015-03-01

    Photoluminescent hydrogels have emerged as novel soft materials with potential applications in many fields. Although many photoluminescent hydrogels have been fabricated, their scope of usage has been severely limited by their poor mechanical performance. Here, a facile strategy is reported for preparing lanthanide (Ln)-alginate/polyacrylamide (PAAm) hydrogels with both high toughness and photoluminescence, which has been achieved by doping Ln(3+) ions (Ln = Eu, Tb, Eu/Tb) into alginate/PAAm hydrogel networks, where Ln(3+) ions serve as both photoluminescent emitters and physical cross-linkers. The resulting hydrogels exhibit versatile advantages including excellent mechanical properties (∼ MPa strength, ≈ 20 tensile strains, ≈ 10(4) kJ m(-3) energy dissipation), good photoluminescent performance, tunable emission color, excellent processability, and cytocompatibility. The developed tough photoluminescent hydrogels hold great promises for expanding the usage scope of hydrogels.

  4. High-resolution steady-state and time-resolved luminescence studies on the complexes of Eu(III) with aromatic or aliphatic carboxylic acids.

    Science.gov (United States)

    Marmodée, Bettina; de Klerk, Joost S; Ariese, Freek; Gooijer, Cees; Kumke, Michael U

    2009-10-12

    Eu(III) luminescence spectroscopy, both in the steady-state and the time-resolved mode, is an appropriate technique to study the properties of complexes between heavy metal ions and humic substances (HS), which play a key role in the distribution of metal species in the environment. Unfortunately, room temperature luminescence spectra of Eu(III) complexes with aromatic and aliphatic carboxylic acids - model compounds of HS binding sites - are too broad to fully exploit their potential analytical information content. It is shown that under cryogenic conditions fluorescence-line-narrowing (FLN) is achieved, and the highly resolved spectra provide detailed information on the complexes. Ten model ligands were investigated. Total luminescence spectra (TLS) were recorded, using the (5)D(0)(7)F(1) and (5)D(0)-->(7)F(2) transitions for emission. The energy of the excitation transition depends on the ligand involved and the structure and composition of the complex. For most ligands, discontinuities in the high-resolution TLS indicated that more species, i.e. distinct complex structures, coexisted in the sample. Selective excitation was performed to measure the species-associated luminescence decay times tau. The latter strongly depend on nearby OH oscillators from coordinating water molecules or ligand hydroxyl groups. Furthermore, the asymmetry ratios r, defined as the intensity ratio of the (5)D(0)-->(7)F(2) and (5)D(0)-->(7)F(1) transitions, were calculated and the variation of the excitation energy E(exc) with the splitting of the (7)F(1) triplet (DeltaE) was determined, which yielded the crystal field strength parameter N(nu)(B(2q)), as well as the crystal field parameters B(20) and B(22). An in-depth analysis of the results is presented, providing detailed information on the number of coexisting complexes, their stoichiometry, the number of water molecules in the first coordination sphere and their geometry (symmetry point group).

  5. Lanthanide doped BaTiO{sub 3}−SrTiO{sub 3} solid-solution phosphors: Structure, optical spectroscopy and upconverted temperature sensing behavior

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Daqin, E-mail: dqchen@hdu.edu.cn; Xu, Wei; Zhou, Yang; Chen, Yan, E-mail: chenyan@hdu.edu.cn

    2016-08-15

    Lanthanide doped Ba{sub 1-x}Sr{sub x}TiO{sub 3} (x = 0–1) solid-solution phosphors were successfully prepared by a conventional solid-state reaction. Using Eu{sup 3+} dopants as the structural probe, the variation of {sup 5}D{sub 0} → {sup 7}F{sub 2}/{sup 5}D{sub 0} → {sup 7}F{sub 1} emission intensity ratio with increase of Eu{sup 3+} content and the excitation-wavelength-dependent luminescence in the Ba{sub 1-x}Sr{sub x}TiO{sub 3} sample were demonstrated to be originated from the different emission behaviors of Eu{sup 3+} in Ba{sup 2+}/Sr{sup 2+} site and Ti{sup 4+} site. Furthermore, upconversion luminescence for the Yb{sup 3+}/Er{sup 3+} co-doped Ba{sub 1-x}Sr{sub x}TiO{sub 3} samples were investigated, and it was found that the emission intensity of Yb{sup 3+}/Er{sup 3+}: Ba{sub 0.5}Sr{sub 0.5}TiO{sub 3} phosphor was about 5 and 2 times as high as those of Yb{sup 3+}/Er{sup 3+}: BaTiO{sub 3} and Yb{sup 3+}/Er{sup 3+}: SrTiO{sub 3} ones. Using the investigated Yb{sup 3+}/Er{sup 3+}: Ba{sub 0.5}Sr{sub 0.5}TiO{sub 3} solid-solution as the optical thermometric medium, the temperature sensitivity was determined to be 0.76% K{sup −1} at the temperature of 610 K based on the temperature-dependent fluorescence intensity ratio of the thermally coupled {sup 2}H{sub 11/2} and {sup 4}S{sub 3/2} emitting-states of Er{sup 3+}. - Highlights: • Lanthanide doped Ba{sub 1-x}Sr{sub x}TiO{sub 3} (x = 0–1) solid-solutions were fabricated. • Excitation-wavelength-dependent Eu{sup 3+} emissions were recorded. • Enhanced Er{sup 3+} luminescence was realized by partial substitution of Ba{sup 2+} by Sr{sup 2+}. • T-sensitive emissions of two Er{sup 3+} thermally coupled states were observed. • The upconversion phosphor exhibited a high sensitivity of 0.76% K{sup −1}.

  6. Template-free synthesis and luminescent properties of hollow Ln:YOF (Ln = Eu or Er + Yb) microspheres

    Energy Technology Data Exchange (ETDEWEB)

    Martinez-Castro, E. [Instituto de Ciencia de Materiales de Sevilla (CSIC-US), Americo Vespucio 49, Isla de La Cartuja, 41092 Sevilla (Spain); García-Sevillano, J.; Cussó, F. [Dpto. Física de Materiales, C-04, Universidad Autónoma de Madrid, Avda. Francisco Tomás y Valiente, 7, 28049 Madrid (Spain); Ocaña, M., E-mail: mjurado@icmse.csic.es [Instituto de Ciencia de Materiales de Sevilla (CSIC-US), Americo Vespucio 49, Isla de La Cartuja, 41092 Sevilla (Spain)

    2015-01-15

    Highlights: • Hollow lanthanide doped YOF spheres have been synthesised through a template-free procedure. • Strong red emissions are observed for Eu-doped spheres under UV illumination. • Concentration quenching of luminescence takes place in the spheres at very high Eu doping levels. • Bright red emission is observed for Er, Yb codoped spheres, making this matrix advantageous for biomedical imaging. - Abstract: A method for the synthesis of hollow lanthanide doped yttrium oxyfluoride (YOF) spheres in the micrometer size range with cubic structure based on the pyrolysis at 600 °C of liquid aerosols generated from aqueous solutions containing the corresponding rare earth chlorides and trifluoroacetic acid has been developed. This procedure, which has been used for the first time for the synthesis of YFO based materials, is simpler and advantageous when compared with other methods usually employed for the production of hollow spheres since it does not require the use of sacrificial templates. In addition, it is continuous, which is desirable because of practical reasons. The procedure is also suitable for doping the YOF spheres with europium cations resulting in down converting red phosphors when activated with UV light, or for co-doping with both Er{sup 3+} and Yb{sup 3+} giving rise to up-converting phosphors, which emit intense red light under near infrared (NIR) irradiation. Because of their optical properties and hollow architecture, the developed materials may find applications in optoelectronic devices and biotechnology.

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

    OpenAIRE

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

    2014-01-01

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

  8. Progress in phosphors and filters for luminescent solar concentrators

    OpenAIRE

    De Boer, D.K.G.; Broer, D. J.; Debije, M.G.; Keur, W.; Meijerink, A.|info:eu-repo/dai/nl/075044986; Ronda, R.C.; Verbunt, P.P.C.

    2012-01-01

    Luminescent solar concentrators would allow for high concentration if losses by reabsorption and escape could be minimized. We introduce a phosphor with close-to-optimal luminescent properties and hardly any reabsorption. A problem for use in a luminescent concentrator is the large scattering of this material; we discuss possible solutions for this. Furthermore, the use of broad-band cholesteric filters to prevent escape of luminescent radiation from this phosphor is investigated both experim...

  9. Progress in phosphors and filters for luminescent solar concentrators

    NARCIS (Netherlands)

    de Boer, D.K.G.; Broer, D.J.; Debije, M.G.; Keur, W.; Meijerink, A.; Ronda, R.C.; Verbunt, P.P.C.

    2012-01-01

    Luminescent solar concentrators would allow for high concentration if losses by reabsorption and escape could be minimized. We introduce a phosphor with close-to-optimal luminescent properties and hardly any reabsorption. A problem for use in a luminescent concentrator is the large scattering of

  10. Progress in phosphors and filters for luminescent solar concentrators

    NARCIS (Netherlands)

    De Boer, D.K.G.; Broer, D.J.; Debije, M.G.; Keur, W.C.; Meijerink, A.; Ronda, C.R.; Verbunt, P.P.C.

    2012-01-01

    Luminescent solar concentrators would allow for high concentration if losses by reabsorption and escape could be minimized. We introducea phosphor with close-to-optimal luminescent properties and hardlyany reabsorption. A problem for use in a luminescent concentrator isthe large scattering of this

  11. Progress in phosphors and filters for luminescent solar concentrators

    NARCIS (Netherlands)

    De Boer, D.K.G.; Broer, D.J.; Debije, M.G.; Keur, W.C.; Meijerink, A.; Ronda, C.R.; Verbunt, P.P.C.

    2012-01-01

    Luminescent solar concentrators would allow for high concentration if losses by reabsorption and escape could be minimized. We introducea phosphor with close-to-optimal luminescent properties and hardlyany reabsorption. A problem for use in a luminescent concentrator isthe large scattering of this m

  12. Development of a fluorescent label tool based on lanthanide nanophosphors for viral biomedical application

    Science.gov (United States)

    Le, Quoc Minh; Huong Tran, Thu; Huong Nguyen, Thanh; Khuyen Hoang, Thi; Binh Nguyen, Thanh; Do, Khanh Tung; Tran, Kim Anh; Hien Nguyen, Dang; Luan Le, Thi; Quy Nguyen, Thi; Dung Dang, Mai; Thu Nguyen, Nu Anh; Nguyen, Van Man

    2012-09-01

    We report for the first time the preparation of luminescent lanthanide nanomaterial (LLN) linked bioconjugates and their application as a label tool for recognizing virus in the processing line of vaccine industrial fabrication. Several LLNs with the nanostructure forms of particles or rods/wires with europium (III) and terbium (III) ions in lattices of vanadate, phosphate and metal organic complex were prepared to develop novel fluorescent conjugates able to be applied as labels in fluorescence immunoassay analysis of virus/vaccine. With regard to the LLNs, we have successfully synthesized nanoparticles around 10 nm of YVO4:Eu(III), with high emission in the red spectral region, nanorod and nanowire of TbPO4·H2O and Eu1-xTbxPO4·H2O, width 5-7 nm and length 300 nm, showing very bright luminescence in green, and core/shell nanosized Eu(III) and Tb(III)/Eu(III) complexes with naphthoyl trifluoroacetone and tri-n-octylphosphineoxide (Eu.NTA.TOPO@PVP, EuXTb1-X.NTA.TOPO). The appropriated core/shell structures can play a double role, one for enhancing luminescence efficiency and another for providing nanophosphors with better stability in water media for facilitating the penetration of nanophosphor core into a biomedical environment. The organic functionalizations of the obtained LLNs were done through their surface encapsulation with a functional polysiloxane including active groups such as amine (NH2), thiocyanate (SCN) or mecarpto (SH). The properties of functional sol-gel matrix have great influence on the luminescence properties, especially luminescence intensity of YVO4:Eu(III), Eu.NTA.TOPO@PVP, TbPO4·H2O and EuxTb1-xPO4·H2O. Bioconjugation processes of the functionalized LLNs have been studied with some bioactive molecules such as biotin, protein immunoglobulin G (IgG) or bovine serum albumin (BSA). The results of LLN-bioconjugate linking with IgG for recognizing virus (vaccine) will be presented in brief. It is consistent to state that the LLN bioconjugates

  13. Joint effect of ferromagnetic and non-ferromagnetic cations for adjusting room temperature ferromagnetism of highly luminescent CuNiInS quaternary nanocrystals

    Science.gov (United States)

    Shen, Jin; Wang, Chunlei; Xu, Shuhong; Lv, Changgui; Zhang, Ruohu; Cui, Yiping

    2017-01-01

    In this work, highly luminescent quaternary CuNiInS nanocrystals (NCs) are put forward as a good prototype for investigating defect-induced room temperature ferromagnetism. A ferromagnetic Ni cation can preserve the strong luminescence of NCs without introducing intermediate energy levels in the center of the forbidden band. The strong luminescence of NCs is used as an indicator for monitoring the concentration of vacancy defects inside them, facilitating the investigation of the origin of room temperature ferromagnetism in CuNiInS NCs. Our results reveal that the patching of Cu vacancies ({{{{V}}}{{Cu}}}-) with Ni will result in bound magnetic polarons composed of both {{{{V}}}{{Cu}}}- and a substitution of Cu by Ni ({{{{Ni}}}{{Cu}}}+), giving rise to the room temperature ferromagnetism of CuNiInS NCs. Either the ferromagnetic Ni or the non-ferromagnetic Cu cation can tune the magnetism of CuNiInS NCs because of the change of bound magnetic polaron concentration at the altered concentration ratio of {{{{V}}}{{Cu}}}- and {{{{Ni}}}{{Cu}}}+.

  14. Analysis of multinuclear lanthanide-induced shifts. 4. Some consequences of the lanthanide contraction

    Science.gov (United States)

    Peters, Joop A.

    The effects of the lanthanide contraction on lanthanide-induced shifts are estimated using simulated structures for a set of lanthanide chelates. The variations of the Ln-donor distances cause small conformational changes in the coordination polyhedron of the Ln(III) cation, and the induced pseudocontact shifts for a series of Ln complexes vary gradually going from La(III) to Lu(III). As a result of data manipulation these gradual variations may sometimes show up as an abrupt break in the middle of the lanthanide series.

  15. Fluorescence Spectra Studies on the Interaction between Lanthanides and Calmodulin

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    The conformation of Calmodulin(CaM) induced by lanthanides has been examined using fluorescence methods.With the addition of lanthanide (Ln3+), the intrinsic fluorescence intensity of CaM without calcium ions (Apo-CaM) first increases and then decreases.Ln3+ causes the decrease of intrinsic fluorescence intensity of calcium saturated CaM (Ca2+4-CaM) only at high concentrations.At low concentrations, Ln3+ results not only in the enhancement of fluorescence intensity of Apo-CaM, but also in a blue shift of the maximum emission wavelengh of dansyl labeled calmodulin(Apo-D-CaM).The molecular mechanism of the interaction between Ln3+ and CaM has been discussed in the light of the fluorescence spectra.

  16. Chemical and structural changes in Ln{sub 2}NiO{sub 4+δ} (Ln=La, Pr or Nd) lanthanide nickelates as a function of oxygen partial pressure at high temperature

    Energy Technology Data Exchange (ETDEWEB)

    Flura, Aurélien; Dru, Sophie; Nicollet, Clément; Vibhu, Vaibhav; Fourcade, Sébastien; Lebraud, Eric; Rougier, Aline; Bassat, Jean-Marc; Grenier, Jean-Claude, E-mail: grenier@icmcb-bordeaux.cnrs.fr

    2015-08-15

    The chemical stability of lanthanide nickelates Ln{sub 2}NiO{sub 4+δ} (Ln=La, Pr or Nd) has been studied in the temperature range 25–1300 °C, either in air or at low pO{sub 2} (down to 10{sup −4} atm). Thermal gravimetry analysis (TGA) measurements coupled with X-ray diffraction (XRD) characterization have shown that all compounds retain their K{sub 2}NiF{sub 4}-type structure in these conditions, while remaining over-stoichiometric in oxygen up to 1000 °C. Only Nd{sub 2}NiO{sub 4+δ} starts to decompose into Nd{sub 2}O{sub 3} and NiO above 1000 °C, at pO{sub 2}=10{sup −4} atm. In addition, a careful analysis of the lanthanide nickelates structural features has been performed by in situ XRD, as a function of temperature and pO{sub 2}. For all compounds, a structural transition has been always observed in the temperature range 200–400 °C, in air or at pO{sub 2}=10{sup −4} atm. In addition, their cell volume did not vary upon the variation of the oxygen partial pressure. Therefore, these materials do not exhibit a chemical expansion in these conditions, which is beneficial for a fuel cell application as cathode layers. Additional dilatometry measurements have revealed that a temperature as high as 950 °C for Pr{sub 2}NiO{sub 4+δ} or 1100 °C for La{sub 2}NiO{sub 4+δ} and Nd{sub 2}NiO{sub 4+δ} has to be reached in order to begin the sintering of the material particles, which is of primary importance to obtain an efficient electronic/ionic conduction in the corresponding designed cathode layers. Besides, excellent matching was found between the thermal expansion coefficients of lanthanide nickelates and SOFC electrolytes such as 8wt% yttria stabilized zirconia (8YSZ) or Ce{sub 0.8}Gd{sub 0.2}O{sub 2−δ} (GDC), at least from 400 °C up to 1400 °C in air or up to 1200 °C at pO{sub 2}=10{sup −4} atm. - Graphical abstract: This study reports the good chemical stability of oxygen overstoichiometric Ln2NiO4+δ(Ln = La, Pr or Nd) at high temperatures

  17. 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....

  18. Lanthanide phosphonates: Synthesis, thermal stability and magnetic characterization

    Energy Technology Data Exchange (ETDEWEB)

    Amghouz, Z., E-mail: amghouz.uo@uniovi.es [Departamentos de Quimica Fisica y Analitica y Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Garcia, J.R.; Garcia-Granda, S. [Departamentos de Quimica Fisica y Analitica y Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Clearfield, A. [Department of Chemistry, Texas A and M University, College Station, TX 77842-3012 (United States); Rodriguez Fernandez, J.; Pedro, I. de [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Blanco, J.A. [Departamento de Fisica, Universidad de Oviedo, 33007 Oviedo (Spain)

    2012-09-25

    Highlights: Black-Right-Pointing-Pointer Report of the complete series of lanthanide 1,4-phenylbis(phosphonate). Black-Right-Pointing-Pointer Synthesis under conventional hydrothermal synthesis or microwave-assisted hydrothermal synthesis. Black-Right-Pointing-Pointer Cation size is the key factor for the structural and particles size variations. Black-Right-Pointing-Pointer Thermal behaviour is characterized by unusual very high thermal stability. - Abstract: Series of novel organic-inorganic hybrids materials based on trivalent lanthanides (Ln = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and 1,4-phenylbis(phosphonate) obtained under hydrothermal conditions either by oven heat or microwave irradiation. The anhydrous compounds containing La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Ho, are isostructural. However, the compounds based on Y, Er, Tm, Yb, and Lu are hydrated and their structures have not yet been solved. The series of compounds are characterized by PXRD, TEM, SEM-EDX and thermal analyses (TG-MS and DSC). TEM study show a variable particles size with a minimum mean-particle size of ca. 30 nm. These compounds exhibit unusual very high thermal stability. The size of particles and the thermal stability are depending on lanthanide(III) cation features. All the investigated materials show paramagnetic behaviour. The magnetic susceptibility data follow a Curie-Weiss laws with paramagnetic effective moments in good agreement with those expected for Ln{sup 3+} free ions.

  19. 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.

  20. The effect of high pressure on the luminescent properties of coumarin 153

    CERN Document Server

    Li Hong; He Li Ming; Wu Shi Kang; Li Yi; Yang Guo Qiang

    2002-01-01

    A dual-fluorescence emitting behaviour of coumarin 153 powder has been detected at high pressure while at ambient pressure the dye exhibits only single-band emission. Because of the strong electron-withdrawal group at site 7, these two fluorescent peaks can be ascribed to local excited state emission and charge transfer state emission, respectively.

  1. Simultaneous phase and size control of upconversion nanocrystals through lanthanide doping

    KAUST Repository

    Wang, Feng

    2010-02-25

    Doping is a widely applied technological process in materials science that involves incorporating atoms or ions of appropriate elements into host lattices to yield hybrid materials with desirable properties and functions. For nanocrystalline materials, doping is of fundamental importance in stabilizing a specific crystallographic phase, modifying electronic properties, modulating magnetism as well as tuning emission properties. Here we describe a material system in which doping influences the growth process to give simultaneous control over the crystallographic phase, size and optical emission properties of the resulting nanocrystals. We show that NaYF 4 nanocrystals can be rationally tuned in size (down to ten nanometres), phase (cubic or hexagonal) and upconversion emission colour (green to blue) through use of trivalent lanthanide dopant ions introduced at precisely defined concentrations. We use first-principles calculations to confirm that the influence of lanthanide doping on crystal phase and size arises from a strong dependence on the size and dipole polarizability of the substitutional dopant ion. Our results suggest that the doping-induced structural and size transition, demonstrated here in NaYF 4 upconversion nanocrystals, could be extended to other lanthanide-doped nanocrystal systems for applications ranging from luminescent biological labels to volumetric three-dimensional displays. © 2010 Macmillan Publishers Limited. All rights reserved.

  2. Optimizing millisecond time scale near-infrared emission in polynuclear chrome(III)-lanthanide(III) complexes.

    Science.gov (United States)

    Aboshyan-Sorgho, Lilit; Nozary, Homayoun; Aebischer, Annina; Bünzli, Jean-Claude G; Morgantini, Pierre-Yves; Kittilstved, Kevin R; Hauser, Andreas; Eliseeva, Svetlana V; Petoud, Stéphane; Piguet, Claude

    2012-08-01

    This work illustrates a simple approach for optimizing long-lived near-infrared lanthanide-centered luminescence using trivalent chromium chromophores as sensitizers. Reactions of the segmental ligand L2 with stoichiometric amounts of M(CF(3)SO(3))(2) (M = Cr, Zn) and Ln(CF(3)SO(3))(3) (Ln = Nd, Er, Yb) under aerobic conditions quantitatively yield the D(3)-symmetrical trinuclear [MLnM(L2)(3)](CF(3)SO(3))(n) complexes (M = Zn, n = 7; M = Cr, n = 9), in which the central lanthanide activator is sandwiched between the two transition metal cations. Visible or NIR irradiation of the peripheral Cr(III) chromophores in [CrLnCr(L2)(3)](9+) induces rate-limiting intramolecular intermetallic Cr→Ln energy transfer processes (Ln = Nd, Er, Yb), which eventually produces lanthanide-centered near-infrared (NIR) or IR emission with apparent lifetimes within the millisecond range. As compared to the parent dinuclear complexes [CrLn(L1)(3)](6+), the connection of a second strong-field [CrN(6)] sensitizer in [CrLnCr(L2)(3)](9+) significantly enhances the emission intensity without perturbing the kinetic regime. This work opens novel exciting photophysical perspectives via the buildup of non-negligible population densities for the long-lived doubly excited state [Cr*LnCr*(L2)(3)](9+) under reasonable pumping powers.

  3. Mesomorphism of Lanthanide(Ⅲ) 4-Hexyloxybenzoates

    Institute of Scientific and Technical Information of China (English)

    Liesbet Jongen; Bart Goderis; Igor P Dolbnya; Koen Binnemans

    2004-01-01

    The 4-alkoxybenzoic acids are well-known liquid crystals showing several mesophases(nematic,smectic C phase or both)depending on the alkoxy chain length and whereby the rigid core of the mesogen is formed by intermolecular hydrogen bonds.In this paper it is shown that the thermal behaviour of lanthanide salts of 4-hexyloxybenzoic acids depends on the lanthanide ion(Ln=La,Pr,Nd,Sm,Eu).The lanthanum(Ⅲ)and praseodymium(Ⅲ)4-hexyloxybenzoates exhibit a smectic A mesophase.No mesophase is found for the corresponding compounds of heavier lanthanides.The thermal properties of the lanthanide(Ⅲ)4-hexyloxybenzoates were investigated by differential scanning calorimetry(DSC),polarising thermo-optical microscopy and synchrotron X-ray radiation.

  4. Polar-solvent-free colloidal synthesis of highly luminescent alkylammonium lead halide perovskite nanocrystals

    Science.gov (United States)

    Vybornyi, Oleh; Yakunin, Sergii; Kovalenko, Maksym V.

    2016-03-01

    A novel synthesis of hybrid organic-inorganic lead halide perovskite nanocrystals (CH3NH3PbX3, X = Br or I) that does not involve the use of dimethylformamide or other polar solvents is presented. The reaction between methylamine and PbX2 salts is conducted in a high-boiling nonpolar solvent (1-octadecene) in the presence of oleylamine and oleic acid as coordinating ligands. The resulting nanocrystals are characterized by high photoluminescence quantum efficiencies of 15-50%, outstanding phase purity and tunable shapes (nanocubes, nanowires, and nanoplatelets). Nanoplatelets spontaneously assemble into micrometer-length wires by face-to-face stacking. In addition, we demonstrate amplified spontaneous emission from thin films of green-emitting CH3NH3PbBr3 nanowires with low pumping thresholds of 3 μJ cm-2.A novel synthesis of hybrid organic-inorganic lead halide perovskite nanocrystals (CH3NH3PbX3, X = Br or I) that does not involve the use of dimethylformamide or other polar solvents is presented. The reaction between methylamine and PbX2 salts is conducted in a high-boiling nonpolar solvent (1-octadecene) in the presence of oleylamine and oleic acid as coordinating ligands. The resulting nanocrystals are characterized by high photoluminescence quantum efficiencies of 15-50%, outstanding phase purity and tunable shapes (nanocubes, nanowires, and nanoplatelets). Nanoplatelets spontaneously assemble into micrometer-length wires by face-to-face stacking. In addition, we demonstrate amplified spontaneous emission from thin films of green-emitting CH3NH3PbBr3 nanowires with low pumping thresholds of 3 μJ cm-2. Electronic supplementary information (ESI) available: Materials and methods, additional figures. See DOI: 10.1039/c5nr06890h

  5. $Er^{3+}$ luminescence as a sensor of high pressure and strong external magnetic fields

    NARCIS (Netherlands)

    Valiente, R.; Millot, M.; Rodriguez, F.; Gonzalez, J.; Broto, J-M.; George, S.; Garcia-Revilla, S.; Romanyuk, Y.; Pollnau, M.

    2009-01-01

    In this paper, we present the preliminary results of the combined effect of high pressure (up to 7.5 GPa) and strong external magnetic fields (up to 28.5 T) on the photoluminescence (PL) properties of $Er^{3+}–Yb^{3+}$ co-doped single-crystal thin films of well-oriented $KY(WO_4)_2$ at low temperat

  6. Formation mechanism of highly luminescent silica capsules incorporating multiple hydrophobic quantum dots with various emission wavelengths.

    Science.gov (United States)

    Li, Chunliang; Murase, Norio

    2013-12-01

    A synthesis process was reconsidered for encapsulating hydrophobic quantum dots (QDs) into silica capsules with high photoluminescent (PL) efficiency. The process comprises three steps: silanization of QD surfaces, seed formation by assembly of the QDs, and coating of the QD seeds with a silica shell. Analysis of the encapsulation mechanism enabled this process to be adapted for application to CdSe-based core-shell QDs with various organic ligands such as oleic acid and with various emission wavelengths. Formation of the seeds is the key step in synthesizing the silica capsules, so that they have high PL efficiency. Due to the differences in QD size and in the affinity of the ligands on their surfaces, the concentration of QDs used in the synthesis must be optimized to maximize emission efficiency. Contrary to an initial assumption, several ligands remained on the QD surfaces even after the QDs were transferred from organic solution to water. This greatly affected the size and PL efficiency of the seeds. Judicious selection of the conditions for seed and silica capsule synthesis resulted in seeds with PL efficiency greater than 70% and in silica capsules encapsulating multiple CdSe/CdZnS QDs with PL efficiency as high as 41%. Silica capsules incorporating QDs with various emission peak wavelengths from green to red were also prepared. The process presented serves as a guideline for encapsulating various types of hydrophobic QDs into silica capsules for biological tagging applications.

  7. Lanthanide(III) complexation with an amide derived pyridinophane.

    Science.gov (United States)

    Castro, Goretti; Bastida, Rufina; Macías, Alejandro; Pérez-Lourido, Paulo; Platas-Iglesias, Carlos; Valencia, Laura

    2015-02-16

    Herein we report a detailed investigation of the solid state and solution structures of lanthanide(III) complexes with the 18-membered pyridinophane ligand containing acetamide pendant arms TPPTAM (TPPTAM = 2,2',2″-(3,7,11-triaza-1,5,9(2,6)-tripyridinacyclododecaphane-3,7,11-triyl)triacetamide). The ligand crystallizes in the form of a clathrated hydrate, where the clathrated water molecule establishes hydrogen-bonding interactions with the amide NH groups and two N atoms of the macrocycle. The X-ray structures of 13 different Ln(3+) complexes obtained as the nitrate salts (Ln(3+) = La(3+)-Yb(3+), except Pm(3+)) have been determined. Additionally, the X-ray structure of the La(3+) complex obtained as the triflate salt was also obtained. In all cases the ligand provides 9-fold coordination to the Ln(3+) ion, ten coordination being completed by an oxygen atom of a coordinated water molecule or a nitrate or triflate anion. The bond distances of the metal coordination environment show a quadratic change along the lanthanide series, as expected for isostructural series of Ln(3+) complexes. Luminescence lifetime measurements obtained from solutions of the Eu(3+) and Tb(3+) complexes in H2O and D2O point to the presence of a water molecule coordinated to the metal ion in aqueous solutions. The analysis of the Ln(3+)-induced paramagnetic shifts indicates that the complexes are ten-coordinated throughout the lanthanide series from Ce(3+) to Yb(3+), and that the solution structure is very similar to the structures observed in the solid state. The complexes of the light Ln(3+) ions are fluxional due to a fast Δ(λλλλλλ) ↔ Λ(δδδδδδ) interconversion that involves the inversion of the macrocyclic ligand and the rotation of the acetamide pendant arms. The complexes of the small Ln(3+) ions are considerably more rigid, the activation free energy determined from VT (1)H NMR for the Lu(3+) complex being ΔG(⧧)298 = 72.4 ± 5.1 kJ mol(-1).

  8. High Luminescence Efficiency in MoS2 Grown by Chemical Vapor Deposition.

    Science.gov (United States)

    Amani, Matin; Burke, Robert A; Ji, Xiang; Zhao, Peida; Lien, Der-Hsien; Taheri, Peyman; Ahn, Geun Ho; Kirya, Daisuke; Ager, Joel W; Yablonovitch, Eli; Kong, Jing; Dubey, Madan; Javey, Ali

    2016-07-26

    One of the major challenges facing the rapidly growing field of two-dimensional (2D) transition metal dichalcogenides (TMDCs) is the development of growth techniques to enable large-area synthesis of high-quality materials. Chemical vapor deposition (CVD) is one of the leading techniques for the synthesis of TMDCs; however, the quality of the material produced is limited by defects formed during the growth process. A very useful nondestructive technique that can be utilized to probe defects in semiconductors is the room-temperature photoluminescence (PL) quantum yield (QY). It was recently demonstrated that a PL QY near 100% can be obtained in MoS2 and WS2 monolayers prepared by micromechanical exfoliation by treating samples with an organic superacid: bis(trifluoromethane)sulfonimide (TFSI). Here we have performed a thorough exploration of this chemical treatment on CVD-grown MoS2 samples. We find that the as-grown monolayers must be transferred to a secondary substrate, which releases strain, to obtain high QY by TFSI treatment. Furthermore, we find that the sulfur precursor temperature during synthesis of the MoS2 plays a critical role in the effectiveness of the treatment. By satisfying the aforementioned conditions we show that the PL QY of CVD-grown monolayers can be improved from ∼0.1% in the as-grown case to ∼30% after treatment, with enhancement factors ranging from 100 to 1500× depending on the initial monolayer quality. We also found that after TFSI treatment the PL emission from MoS2 films was visible by eye despite the low absorption (5-10%). The discovery of an effective passivation strategy will speed the development of scalable high-performance optoelectronic and electronic devices based on MoS2.

  9. High resolution optically stimulated luminescence dating of a sediment core from the southwestern Sea of Okhotsk

    DEFF Research Database (Denmark)

    Sugisaki, S.; Buylaert, J. P.; Murray, A. S.;

    2012-01-01

    in application to a 19 m marine sediment core (MR0604-PC04A) taken from the southwestern Sea of Okhotsk, immediately to the north of Hokkaido, Japan. Fine-grained quartz (4 to 11 mu m) was chosen as the dosimeter, and a single-aliquot regenerative-dose protocol was used for the determination of equivalent dose...... (D-e), with stimulation by both infrared and blue light. The suitability of the measurement procedure was confirmed using dose recovery tests. A high resolution record (similar to 2 OSL ages/m) identified clear sedimentation rate changes down the core. The OSL ages are significantly dependent...

  10. Stored Luminescence Computed Tomography

    CERN Document Server

    Cong, Wenxiang; Wang, Ge

    2013-01-01

    The phosphor nanoparticles made of doped semiconductors, pre-excited by well-collimated X-ray radiation, were recently reported for their light emission upon NIR light stimulation. The characteristics of X-ray energy storage and NIR stimulated emission is highly desirable to design targeting probes and improve molecular and cellular imaging. Here we propose stored luminescence computed tomography (SLCT), perform realistic numerical simulation, and demonstrate a much-improved spatial resolution in a preclinical research context. The future opportunities are also discussed along this direction.

  11. A luminescent nanocrystal stress gauge

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Charina; Koski, Kristie; Olson, Andrew; Alivisatos, Paul

    2010-10-25

    Microscale mechanical forces can determine important outcomes ranging from the site of material fracture to stem cell fate. However, local stresses in a vast majority of systems cannot be measured due to the limitations of current techniques. In this work, we present the design and implementation of the CdSe/CdS core/shell tetrapod nanocrystal, a local stress sensor with bright luminescence readout. We calibrate the tetrapod luminescence response to stress, and use the luminescence signal to report the spatial distribution of local stresses in single polyester fibers under uniaxial strain. The bright stress-dependent emission of the tetrapod, its nanoscale size, and its colloidal nature provide a unique tool that may be incorporated into a variety of micromechanical systems including materials and biological samples to quantify local stresses with high spatial resolution.

  12. Micro-modulated luminescence tomography

    CERN Document Server

    Cong, Wenxiang; Wang, Chao; Wang, Ge

    2013-01-01

    Imaging depth of optical microscopy has been fundamentally limited to millimeter or sub-millimeter due to light scattering. X-ray microscopy can resolve spatial details of few microns deeply inside a sample but the contrast resolution is still inadequate to depict heterogeneous features at cellular or sub-cellular levels. To enhance and enrich biological contrast at large imaging depth, various nanoparticles are introduced and become essential to basic research and molecular medicine. Nanoparticles can be functionalized as imaging probes, similar to fluorescent and bioluminescent proteins. LiGa5O8:Cr3+ nanoparticles were recently synthesized to facilitate luminescence energy storage with x-ray pre-excitation and the subsequently stimulated luminescence emission by visible/near-infrared (NIR) light. In this paper, we suggest a micro-modulated luminescence tomography (MLT) approach to quantify a nanophosphor distribution in a thick biological sample with high resolution. Our numerical simulation studies demonst...

  13. Highly luminescent N, S- Co-doped carbon dots and their direct use as mercury(II) sensor

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yu [Key Lab of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Department of Advanced Organic Materials Science and Engineering, Kyungpook National University, Daegu, 702-701 (Korea, Republic of); Kim, Sung-Hoon, E-mail: shokim@knu.ac.kr [Department of Advanced Organic Materials Science and Engineering, Kyungpook National University, Daegu, 702-701 (Korea, Republic of); Feng, Liang, E-mail: fengl@dicp.ac.cn [Key Lab of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)

    2015-08-26

    Heteroatom doping has been proven as an efficient way to improve the fluorescent efficiency of carbon dots. Co-doping with heteroatoms may introduce more active sites to carbon dots, which would broaden applications of CDs in sensing. In this work, highly luminescent nitrogen and sulfur co-doped carbon dots (NSCDs) were synthesized through a facile one-step microwave assisted method by using citric acid and rubeanic acid as carbon, nitrogen, and sulfur sources. The well-isolated NSCDs not only exhibit an enhanced fluorescent efficiency with a relatively high quantum yield up to 17.6%, but also show potential use as a multi-sensing platform based on their fluorescence “on-off-on” and color changing behaviors. The NSCDs can be directly used for the selective determination of mercury cations without any functionalization. The detection limit is approximately calculated as 0.18 μM and linear range is 0–20 μM. The sensing mechanism is proposed as coordination reaction induced by oligomers upon the carbon core. Furthermore, in the presence of cyanide anions, the fluorescence shows linear recovery associated with the concentration of cyanide, indicating its potential usage for the detection of cyanide ion. The optimized pH range for such fluorescence “on-off-on” sensing system is investigated as pH 6–8, suggesting potential applications in bio-sensing and imaging area. In addition, by adding hydrosulfide anion to NSCDs@Hg{sup 2+} complex, a notable color change could be clearly observed due to the formation of fuscous HgS. In application, a handy test paper for direct and rapid detection of Hg{sup 2+} is manufactured for the evaluation of usage of NSCDs in the real circumstance. - Highlights: • NSCDs were synthesized by using citric acid and rubeanic acid. • NSCDs exhibited an enhanced fluorescent efficiency with high QY up to 17.6%. • NSCDs presented good sensing performance to mercury ions. • NSCDs showed potential use as a multi-sensing platform.

  14. Novel cookie-with-chocolate carbon dots displaying extremely acidophilic high luminescence

    Science.gov (United States)

    Lu, Siyu; Zhao, Xiaohuan; Zhu, Shoujun; Song, Yubin; Yang, Bai

    2014-10-01

    A fluorescent carbon dot with a cookie-with-chocolate film structure (about 5 × 5 μm2) showed a high fluorescence quantum yield (61.12%) at low pH. It was hydrothermally synthesized from l-serine and l-tryptophan. The formation mechanism of the film with carbon dots (CDs) was investigated. The film structure was formed by hydrogen bonding and π-π stacking interactions between aromatic rings. The strong blue fluorescence of the CDs increased under strong acidic conditions owing to the changes in the N-groups. These cookie-like CDs are attractive for their potential use as effective fluorescent probes for the sensitive detection of aqueous H+ and Fe3+.A fluorescent carbon dot with a cookie-with-chocolate film structure (about 5 × 5 μm2) showed a high fluorescence quantum yield (61.12%) at low pH. It was hydrothermally synthesized from l-serine and l-tryptophan. The formation mechanism of the film with carbon dots (CDs) was investigated. The film structure was formed by hydrogen bonding and π-π stacking interactions between aromatic rings. The strong blue fluorescence of the CDs increased under strong acidic conditions owing to the changes in the N-groups. These cookie-like CDs are attractive for their potential use as effective fluorescent probes for the sensitive detection of aqueous H+ and Fe3+. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03965c

  15. Pure Cs4PbBr6: Highly Luminescent Zero-Dimensional Perovskite Solids

    KAUST Repository

    Saidaminov, Makhsud I.

    2016-09-26

    So-called zero-dimensional perovskites, such as Cs4PbBr6, promise outstanding emissive properties. However, Cs4PbBr6 is mostly prepared by melting of precursors that usually leads to a coformation of undesired phases. Here, we report a simple low-temperature solution-processed synthesis of pure Cs4PbBr6 with remarkable emission properties. We found that pure Cs4PbBr6 in solid form exhibits a 45% photoluminescence quantum yield (PLQY), in contrast to its three-dimensional counterpart, CsPbBr3, which exhibits more than 2 orders of magnitude lower PLQY. Such a PLQY of Cs4PbBr6 is significantly higher than that of other solid forms of lower-dimensional metal halide perovskite derivatives and perovskite nanocrystals. We attribute this dramatic increase in PL to the high exciton binding energy, which we estimate to be ∼353 meV, likely induced by the unique Bergerhoff–Schmitz–Dumont-type crystal structure of Cs4PbBr6, in which metal-halide-comprised octahedra are spatially confined. Our findings bring this class of perovskite derivatives to the forefront of color-converting and light-emitting applications.

  16. Luminescent tracks of high-energy photoemitted electrons accelerated by plasmonic fields

    Directory of Open Access Journals (Sweden)

    Di Vece Marcel

    2015-12-01

    Full Text Available The emission of an electron from a metal nanostructure under illumination and its subsequent acceleration in a plasmonic field forms a platform to extend these phenomena to deposited nanoparticles, which can be studied by state-of-the-art confocal microscopy combined with femtosecond optical excitation. The emitted and accelerated electrons leave defect tracks in the immersion oil, which can be revealed by thermoluminescence. These photographic tracks are read out with the confocal microscope and have a maximum length of about 80 μm, which corresponds to a kinetic energy of about 100 keV. This energy is consistent with the energy provided by the intense laser pulse combined with plasmonic local field enhancement. The results are discussed within the context of the rescattering model by which electrons acquire more energy. The visualization of electron tracks originating from plasmonic field enhancement around a gold nanoparticle opens a new way to study with confocal microscopy both the plasmonic properties of metal nano objects as well as high energy electron interaction with matter.

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

    Science.gov (United States)

    Lessmann, J J; Horrocks, W D

    2000-07-24

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

  18. High temperature luminescence of Dy3+ in crystalline silicon in the optical communication and eye-safe spectral regions.

    Science.gov (United States)

    Lourenço, M A; Mustafa, Z; Ludurczak, W; Wong, L; Gwilliam, R M; Homewood, K P

    2013-09-15

    We report on photoluminescence in the 1.3 and 1.7 μm spectral ranges in silicon doped with dysprosium. This is attributed to the Dy3+ internal transitions between the second Dy3+ excited state and the ground state, and between the third Dy3+ excited state and the ground state. Luminescence is achieved by Dy implantation into Si substrates codoped with boron, to form dislocation loops, and show a strong dependence on fabrication process. The spectra consist of several sharp lines with the strongest emission at 1736 nm, observed up to 200 K. No Dy3+ luminescence is observed in samples without B codoping, showing the paramount importance of dislocation loops to enable the Dy emission.

  19. Dual-emissive nanoarchitecture of lanthanide-complex-modified silica particles for in vivo ratiometric time-gated luminescence imaging of hypochlorous acid† †Electronic supplementary information (ESI) available: Characterization of the new compounds, Fig. S1–S12 and a video showing the real-time uptake and accumulation of HClO in living Daphnia magna using the RTLNP as a probe. See DOI: 10.1039/c6sc02243j Click here for additional data file. Click here for additional data file.

    Science.gov (United States)

    Ma, Hua; Wang, Yuanxiu; Cong, Deyuan; Jiang, Yufei

    2017-01-01

    We have developed a ratiometric time-gated luminescence sensory system for in vivo imaging of hypochlorous acid (HClO) by preparing a dual-emissive nanoarchitecture of europium- and terbium-complex-modified silica nanoparticles. The design of this nanoarchitecture is based on our new finding that the strong, long-lived luminescence of the β-diketonate–Eu3+ complex can be rapidly and selectively quenched by HClO. Therefore, the β-diketonate–Eu3+ complex was decorated on the surface of the silica nanoparticles for responding to HClO, while a HClO-insensitive luminescent terbium complex was immobilized in the inner solid core of the nanoparticles to serve as an internal standard. This nanosensing probe combines the advantages of both ratiometric and time-gated detection modes to afford high accuracy and sensitivity. Upon exposure to HClO, the nanoprobe displayed a remarkable luminescence color change from red to green, and the intensity ratio of the green over the red luminescence (I 539/I 607) showed a rapid, sensitive and selective response to HClO. Additionally, the feasibility of using the nanoprobe for intracellular detection of exogenous and endogenous HClO and for real-time mapping of HClO in small laboratory animals has been demonstrated via ratiometric time-gated luminescence imaging microscopy. The results reveal that the constructed nanoarchitecture cloud is a favorable and useful sensing probe for the real-time imaging of HClO in vivo with high specificity and contrast. PMID:28451159

  20. Progress in phosphors and filters for luminescent solar concentrators.

    Science.gov (United States)

    de Boer, Dick K G; Broer, Dirk J; Debije, Michael G; Keur, Wilco; Meijerink, Andries; Ronda, Cees R; Verbunt, Paul P C

    2012-05-07

    Luminescent solar concentrators would allow for high concentration if losses by reabsorption and escape could be minimized. We introduce a phosphor with close-to-optimal luminescent properties and hardly any reabsorption. A problem for use in a luminescent concentrator is the large scattering of this material; we discuss possible solutions for this. Furthermore, the use of broad-band cholesteric filters to prevent escape of luminescent radiation from this phosphor is investigated both experimentally and using simulations. Simulations are also used to predict the ultimate performance of luminescent concentrators.

  1. Guest-induced SC-SC transformation within the first K/Cd heterodimetallic triazole complex: a luminescent sensor for high-explosives and cyano molecules.

    Science.gov (United States)

    Wang, Ying; Jia, Wei; Chen, Ran; Zhao, Xiao-Jun; Wang, Zhong-Liang

    2017-01-03

    The first K/Cd heterodimetallic complex {[Cd1.5(TTPE)1.5Cl3K(H2O)3]·3H2O}n (1b) based on triazole has been generated from {[Cd(TTPE)(HCOO)](NO3)·3DMAC·H2O}n (1) during the ion- and solvent-exchange experiment in an irreversible SC-SC transformation. Based on its luminescence properties, we have, for the first time, demonstrated that 1b is a heterodimetallic sensor for detection of high-explosives and cyano molecules.

  2. Synthesis and Characterization of La-Doped Luminescent Multilayer Films

    Directory of Open Access Journals (Sweden)

    Tianlei Wang

    2017-01-01

    Full Text Available In this work, we have successfully designed ordered luminescent multilayer films based on La-doped nonmagnetic or magnetic inorganic nanostructure with electronic microenvironment (EM. The inorganic nanosheets with opposite charge can assemble EM between the interlayers. At the same time, their elements on nanosheets of layer double hydroxides (LDHs are facile to be replaced so that we can introduce transition metal or lanthanide elements. Besides, ferromagnetic effect (FE can be formed in this microenvironment due to introducing transition metal on LDHs nanosheets. As a result, we confirm that EM, FE, and doping La element in the LDHs can affect the vibration of backbone of chromophores and then prolong the luminescent lifetime, which suggests a new pathway for developing the novel light-emitting thin films.

  3. Lanthanide bimetallic helicates for in vitro imaging and sensing.

    Science.gov (United States)

    Bünzli, Jean-Claude G; Chauvin, Anne-Sophie; Vandevyver, Caroline D B; Bo, Song; Comby, Steve

    2008-01-01

    As the need for targeting luminescent biolabels increases, for mapping selected analytes, imaging of cells and organs, and tracking in cellulo processes, lanthanide bimetallic helicates are emerging as versatile bioprobes. The wrapping of three ligand strands around two metallic centers by self-assembly affords robust molecular edifices with tunable chemical and photophysical properties. In addition, heterometallic helical chelates can be assembled leading to bioprobes with inherent chiral properties. In this paper, we review the literature demonstrating that neutral [Ln(2)(L(CX))(3)] (x=1-3) helicates represent a viable alternative to existing chelating agents for bio-analyses, while featuring specific enhanced properties. These bimetallic chelates self-assemble in water, and at physiological pH the 2:3 (Ln:L(CX)) complex is by far the dominant species, conditional stability constants logbeta(23) being in the range 23-30. The metal ions are 9-coordinate and lie in sites with slightly distorted D(3) symmetry. Efficient protection from water interaction by the tightly wrapped ligand strands results in sizeable photophysical properties, with quantum yields up to 24% for Eu(III) and 11% for Tb(III), while the luminescence of several other visible and/or near-infrared emitting Ln(III) ions is also sensitized. Noncytotoxicity for all the helicates is established for several living cell lines including HeLa, HaCat, MCF-7, 5D10, and Jurkat. We present new data pertaining to the live cell imaging ability of [Eu(2)(L(C1))(3)] and compare the three systems with x=1-3 with respect to thermodynamic stability, photophysics, cell-permeation ability, and targeting capability for sensing in cellulo processes. Prospects of derivatization for characterizing specific biological interactions are discussed.

  4. Fabrication and characterization of dual-functional ultrafine composite fibers with phase-change energy storage and luminescence properties

    Science.gov (United States)

    Xi, Peng; Zhao, Tianxiang; Xia, Lei; Shu, Dengkun; Ma, Menjiao; Cheng, Bowen

    2017-01-01

    Ultrafine composite fibers consisting of a thermoplastic polyurethane solid-solid phase-change material and organic lanthanide luminescent materials were prepared through a parallel electrospinning technique as an innovative type of ultrafine, dual-functional fibers containing phase-change and luminescent properties. The morphology and structure, thermal energy storage, and luminescent properties of parallel electrospun ultrafine fibers were investigated. Scanning electron microscopy (SEM) images showed that the parallel electrospun ultrafine fibers possessed the desired morphologies with smaller average fiber diameters than those of traditional mixed electrospun ultrafine fibers. Transmission electron microscopy (TEM) images revealed that the parallel electrospun ultrafine fibers were composed of two parts. Polymeric phase-change materials, which can be directly produced and spun, were used to provide temperature stability, while a mixture of polymethyl methacrylate and an organic lanthanide complex acted as the luminescent unit. Differential scanning calorimetry (DSC) and luminescence measurements indicated that the unique structure of the parallel electrospun ultrafine fibers provides the products with good thermal energy storage and luminescence properties. The fluorescence intensity and the phase-change enthalpy values of the ultrafine fibers prepared by parallel electrospinning were respectively 1.6 and 2.1 times those of ultrafine fibers prepared by mixed electrospinning.

  5. Fabrication and characterization of dual-functional ultrafine composite fibers with phase-change energy storage and luminescence properties.

    Science.gov (United States)

    Xi, Peng; Zhao, Tianxiang; Xia, Lei; Shu, Dengkun; Ma, Menjiao; Cheng, Bowen

    2017-01-09

    Ultrafine composite fibers consisting of a thermoplastic polyurethane solid-solid phase-change material and organic lanthanide luminescent materials were prepared through a parallel electrospinning technique as an innovative type of ultrafine, dual-functional fibers containing phase-change and luminescent properties. The morphology and structure, thermal energy storage, and luminescent properties of parallel electrospun ultrafine fibers were investigated. Scanning electron microscopy (SEM) images showed that the parallel electrospun ultrafine fibers possessed the desired morphologies with smaller average fiber diameters than those of traditional mixed electrospun ultrafine fibers. Transmission electron microscopy (TEM) images revealed that the parallel electrospun ultrafine fibers were composed of two parts. Polymeric phase-change materials, which can be directly produced and spun, were used to provide temperature stability, while a mixture of polymethyl methacrylate and an organic lanthanide complex acted as the luminescent unit. Differential scanning calorimetry (DSC) and luminescence measurements indicated that the unique structure of the parallel electrospun ultrafine fibers provides the products with good thermal energy storage and luminescence properties. The fluorescence intensity and the phase-change enthalpy values of the ultrafine fibers prepared by parallel electrospinning were respectively 1.6 and 2.1 times those of ultrafine fibers prepared by mixed electrospinning.

  6. High pressure and time-resolved luminescence spectra of Ca3Y2(SiO4)3 doped with Eu2+ and Eu3+.

    Science.gov (United States)

    Baran, A; Mahlik, S; Grinberg, M; Zych, E

    2013-01-16

    Tricalcium diyttrium trisilicon oxide, Ca(3)Y(2)(SiO(4))(3) doped with Eu(2+) and Eu(3+) belongs to a very limited number of hosts able to accommodate both Eu(3+) and Eu(2+) ions, which might make it useful for white light emitting diodes (WLEDs) based on UV chip technology. In this contribution we present a detailed study of photoluminescence kinetics and high pressure spectroscopy of Eu(3+) and Eu(2+) doped Ca(3)Y(2)(SiO(4))(3). At ambient pressure and room temperature, under excitation with near-UV radiation, a broad emission band from 400 to 550 nm due to the 4f(6)5d(1)→4f(7)((8)S(7/2)) transition in Eu(2+) was observed, as well as several emission peaks in the region between 550 and 710 nm, ascribed to the (5)D(0)→ (7)F(J) (J = 0-4) transitions in Eu(3+). The bluish green luminescence related to Eu(2+) in the Ca(3)Y(2)(SiO(4))(3) exhibits a small red pressure-induced shift reaching -5.2 cm(-1)/kbar. The red shifts of the luminescence lines related to Eu(3+) ion emission vary from 0.15 to -0.54 cm(-1)/kbar. Time-resolved photoluminescence was measured at different temperatures and pressures. Luminescence decay traces were studied for the bluish green emission band of Eu(2+) and for the red emission peak due to the (5)D(0) →  (7)F(2) transition of Eu(3+). Decay times slightly decreased with increasing pressure.

  7. Spectral intensities in trivalent lanthanide systems

    Energy Technology Data Exchange (ETDEWEB)

    Acevedo, Roberto [Facultad de Ingenieria, Universidad Mayor, Avenida Manuel Montt 367, Postal code 7500994, Providencia, Santiago (Chile)], E-mail: roberto.acevedo@umayor.cl; Soto-Bubert, Andres; Bosch, Paul [Instituto de Ciencias Basicas, Facultad de Ingenieria, Universidad Diego Portales, Avenida Ejercito 441, Casilla 298-V, Santiago (Chile); Strek, Wieslaw [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okoelna 2, 50-422 Wroclaw (Poland)

    2008-08-11

    The main goal of this research work is to rationalize the rich vibronic structure of lanthanide type crystals, such as Cs{sub 2}NaDyCl{sub 6} and Cs{sub 2}NaHoCl{sub 6}, in the space group Fm3m(O{sub h}{sup 5}). These systems are known to be highly relativistic and as a consequence, major corrections to previous model calculations should be taken into account so as to explain from a semi-quantitative viewpoint, the observed spectral intensities. We have decided to tackle this study taking special care, of both the physics and the chemistry involved with special emphasis on the theoretical model to be employed as well as, in the strategy to be followed to rationalize the available experimental data. This paper aims to advance our understanding of the intensity mechanisms, associated with observed radiative transitions, say for complex highly relativistic systems, in the solid state physics. The spectral intensities associated with superpositions (juxtapositions) of peaks and/or bands in the absortion and emission spectra are considered in detail and a preliminary working methodology is put forward with reference to the Cs{sub 2}NaDyCl{sub 6} and Cs{sub 2}NaHoCl{sub 6} crystals.

  8. Highly sensitive and selective cartap nanosensor based on luminescence resonance energy transfer between NaYF4:Yb,Ho nanocrystals and gold nanoparticles.

    Science.gov (United States)

    Wang, Zhijiang; Wu, Lina; Shen, Baozhong; Jiang, Zhaohua

    2013-09-30

    Fluorescent detection is an attractive method for the detection of toxic chemicals. However, most chemosensors that are currently utilized in fluorescent detection are based on organic dyes or quantum dots, which suffer from instability, high background noise and interference from organic impurities in solution, which can also be excited by UV radiation. In the present research, we developed a novel NaYF4:Yb,Ho/Au nanocomposite-based chemosensor with high sensitivity (10 ppb) and selectivity over competing analytes for the detection of the insecticide cartap. This nanosensor is excited with a 970-nm laser instead of UV radiation to give an emission peak at 541 nm. In the presence of cartap, the nanocomposites aggregate, resulting in enhanced luminescence resonance energy transfer between the NaYF4:Yb,Ho nanocrystals and the gold nanoparticles, which decreases the emission intensity at 541 nm. The relative luminescence intensity at 541 nm has a linear relationship with the concentration of cartap in the solution. Based on this behavior, the developed nanosensor successfully detected cartap in farm produce and water samples with satisfactory results.

  9. Wideband luminescence of high-density InAs quantum dots on GaAsSb/GaAs layers

    Science.gov (United States)

    Osaka, Yuji; Tanabe, Hiroyuki; Yamada, Kazuhiro; Yamaguchi, Koichi

    2013-09-01

    In order to achieve wideband luminescence, ultrahigh density InAs quantum dots (QDs) were grown on GaAsSb buffer layers by molecular beam epitaxy under various growth conditions. Ultrahigh density of 3.8-5.2×1011 cm-2 and large size fluctuation were obtained. Photoluminescence (PL) spectra of ultrahigh density QD layers were changed by adjusting the growth conditions. Three ultrahigh density QD layers with different PL spectra were stacked on GaAs (001) substrate. The PL spectrum of edge emission revealed strong intensity and a broad linewidth of 194 nm. The presented QD structures are expected for development of wideband superluminescent diodes.

  10. Systematic development of new thermoluminescence and optically stimulated luminescence materials

    Energy Technology Data Exchange (ETDEWEB)

    Yukihara, E.G., E-mail: eduardo.yukihara@okstate.edu [Physics Department, 145 Physical Sciences II, Oklahoma State University, Stillwater, OK 74078 (United States); Milliken, E.D.; Oliveira, L.C. [Physics Department, 145 Physical Sciences II, Oklahoma State University, Stillwater, OK 74078 (United States); Orante-Barron, V.R. [Departamento de Investigacion en Polimeros y Materiales, Universidad de Sonora, Hermosillo, Sonora 83000, Mexico (Mexico); Jacobsohn, L.G. [Center for Optical Materials Science and Engineering Technologies (COMSET), and School of Materials Science and Engineering, Clemson University, Clemson, SC (United States); Blair, M.W. [Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

    2013-01-15

    This paper presents an overview of a systematic study to develop new thermoluminescence (TL) and optically stimulated luminescence (OSL) materials using solution combustion synthesis (SCS) for applications such as personal OSL dosimetry, 2D dose mapping, and temperature sensing. A discussion on the material requirements for these applications is included. We present X-ray diffraction (XRD) data on single phase materials obtained with SCS, as well as radioluminescence (RL), TL and OSL data of lanthanide-doped materials. The results demonstrate the possibility of producing TL and OSL materials with sensitivity similar to or approaching those of commercial TL and OSL materials used in dosimetry (e.g., LiF:Mg,Ti and Al{sub 2}O{sub 3}:C) using SCS. The results also show that the luminescence properties can be improved by Li co-doping and annealing. The presence of an atypical TL background and anomalous fading are discussed and deserve attention in future investigations. We hope that these preliminary results on the use of SCS for production of TL and OSL materials are helpful to guide future efforts towards the development of new luminescence materials for different applications. - Highlights: Black-Right-Pointing-Pointer TL and OSL material produced with sensitivity similar to commercial materials. Black-Right-Pointing-Pointer Luminescence properties improved by Li co-doping and annealing. Black-Right-Pointing-Pointer The presence of atypical TL background and anomalous fading observed.

  11. Lanthanide Metal-Organic Framework Materials

    Science.gov (United States)

    Hsieh, Ping-Yen; Green, Mark A.; Briber, Robert M.

    2009-03-01

    A series of lanthanide metal-organic framework materials (MOF) with variable organic linkages including benzene-dicarboxylic acid (BDC); 1,3,5-benzene-tricarboxylic acid (BTC); and 1,3,5-tris(4-carboxyphenyl)benzene (BTB) have been synthesized. The low density and high porosity of MOFs make them candidates molecular sieve or hydrogen storage materials. The crystal structures have been determined using a combination of single crystal X-ray diffractometer and synchrotron powder X-ray diffraction work. Holmium with the BDC ligand material (Ho-BDC) crystallizes in a monoclinic C2/c space group, with lattice parameters of a = 17.06 å, b = 10.67 å, c = 10.57 å, b = 96.12^o. The crystal structure of Ho-BTC is in tetragonal P 41 2 2 space group and Ho-BTB is in a triclinic P-1 space group. A comprehensive examination of Ho-MOF with different ligands by x-ray and thermogravimetric analysis shows that there is a stable nanoporous structure for dehydrated Ho-BTC up to 250^oC. The same phenomenon is not observed in the Ho-BDC and Ho-BTB materials. The collapsed structure with BDC and BTB indicates the stability of dehydrated samples is strongly related to the interactions between the metal and the organic linkers.

  12. Structural Effects of Lanthanide Dopants on Alumina

    Science.gov (United States)

    Patel, Ketan; Blair, Victoria; Douglas, Justin; Dai, Qilin; Liu, Yaohua; Ren, Shenqiang; Brennan, Raymond

    2017-01-01

    Lanthanide (Ln3+) doping in alumina has shown great promise for stabilizing and promoting desirable phase formation to achieve optimized physical and chemical properties. However, doping alumina with Ln elements is generally accompanied by formation of new phases (i.e. LnAlO3, Ln2O3), and therefore inclusion of Ln-doping mechanisms for phase stabilization of the alumina lattice is indispensable. In this study, Ln-doping (400 ppm) of the alumina lattice crucially delays the onset of phase transformation and enables phase population control, which is achieved without the formation of new phases. The delay in phase transition (θ → α), and alteration of powder morphology, particle dimensions, and composition ratios between α- and θ-alumina phases are studied using a combination of solid state nuclear magnetic resonance, electron microscopy, digital scanning calorimetry, and high resolution X-ray diffraction with refinement fitting. Loading alumina with a sparse concentration of Ln-dopants suggests that the dopants reside in the vacant octahedral locations within the alumina lattice, where complete conversion into the thermodynamically stable α-domain is shown in dysprosium (Dy)- and lutetium (Lu)-doped alumina. This study opens up the potential to control the structure and phase composition of Ln-doped alumina for emerging applications.

  13. Structural Effects of Lanthanide Dopants on Alumina

    Energy Technology Data Exchange (ETDEWEB)

    Patel, Ketan; Blair, Victoria; Douglas, Justin; Dai, Qilin; Liu, Yaohua; Ren, Shenqiang; Brennan, Raymond

    2017-01-06

    Lanthanide (Ln3+) doping in alumina has shown great promise for stabilizing and promoting desirable phase formation to achieve optimized physical and chemical properties. However, doping alumina with Ln elements is generally accompanied by formation of new phases (i.e. LnAlO3, Ln2O3), and therefore inclusion of Ln-doping mechanisms for phase stabilization of the alumina lattice is indispensable. In this study, Ln-doping (400 ppm) of the alumina lattice crucially delays the onset of phase transformation and enables phase population control, which is achieved without the formation of new phases. The delay in phase transition (θ → α), and alteration of powder morphology, particle dimensions, and composition ratios between α- and θ-alumina phases are studied using a combination of solid state nuclear magnetic resonance, electron microscopy, digital scanning calorimetry, and high resolution X-ray diffraction with refinement fitting. Loading alumina with a sparse concentration of Ln-dopants suggests that the dopants reside in the vacant octahedral locations within the alumina lattice, where complete conversion into the thermodynamically stable α-domain is shown in dysprosium (Dy)- and lutetium (Lu)-doped alumina. This study opens up the potential to control the structure and phase composition of Ln-doped alumina for emerging applications.

  14. Curvature of the Lanthanide Contraction: An Explanation

    Energy Technology Data Exchange (ETDEWEB)

    Raymond, Kenneth; Wellman, Daniel; Sgarlata, Carmelo; Hill, Aru

    2009-12-21

    A number of studies have shown that for isostructural series of the lanthanides (elements La through Lu), a plot of equivalent metal-ligand bond lengths versus atomic number differs significantly from linearity and can be better fit as a quadratic equation. However, for hydrogen type wave functions, it is the inverse of the average distance of the electron from the nucleus (an estimate of size) that varies linearly with effective nuclear charge. This generates an apparent quadratic dependence of radius with atomic number. Plotting the inverse of lanthanide ion radii (the observed distance minus the ligand size) as a function of effective nuclear charge gives very good linear fits for a variety of lanthanide complexes and materials. Parameters obtained from this fit are in excellent agreement with the calculated Slater shielding constant, k.

  15. Synthetic rubbers prepared by lanthanide coordination catalysts

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    China is rich in rare earth resources. Rare earth elements, also named lanthanides, are number 58 to number 81 elements in the elemental periodic table. They have unique electronic structures and may form various coordination compounds. In the early 1960s, researchers at the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences (CIAC) found the catalytic activities of lanthanide compounds in stereospecific polymerization of conjugated dienes, and published the first paper on this topic in 1964. On the basis of this finding, CIAC launched extensive research activities on lanthanide compounds as diene polymerization catalysts, from a series of fundamental research to the efforts of industrializing the rare earth catalyzed cis-1,4-polybutatine rubber and cis-1,4-polyisoprene rubber. This review aims to summarize the progress in this field in the past half century.

  16. Highly improved upconversion luminescence in NaGd(WO₄)₂:Yb³⁺/Tm³⁺ inverse opal photonic crystals.

    Science.gov (United States)

    Wang, Yunfeng; Xu, Wen; Cui, Shaobo; Xu, Sai; Yin, Ze; Song, Hongwei; Zhou, Pingwei; Liu, Xiaoyan; Xu, Lin; Cui, Haining

    2015-01-28

    The upconversion luminescence (UCL) of rare earth (RE) ions doped nanomaterials has attracted extensive interest because of its wide and great potential applications. However, the lower UCL efficiency is still an obstacle for real applications. Photonic modulation is a novel way to improve the efficiency of UCL. In this work, NaGd(WO4)2:Yb(3+)/Tm(3+) inverse opal photonic crystals (IOPCs) were fabricated through the polymethylmethacrylate (PMMA) template and the modification of the IOPC structure on the emission spectra and dynamics of Tm(3+) ions was systemically studied. It is interesting to observe that in the IOPCs, the high-order UCL (1)D2-(3)H6/(3)F4 was relatively enhanced. At the same time, the local thermal effect induced by laser irradiation was suppressed. Furthermore, the overall intensity ratio of visible UCL to near-infrared (NIR) down-conversion luminescence (DCL) was 2.8-8 times improved than that of the grinded reference (REF) and independent of the photonic stop band (PSB). The studies on UCL dynamics indicated that the nonradiative transition rate of Tm(3+) was considerably suppressed. The facts above indicated that in the IOPCs the UCL efficiency of Tm(3+) was largely improved due to the periodic macroporous structure.

  17. Three-Photon Luminescence of Gold Nanorods Excited by 1040 nm Femtosecond Laser for High Contrast Tissue and In Vivo Imaging

    Science.gov (United States)

    Wang, Shaowei; Zhao, Xinyuan; Zhang, Hequn; Cai, Fuhong; Qian, Jun

    2016-01-01

    Gold Nanorods (GNRs) with tunable aspect ratios can strongly absorb and scatter light in the NIR region due to their localized surface plasmon resonance (LSPR) property, and have been demonstrated to exhibit strong plasmon enhanced multiphoton luminescence (MPL) with brightness many times stronger than the conventional organic chromophores. In this study, we synthesized GNRs with longitudinal LSPR peak at 1036 nm to match our home-built light source 1040 nm femtosecond laser, which locates in the “optical window” where the tissue absorbs relatively little light. PEGylated GNRs with great biocompatibility were intravenously injected through the tail vein into mice. Excited by 1040 nm laser, the GNRs exhibit bright three-photon luminescence (3PL) signals while circulating in the blood vessels. The use of GNRs as bright contrast agents for 3PL imaging of mouse ear blood vessels in vivo was demonstrated. And GNRs targeted in tissues can be excited by 1040 nm laser and could be clearly visualized with no autofluorescence background. These results indicated that 3PL of GNRs is very promising for deep in vivo bioimaging and assessing the distribution of GNRs in tissues with high contrast.

  18. Selective phase synthesis of a high luminescence Gd{sub 2}O{sub 3}:Eu nanocrystal phosphor through direct solution combustion

    Energy Technology Data Exchange (ETDEWEB)

    Xia Guodong; Wang Sumei; Zhou Shengming [Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China); Xu Jun, E-mail: xiagd@hotmail.com, E-mail: zhousm@mail.siom.ac.cn [Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201800 (China)

    2010-08-27

    A Gd{sub 2}O{sub 3}:Eu nanocrystal phosphor has been directly synthesized by a mild solution combustion method with a single step approach while avoiding further thermal annealing. The as-combusted Gd{sub 2}O{sub 3}:Eu powders have been characterized by x-ray diffraction, infrared spectroscopy, transmission electron microscopy and photoluminescence spectra. The ratio of citric acid to metal nitrate (C/M) has a critical impact on the phase composition and crystallization of as-combusted Gd{sub 2}O{sub 3}:Eu. An optimal C/M ratio of 0.7 gave highly crystalline powders with a single cubic phase, and a high luminescence intensity comparable with that of a commercial Y{sub 2}O{sub 3}:Eu phosphor, even without further thermal annealing. This direct solution combustion method can be used to prepare a variety of high quality oxide nanocrystals.

  19. Facile preparation of highly luminescent CdTe quantum dots within hyperbranched poly(amidoamine)s and their application in bio-imaging.

    Science.gov (United States)

    Shi, Yunfeng; Liu, Lin; Pang, Huan; Zhou, Hongli; Zhang, Guanqing; Ou, Yangyan; Zhang, Xiaoyin; Du, Jimin; Xiao, Wangchuan

    2014-03-13

    A new strategy for facile preparation of highly luminescent CdTe quantum dots (QDs) within amine-terminated hyperbranched poly(amidoamine)s (HPAMAM) was proposed in this paper. CdTe precursors were first prepared by adding NaHTe to aqueous Cd2+ chelated by 3-mercaptopropionic sodium (MPA-Na), and then HPAMAM was introduced to stabilize the CdTe precursors. After microwave irradiation, highly fluorescent and stable CdTe QDs stabilized by MPA-Na and HPAMAM were obtained. The CdTe QDs showed a high quantum yield (QY) up to 58%. By preparing CdTe QDs within HPAMAM, the biocompatibility properties of HPAMAM and the optical, electrical properties of CdTe QDs can be combined, endowing the CdTe QDs with biocompatibility. The resulting CdTe QDs can be directly used in biomedical fields, and their potential application in bio-imaging was investigated.

  20. Separation and determination of lanthanides, thorium and uranium using a dual gradient in reversed-phase liquid chromatography.

    Science.gov (United States)

    Raut, Narendra M; Jaison, P G; Aggarwal, Suresh K

    2004-10-15

    Separation and determination of lanthanides, Th and U is of great relevance in different fields of science and technology. Reversed-phase high-performance liquid chromatography (RP-HPLC) using alpha-hydroxy isobutyric acid (alpha-HIBA) as an eluent on reversed-phase column modified to cation exchanger has been reported to achieve the separation. However, under those conditions, Th and U are eluted amongst lanthanides, making their quantification difficult due to overlapping with some of the lanthanides peaks. In this work, different chromatographic parameters (concentrations of eluent and ion interaction reagent, pH, etc.) were studied systematically to arrive at optimum chromatographic conditions. Using the dual (concentration and pH) gradient conditions, lanthanides, Th and U could be separated in 11 min by RP-HPLC with sequential elution of Th and U after the elution of all the lanthanides. The separation methodology was tested using SY-3 rock sample for the separation and determination of lanthanides, Th and U. The method allows an accurate determination of these elements in a single run using a single column. Also, the method is fast and cost-effective compared to the reported methods.

  1. Synthesis and characterization of two one-dimensional lanthanide coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Yin Mingcai; Sun Jutang

    2004-11-03

    Two lanthanide coordination polymers [Eu(H{sub 2}sal)(Hsal)(sal){center_dot}H{sub 2}O]{sub n} (1) and {l_brace}[Tb(FUR){sub 3}(H{sub 2}O){sub 2}]{center_dot}DMF{r_brace}{sub n} (2) (H{sub 2}sal, salicylic acid; Hsal{sup -}, o-HOC{sub 6}H{sub 4}CO{sub 2}{sup -}; HFUR, {alpha}-furancarboxylic acid; DMF, N,N-dimethylformamide) were synthesized and characterized by elemental analysis, TG, IR, and luminescence spectra. The crystal structures were determined by X-ray single crystal analysis. Both complexes are one-dimensional polymers. Probably the luminescence quenching of complex 1 is assigned to its special one-dimensional ribbon structure. The vibration energy level caused by the one-dimensional ribbon and located between {sup 5}D{sub 0} and {sup 7}F{sub j} maybe is the main reason. Complex 2 displays intense green luminescence under the excitation of UV light. The emission bands at 486, 541, 584, and 618 nm are attributed to the characteristic {sup 5}D{sub 4}{yields}{sup 7}F{sub j} (j = 6, 5, 4, 3) transitions of Tb(III) ions, respectively.

  2. Multi-modal imaging and cancer therapy using lanthanide oxide nanoparticles: current status and perspectives.

    Science.gov (United States)

    Park, J Y; Chang, Y; Lee, G H

    2015-01-01

    Biomedical imaging is an essential tool for diagnosis and therapy of diseases such as cancers. It is likely true that medicine has developed with biomedical imaging methods. Sensitivity and resolution of biomedical imaging methods can be improved with imaging agents. Furthermore, it will be ideal if imaging agents could be also used as therapeutic agents. Therefore, one dose can be used for both diagnosis and therapy of diseases (i.e., theragnosis). This will simplify medical treatment of diseases, and will be also a benefit to patients. Mixed (Ln(1x)Ln(2y)O3, x + y = 2) or unmixed (Ln2O3) lanthanide (Ln) oxide nanoparticles (Ln = Eu, Gd, Dy, Tb, Ho, Er) are potential multi-modal imaging and cancer therapeutic agents. The lanthanides have a variety of magnetic and optical properties, useful for magnetic resonance imaging (MRI) and fluorescent imaging (FI), respectively. They also highly attenuate X-ray beam, useful for X-ray computed tomography (CT). In addition gadolinium-157 ((157)Gd) has the highest thermal neutron capture cross section among stable radionuclides, useful for gadolinium neutron capture therapy (GdNCT). Therefore, mixed or unmixed lanthanide oxide nanoparticles can be used for multi-modal imaging methods (i.e., MRI-FI, MRI-CT, CT-FI, and MRICT- FI) and cancer therapy (i.e., GdNCT). Since mixed or unmixed lanthanide oxide nanoparticles are single-phase and solid-state, they can be easily synthesized, and are compact and robust, which will be beneficial to biomedical applications. In this review physical properties of the lanthanides, synthesis, characterizations, multi-modal imagings, and cancer therapy of mixed and unmixed lanthanide oxide nanoparticles are discussed.

  3. Optimization of the radio lanthanides separation device; Optimizacion de dispositivo para separacion de radiolantanidos

    Energy Technology Data Exchange (ETDEWEB)

    Vera T, A. L.

    2009-07-01

    At present, cancer is a major cause of mortality in our country, therefore, its prevention, diagnosis and treatment are vital to health systems. The cancer treatment and other diseases, from monoclonal antibodies, peptides, or amino macro aggregates marked with beta particle emitting radionuclides, is a highly promising field. The radioactive lanthanides: Pm, Tb, Ho, and Lu are beta emitters, which possess nuclear and chemical properties, which have shown their feasibility as radioisotopes of radiotherapeutic use. However, these radioisotopes are not available commercially in this connection, the Research Laboratory of Radioactive Materials of the National Institute of Nuclear Research, has developed the methodology of production of these radioisotopes and based on this work is designed, constructed and installed the radio lanthanides separation device for the radioisotopes production routinely. This device is part of the cell, , which has and auxiliary air service, an extraction system and is protected with a 10 cm of lead shielding. The radio lanthanides separation device is manual and easy to handle. The main function of this equipment is the radio lanthanides separation from extractive chromatography through packed columns with a commercial resin (Ln SPS) and coated on the top and bottom by fiberglass. The radio lanthanides separation device comprises a main carrousel where the separation columns and elution containers are mounted. It also has a system of open irradiation vials, carrier samples for columns and glassware. This paper presents a detailed description of the radio lanthanides separation device and its management, which allows the radioisotopes production Pm, Tb, Ho, and Lu from the separation of its parents Nd, Dy, Gd, and Yb respectively. (Author)

  4. Study on Interaction Energy of PAMAM/Lanthanide(Ⅲ) by Molecular Dynamics Method

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    PAMAM/lanthanide(Ⅲ) nanocomposite was studied by molecular simulation method. Molecular simulation enabled study of the lanthanide tetrad effect at atomic level. However, PAMAM dendrimer exhibiting unique properties such as nanometer size and highly functionalized terminal surface provided a novel space for lanthanide(Ⅲ) to show their peculiar tetrad effect. The results showed that total energies of PAMAM/lanthanide(Ⅲ) nanocomposites presented obvious tetrad effect and special double-double effect. Nd, Gd, and Er fell to the lower point and Gd fell to the lowest point in the TE-Ln curve with four groups. In order to explain the tetrad effect, kinetic energy (KE) and potential energy (PE) were analyzed. The KE curve consisted of three W-type parts (La~Pm, Pm~Tb, Tb~Tm, and the latter two W-type part were axial symmetry) and an exception part (Yb~Lu). It also showed that the KE of odd atomic number was higher than the even one's with exception of Yb and Lu. Furthermore, decomposed potential energies gave out the atomic-level subtle difference of lanthanide which present more regulations for Eu(Ⅲ)~Lu(Ⅲ) compared with La(Ⅲ)~Sm(Ⅲ). And also Ho-valley and three platforms (Sm~Eu, Td~Dy, Er~Tm) were discovered that refect the regular change of nanocomposite structures. Additionally, there are distinct correlations between Ebond and EInversion, EAngle and EVDW, ETorsion and ECoul, respectively. Therefore, PAMAM could be used in separation of lanthanide by changing conditions.

  5. Field-induced single-ion magnetic behaviour in a highly luminescent Er{sup 3+} complex

    Energy Technology Data Exchange (ETDEWEB)

    Coutinho, J.T. [Solid State Group, UCQR, IST/CTN, Instituto Superior Técnico, UTL, Estrada Nacional 10, km 139.7, 2695-066 Bobadela LRS (Portugal); Pereira, L.C.J., E-mail: lpereira@ctn.ist.utl.pt [Solid State Group, UCQR, IST/CTN, Instituto Superior Técnico, UTL, Estrada Nacional 10, km 139.7, 2695-066 Bobadela LRS (Portugal); Martín-Ramos, P. [CEMDRX, Physics Department, Universidade de Coimbra, Rua Larga, P-3004-516 Coimbra (Portugal); Higher Polytechnic School of Huesca, University of Zaragoza, Carretera Cuarte, s/n, 22071 Huesca (Spain); Ramos Silva, M. [CEMDRX, Physics Department, Universidade de Coimbra, Rua Larga, P-3004-516 Coimbra (Portugal); Zheng, Y.X.; Liang, X. [State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); Ye, H.Q. [Materials Research Institute and School of Physics and Astronomy Queen Mary University of London, Mile End Road, London E1 4NS (United Kingdom); Peng, Y. [Materials Research Institute and School of Biological and Chemical, Sciences, Queen Mary University of London, Mile End Road, London E1 4NS (United Kingdom); Baker, P.J. [Materials Research Institute and School of Physics and Astronomy Queen Mary University of London, Mile End Road, London E1 4NS (United Kingdom); Wyatt, P.B. [Materials Research Institute and School of Biological and Chemical, Sciences, Queen Mary University of London, Mile End Road, London E1 4NS (United Kingdom); Gillin, W.P. [Materials Research Institute and School of Physics and Astronomy Queen Mary University of London, Mile End Road, London E1 4NS (United Kingdom); College of Physical Science and Technology, Sichuan University, Chengdu 610064 (China)

    2015-06-15

    The magnetic properties of a perfluorinated Er{sup 3+} complex, with record luminescent properties, have been investigated. [Er(F-TPIP){sub 3}] displays thermally activated slow relaxation of the magnetisation under an applied H{sub DC} field of 500 Oe. The effective relaxation barrier E{sub eff} is found to be 26.8 K (18.6 cm{sup −1}). At zero static field, efficient quantum tunnelling of the magnetization occurs. - Highlights: • Under DC field, slow relaxation of magnetisation occurs with a barrier of 27 K. • Efficient quantum tunnelling of magnetization is displayed at zero static field. • The lifetime value of the {sup 4}I{sub 13/2} multiplet is τ = 0.28 ms. • [Er(F-TPIP){sub 3}] complex can be considered a multifunctional material.

  6. Highly luminescent and nontoxic amine-capped nanoparticles from porous silicon: synthesis and their use in biomedical imaging.

    Science.gov (United States)

    Ahire, Jayshree H; Wang, Qi; Coxon, Paul R; Malhotra, Girish; Brydson, Rik; Chen, Rongjun; Chao, Yimin

    2012-06-27

    Stable and brightly luminescent amine-terminated Si nanoparticles (SiNPs) have been synthesized from electrochemically etched porous silicon (PSi). The surface amine termination was confirmed by FTIR, NMR, and XPS studies. The mean diameter of the crystal core of 4.6 nm was measured by transmission electron microscopy (TEM), which is in a good agreement with the size obtained by dynamic light scattering (DLS). The dry, amine-terminated product can be obtained from bulk silicon wafers in less than 4 h. This represents a significant improvement over similar routines using PSi where times of >10 h are common. The emission quantum yield was found to be about 22% and the nanoparticles exhibited an exceptional stability over a wide pH range (4-14). They are resistant to aging over several weeks. The amine-terminated SiNPs showed no significant cytotoxic effects toward HepG2 cells, as assessed with MTT assays.

  7. Fabrication, spectroscopy, and dynamics of highly luminescent core-shell InP@ZnSe quantum dots.

    Science.gov (United States)

    Kim, Mee Rahn; Chung, Jae Hun; Lee, Mihee; Lee, Seonghoon; Jang, Du-Jeon

    2010-10-01

    InP quantum dots of 3 nm in diameter have been prepared using a dehalosilylation reaction and passivated with ZnSe to enhance photoluminescence by 6.8 times. Core-shell InP@ZnSe quantum dots dispersed in n-hexane have then been investigated using time-resolved spectroscopy to understand their photoluminescence dynamics. The observed decay times of 0.1, 7, and 1100 ns have been attributed to the relaxation times of electrons in the conduction band, trap sites, and surface states. The surface-state luminescence of core-shell InP@ZnSe quantum dots having the maximum at 760 nm has been distinguished spectrally and dynamically from their band-edge emission having the maximum at 620 nm or from their trap-site emission having the maximum at 660 nm.

  8. The luminescence properties of rare-earth ions in natural fluorite

    Science.gov (United States)

    Czaja, M.; Bodył-Gajowska, S.; Lisiecki, R.; Meijerink, A.; Mazurak, Z.

    2012-09-01

    For the first time, the luminescence properties of Pr3+, Nd3+ and Tm3+ and Yb3+ ions in fluorite crystal have been obtained by steady-state measurements. In addition, the luminescence spectra of Ce3+, Sm2+, Sm3+, Dy3+, Er3+ and Yb3+ were measured. It was pointed out that λexc. = 415 nm is most suitable for measuring the Ho3+ emission beside the Er3+. The emission of trivalent holmium and erbium ions was measured independently using time-resolved measurements and tentative assignment of luminescence lines to C 3v and C 4v symmetry sites was proposed. Besides for natural fluorite crystal, the transitions between Stark energy levels of lanthanide ions were presented.

  9. Intensity Enhanced Cerenkov Luminescence Imaging Using Terbium-Doped Gd2O2S Microparticles.

    Science.gov (United States)

    Cao, Xin; Chen, Xueli; Kang, Fei; Zhan, Yonghua; Cao, Xu; Wang, Jing; Liang, Jimin; Tian, Jie

    2015-06-10

    Weak intensity and poor penetration depth are two big obstacles toward clinical use of Cerenkov luminescence imaging (CLI). In this proof-of-concept study, we overcame these limitations by using lanthanides-based radioluminescent microparticles (RLMPs), called terbium doped Gd2O2S. The characterization experiment showed that the emission excited by Cerenkov luminescence can be neglected whereas the spectrum experiment demonstrated that the RLMPs can actually be excited by γ-rays. A series of in vitro experiments demonstrated that RLMPs significantly improve the intensity and the penetration capacity of CLI, which has been extended to as deep as 15 mm. In vivo pseudotumor study further prove the huge potential of this enhancement strategy for Cerenkov luminescence imaging in living animal studies.

  10. Luminescence investigations of rare earth doped lead-free borate glasses modified by MO (M = Ca, Sr, Ba)

    Energy Technology Data Exchange (ETDEWEB)

    Janek, Joanna, E-mail: janek.joanna@gmail.com; Sołtys, Marta; Żur, Lidia; Pietrasik, Ewa; Pisarska, Joanna; Pisarski, Wojciech A.

    2016-09-01

    Series of lead-free borate glasses with different oxide modifiers and lanthanide ions were prepared. The effect of oxide modifiers MO (M = Ca, Sr, Ba) on spectroscopic properties of trivalent Ln{sup 3+} (Ln = Eu, Er, Pr) were systematically investigated. Especially, the luminescence spectra of Ln{sup 3+}-doped lead-free borate glasses are presented and discussed in relation to the impact of selective components (CaO, SrO and BaO). Several spectroscopic parameters, such as the fluorescence intensity ratio R/O (Eu{sup 3+}) and measured luminescence lifetimes for the {sup 5}D{sub 0} (Eu{sup 3+}), {sup 4}I{sub 13/2} (Er{sup 3+}) and {sup 1}D{sub 2} (Pr{sup 3+}) excited states of lanthanide ions were analyzed in details. The research proved that spectroscopic properties of trivalent Ln{sup 3+} depend significantly on kind of presence oxide modifiers MO (M = Ca, Sr, Ba) in glass host matrices. - Highlights: • Luminescence of Ln{sup 3+}-doped borate glasses was presented and discussed. • Effect of glass modifiers on spectroscopic properties of rare earths was studied. • Measured luminescence lifetimes of Ln{sup 3+} (Ln = Eu, Er, Pr) were analyzed. • Luminescence intensity ratios R/O (Eu{sup 3+}) were determined.

  11. Centrifugal atomization of lanthanide materials for cryogenic coolers

    Energy Technology Data Exchange (ETDEWEB)

    Osborne, M.G.

    1994-01-04

    Until recently, Pb was the preferred heat exchanger matrix material used in low temperature cryocoolers; however, the heat capacity of Pb drops drastically below {approximately}15K and new matrix materials based on the lanthanide elements have been developed. These materials magnetically order at low temperatures and the entropy change associated with ordering contributes to the materials` heat capacities. The drawback to widespread use of lanthanide intermetallic compounds in cryocoolers has been the difficulty in manufacturing high-quality particulates. The purpose of this project was to develop a technique for producing high-quality powders of lanthanide metals and lanthanide intermetallic compounds for use in cryocooler heat exchangers. A series of atomization experiments was performed using Er{sub 3}Ni, Nd, Nd{sub 3}Ni, and (Er{sub 0.5}Nd{sub 0.5}){sub 3}Ni. Atomization of these materials resulted in particles ranging from mostly spherical to extremely flattened. Analyses of size distributions for the experiments indicate that increased atomization disk speed and superheat result in smaller mean particle diameters and narrower size distributions. Chemical analyses of the atomized powders indicate that the CA/RQB technique produces particulate with much lower interstitial contamination than other techniques. The Er{sub 3}Ni and Nd{sub 3}Ni powders were predominantly of the desired phase and the (Er{sub 0.5}Nd{sub 0.5}){sub 3}Ni powder had one major and possibly three minor phases. The solidification morphology is typically fine dendritic or cellular with finer microstructure spacings near the particle surfaces. The Er{sub 3}Ni powders have higher heat capacities than gas atomized powders reported in literature. The heat capacity of Nd{sub 3}Ni has a peak which does not degrade dramatically with processing. The (Er{sub 0.5}Nd{sub 0.5}){sub 3}Ni material has a higher heat capacity compared to Er{sub 3}Ni, Nd{sub 3}Ni, and Nd at temperatures above 10K.

  12. RI and Target recovery system of Lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Choi, K. H.; Park, U. J.; Jung, S. H.; Kim, J. B.; Moon, J. H.; Nam, S. S.; Jang, K. D. [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2015-10-15

    Separation of adjacent lanthanides is complicated process to obtain pure target nuclide. Several papers have reported that the ionic character change of lanthanides with appropriate chelating agents can isolate the target lanthanides. These specific agents to the metal ion are called as complexing agents including-HIBA, tartaric acid, mandelic acid, lactic acid etc. Radioisotope research division of KAERI has developed separating technique for target lanthanides, total 20mg scale, by using complexing agents and ion-pairing agents in cold state. The reactor-produced radiolanthanides have been pivotal for development of therapeutic radiopharmaceuticals. Some radiolanthanides show excellent theranostic effects in that they have proper Let (Linear Energy Transfer) to induce apoptosis for cancer treatment and gamma ray to use as a tracer for cancer diagnosis. This system was designed for automated separation of the (n,γ) reaction product. Especially, we are focused on getting the carrier free Ho-166 which is the first attempt at KAERI. Even though we have already developed to produce c.a Ho-166(carrier added form), we did not try to develop to produce carrier free Ho-166 since the separating process is difficult as well as production process follows double (n,γ) reaction. After HANARO is re-operated, we are schedule to produce n.c.a Ho by using this recovery system.

  13. Scalar Static Polarizabilities of Lanthanides and Actinides

    CERN Document Server

    Dzuba, V A; Flambaum, V V

    2014-01-01

    We calculate scalar static polarizabilities for lanthanides and actinides, the atoms with open $4f$ or $5f$ subshell. We show that polarizabilities of the low states are approximately the same for all states of given configuration and present a way of calculating them reducing valence space to just two or three valence electrons occupying $6s$ and $5d$ states for lanthanides or $7s$ and $6d$ states for actinides while $4f$ and $5f$ states are considered to be in the core. Configuration interaction technique is used to calculate polarizabilities of lanthanides and actinides for all states of the $4f^n6s^2$ and $4f^{n-1}6s^25d$ configurations of lanthanides and all states of the $5f^{n}7s^2$ and $5f^{n-1}7s^26d$ configurations of actinides. Polarizability of the electron core (including f-orbitals) has been calculated in the RPA approximation.

  14. Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction

    DEFF Research Database (Denmark)

    Escribano, Maria Escudero; Malacrida, Paolo; Hansen, Martin Hangaard

    2016-01-01

    The high platinum loadings required to compensate for the slow kinetics of the oxygen reduction reaction (ORR) impede the widespread uptake of low-temperature fuel cells in automotive vehicles. We have studied the ORR on eight platinum (Pt)–lanthanide and Pt-alkaline earth electrodes, Pt5M, where...

  15. Surface characterization and luminescence properties of AlN doped with RE elements (Sm, Ho, Gd, Tm)

    OpenAIRE

    Balogun, Ismail Ayodele

    2015-01-01

    Rare‐ earth (RE)‐doped III‐nitride broad band‐gap semiconductors have attracted enormous interest as a foundation for optoelectronics devices, which combine the unique luminescence feature of Rare‐earth ions with the electronic properties of the semiconductors. Recent progress toward nitride‐based light emitting diode and light emitting due to electric current devices have been made using crystalline and amorphous AlN and GaN doped with a different lanthanide elements. The Rare‐earth...

  16. Calorimetric approach of lanthanides (3) complexation and extraction by malonamides; Approche calorimetrique de la complexation et de l'extraction des lanthanides (3) par les malonamides

    Energy Technology Data Exchange (ETDEWEB)

    Flandin, J.L

    2001-07-01

    In the field of long lived radionuclides separation, diamides are interesting extractants because of their ability to co-extract trivalent lanthanides and actinides, which is a preliminary and essential step in high level radioactive waste reprocessing. The research carried out contributes to a better understanding of the mechanisms and the aim is the determination of thermodynamics properties ({delta}{sub r}G, {delta}{sub r}H et {delta}{sub r}S) related to the complexation and the extraction of lanthanides(III) by malonamides. The first part of the document deals with the complexation of lanthanides(III) by an hydrosoluble diamide. The experimental results obtained by UV-visible spectrometry, TRLIF, NMR and microcalorimetric titration proved that lanthanides(III)-TEMA interactions in aqueous medium are very weak and that the complexation reaction is endothermic. The TEMA ligand still stays in the second coordination sphere of coordination of the lanthanide ion. The second part of this study focuses on the extraction of neodymium(III) nitrate by a lipophilic diamide which is an exothermic reaction. The influence of the composition of aqueous and organic phases on the thermodynamics properties {delta}{sub r}G et {delta}{sub r}H has been studied by microcalorimetric titration. The most influent parameter is the total concentration in extractant. As a consequence, thermodynamic values are very dependent on the organic phase organisation before and alter extraction. At the same time, this study showed the interest of the calorimetric approach for the analysis of basic reactions like diamide dilution and their organisation as oligomeric aggregates. (author)

  17. High efficiency white luminescence in Tm{sup 3+}/Er{sup 3+}/Yb{sup 3+} tri-doped oxyfluoride glass ceramic microsphere pumped by 976 nm laser

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Jing; Huang, Yantang, E-mail: huangyantang@fzu.edu.cn; Wu, Tianjiao; Huang, Yu; Zhang, Peijin

    2015-01-15

    In this paper, transparent Tm{sup 3+}/Er{sup 3+}/Yb{sup 3+} tri-doped oxyfluoride glass ceramic samples containing LaF{sub 3} nanocrystals were prepared by a melt quenching method, and were subsequently fabricated into transparent microspheres with handles. A new method to study the luminescent properties of Tm{sup 3+}/Er{sup 3+}/Yb{sup 3+} tri-doped oxyfluoride glass ceramic was proposed, which was using the biconical tapered fiber-microsphere coupled structure. The structure has characteristics of low excitation optical power, easy preparation and convenient testing. We obtained strong white light including the blue (471 nm), green (523 nm and 544 nm) and red (651 nm) emission under the excitation of a 976 nm laser diode (LD) and the relationship of the luminous flux of white light versus pump power simultaneously. In addition, the up-conversion (UC) luminescence mechanism of rare earth (RE) ions and the reason of high luminescence efficiency in our experiment were also explained. The white light obtained by UC of 976 nm laser has more advantages than that by down-conversion of blue light. It may be applied in many fields such as background light, lighting, etc. - Highlights: • A new method to study the luminescent properties of glass materials is proposed. • The white light was obtained by up-conversion of 976 nm laser. • The mechanism of up-conversion luminescence was clearly explained. • The advantages of the white luminescence excited by 976 nm were reported.

  18. Luminescence from Tube-Arrest Bubbles in Pure Glycerin

    Institute of Scientific and Technical Information of China (English)

    陈岐岱; 王龙

    2004-01-01

    Single transient cavitation bubble with luminescence has been generated in pure glycerin by using the ‘tube arrest'method. The analyses of high-speed photograph and light emission data suggest that the light emission would be a single bubble sonoluminescence. The luminescence pulse width is observed to wry from sub-nanosecond to about 30 ns. The width and intensity of luminescence pulses increases with the height of the liquid column height and decreases with the liquid temperature.

  19. Synthesis and characterization of Eu(3+), Ti(4+) @ ZnO organosols and nanocrystalline c-ZnTiO3 thin films aiming at high transparency and luminescence.

    Science.gov (United States)

    Aubert, Tangi; Grasset, Fabien; Potel, Michel; Nazabal, Virginie; Cardinal, Thierry; Pechev, Stanislav; Saito, Noriko; Ohashi, Naoki; Haneda, Hajime

    2010-08-01

    By exploiting colloidal properties, such as transparency, rheology and versatile chemistry, we propose to synthesize new photonic nanomaterials based on colloidal solutions and thin films. This contribution highlights our efforts to elaborate and to characterize nanostructures based on the ZnO-TiO2 system. Using a recently developed sol-gel route to synthesize new Ti(4+)@ZnO organosols, we were able to prepare, at relatively low temperature (400 °C) and short annealing time (15 min), highly transparent, luminescent, nanocrystalline Eu(3+) doped c-ZnTiO3 thin films. The organosols and thin films were characterized with UV-visible-near infrared absorption, ellipsometry, photoluminescence spectroscopy, dynamic light scattering, x-ray diffraction and scanning electron microscopy.

  20. Synthesis and characterization of Eu3+,Ti4+@ZnO organosols and nanocrystalline c-ZnTiO3 thin films aiming at high transparency and luminescence

    Science.gov (United States)

    Aubert, Tangi; Grasset, Fabien; Potel, Michel; Nazabal, Virginie; Cardinal, Thierry; Pechev, Stanislav; Saito, Noriko; Ohashi, Naoki; Haneda, Hajime

    2010-08-01

    By exploiting colloidal properties, such as transparency, rheology and versatile chemistry, we propose to synthesize new photonic nanomaterials based on colloidal solutions and thin films. This contribution highlights our efforts to elaborate and to characterize nanostructures based on the ZnO-TiO2 system. Using a recently developed sol-gel route to synthesize new Ti4+@ZnO organosols, we were able to prepare, at relatively low temperature (400 °C) and short annealing time (15 min), highly transparent, luminescent, nanocrystalline Eu3+ doped c-ZnTiO3 thin films. The organosols and thin films were characterized with UV-visible-near infrared absorption, ellipsometry, photoluminescence spectroscopy, dynamic light scattering, x-ray diffraction and scanning electron microscopy.

  1. Synthesis and characterization of Eu3+,Ti4+@ZnO organosols and nanocrystalline c-ZnTiO3 thin films aiming at high transparency and luminescence

    Directory of Open Access Journals (Sweden)

    Tangi Aubert, Fabien Grasset, Michel Potel, Virginie Nazabal, Thierry Cardinal, Stanislav Pechev, Noriko Saito, Naoki Ohashi and Hajime Haneda

    2010-01-01

    Full Text Available By exploiting colloidal properties, such as transparency, rheology and versatile chemistry, we propose to synthesize new photonic nanomaterials based on colloidal solutions and thin films. This contribution highlights our efforts to elaborate and to characterize nanostructures based on the ZnO–TiO2 system. Using a recently developed sol–gel route to synthesize new Ti4+@ZnO organosols, we were able to prepare, at relatively low temperature (400 °C and short annealing time (15 min, highly transparent, luminescent, nanocrystalline Eu3+ doped c-ZnTiO3 thin films. The organosols and thin films were characterized with UV-visible-near infrared absorption, ellipsometry, photoluminescence spectroscopy, dynamic light scattering, x-ray diffraction and scanning electron microscopy.

  2. Design and synthesis of highly luminescent near-infrared-emitting water-soluble CdTe/CdSe/ZnS core/shell/shell quantum dots.

    Science.gov (United States)

    Zhang, Wenjin; Chen, Guanjiao; Wang, Jian; Ye, Bang-Ce; Zhong, Xinhua

    2009-10-19

    Applications of water-dispersible near-infrared (NIR)-emitting quantum dots (QDs) have been hampered by their instability and low photoluminescence (PL) efficiencies. In this paper, water-soluble highly luminescent NIR-emitting QDs were developed through constructing CdTe/CdSe/ZnS core/shell/shell nanostructure. The CdTe/CdSe type-II structure yields the QDs with NIR emission. By varying the size of CdTe cores and the thickness of the CdSe shell, the emission wavelength of the obtained nanostructure can span from 540 to 825 nm. In addition, the passivation of the ZnS shell with a substantially wide bandgap confines the excitons within the CdTe/CdSe interface and isolates them from the solution environment and consequently improves the stability of the nanostructure, especially in aqueous media. An effective shell-coating route was developed for the preparation of CdTe/CdSe core/shell nanostructures by selecting capping reagents with a strong coordinating capacity and adopting a low temperature for shell deposition. An additional ZnS shell was deposited around the outer layer of CdTe/CdSe QDs to form the core/shell/shell nanostructure through the decomposition of single molecular precursor zinc diethyldithiocarbamate in the crude CdTe/CdSe reaction solution. The water solubilization of the initially oil-soluble CdTe/CdSe/ZnS QDs was achieved through ligand replacement by 3-mercaptopropionic acid. The as-prepared water-soluble CdTe/CdSe/ZnS QDs possess PL quantum yields as high as 84% in aqueous media, which is one of the best results for the luminescent semiconductor nanocrystals.

  3. Recent progress in biomedical applications of persistent luminescence nanoparticles.

    Science.gov (United States)

    Wang, Jie; Ma, Qinqin; Wang, Yingqian; Shen, Haijing; Yuan, Quan

    2017-05-18

    Persistent luminescence nanoparticles (PLNPs) are an emerging group of promising luminescent materials that can remain luminescent after the excitation ceases. In the past decade, PLNPs with intriguing optical properties have been developed and their applications in biomedicine have been widely studied. Due to the ultra-long decay time of persistent luminescence, autofluorescence interference in biosensing and bioimaging can be efficiently eliminated. Moreover, PLNPs can remain luminescent for hours, making them valuable in bio-tracing. Also, persistent luminescence imaging can guide cancer therapy with a high signal-to-noise ratio (SNR) and superior sensitivity. Briefly, PLNPs are demonstrated to be a newly-emerging class of functional materials with unprecedented advantages in biomedicine. In this review, we summarized recent advances in the preparation of PLNPs and the applications of PLNPs in biosensing, bioimaging and cancer therapy.

  4. Phosphate modulated luminescence in lanthanum vanadate nanorods- Catechin, polyphenolic ligand

    Science.gov (United States)

    Tamilmani, Vairapperumal; Nair, Balachandran Unni; Sreeram, Kalarical Janardhanan

    2017-08-01

    Rare earth orthovanadates and phosphates offer a very high opportunity for fabrication of nanoscale devices that exploit their luminescence properties. Optimization of luminescence by way of modulation of size, shape, structure, and morphology has been an area of study for several researchers. There has been a debate as to whether doped orthophosphate or orthovanadate is better luminescent material as both are chemically similar. It has been reported earlier that catechin hydrate can play the role of a structure director and thus influence the luminescence properties of orthovanadates. In this work, a catechin modulated the synthesis of Eu-doped lanthanum orthophosphate by phosphate substitution into vanadate host lattice is reported. A mechanistic understanding of the luminescence changes in LaMO4 has been proposed. During the substitution of V with P, catechin modulates the structure between 1D nanorods and nanowires. The host crystal structure, shape, and size influence the luminescence properties in doped LaMO4.

  5. Luminescence techniques: Instrumentation and methods

    DEFF Research Database (Denmark)

    Bøtter-Jensen, L.

    1997-01-01

    This paper describes techniques, instruments and methods used in luminescence dating and environmental dosimetry in many laboratories around the world. These techniques are based on two phenomena - thermally stimulated luminescence and optically stimulated luminescence. The most commonly used...... luminescence stimulation and detection techniques are reviewed and information is given on recent developments in instrument design and on the stale of the art in luminescence measurements and analysis. (C) 1998 Elsevier Science Ltd. All rights reserved....

  6. Synthesis and luminescence property of Li{sub 2}BaP{sub 2}O{sub 7}:Ln{sup 3+} (Ln=Eu, Sm) phosphors

    Energy Technology Data Exchange (ETDEWEB)

    Wani, J.A. [Department of Physics, R.T.M. Nagpur University, Nagpur 440033 (India); Dhoble, N.S. [Department of Chemistry, Sevadal Mahila Mahavidhyalaya, Nagpur 440009 (India); Kokode, N.S. [BCUD Gondwana University, Gadchiroli (India); Deva Prasad Raju, B. [Department of Future studies, Sri Venkateswara University, Tirupati 517502 (India); Dhoble, S.J., E-mail: sjdhoble@rediffmail.com [Department of Physics, R.T.M. Nagpur University, Nagpur 440033 (India)

    2014-03-15

    Phosphate compounds as host materials are always a good choice for lanthanides to exhibit luminescence. The novel phosphors of Li{sub 2}BaP{sub 2}O{sub 7} activated with the trivalent Eu{sup 3+} and Sm{sup 3+} ions were synthesized by high temperature solid state reaction. In characterization, crystallization, morphology and luminescent properties of lithium barium diphosphate were investigated. The excitation and emission spectra were recorded to study the luminescence properties. The as prepared powders of Eu{sup 3+} and Sm{sup 3+} ions doped Li{sub 2}BaP{sub 2}O{sub 7} emit reddish orange light, corresponding to {sup 5}D{sub 0}→{sup 7}F{sub 1}(595 nm) and {sup 4}G{sub 5/2}→{sup 6}H{sub 7/2}(599 nm) transitions, respectively. The study is novel as no such luminescence data are available for this compound. -- Highlights: • Luminescence characterization of Li{sub 2}BaP{sub 2}O{sub 7}:Sm{sup 3+}, Eu{sup 3+} prepared phosphors are first time reported in this paper. • Sm{sup 3+} ions luminescence quenches just after 0.5 mol% in Li{sub 2}BaP{sub 2}O{sub 7}:Sm{sup 3+} phosphor. • Excitation wavelengths are quite far away from mercury, hence Li{sub 2}BaP{sub 2}O{sub 7}:Sm{sup 3+}, Eu{sup 3+} is eco-friendly materials for lighting. • {sup 5}D{sub 0}→{sup 7}F{sub 1} and {sup 4}G{sub 5/2}→{sup 6}H{sub 7/2} transitions are dominant in Li{sub 2}BaP{sub 2}O{sub 7}:Sm{sup 3+}, Eu{sup 3+} indicates local symmetry.

  7. 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)

  8. Syntheses, structures and photoluminescence of lanthanide-organic frameworks assembled from multifunctional N,O-donor ligand

    Energy Technology Data Exchange (ETDEWEB)

    Che, Guang-Bo, E-mail: guangboche@jlnu.edu.cn [Key Laboratory of Preparation and Applications of Environmental Friendly Materials, Jilin Normal University, Chinese Ministry of Education, Siping 136000 (China); Liu, Shu-Yu [Key Laboratory of Preparation and Applications of Environmental Friendly Materials, Jilin Normal University, Chinese Ministry of Education, Siping 136000 (China); Zhang, Qing [Institute of Functional Nano and Soft Materials (FUNSOM), Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215123 (China); Liu, Chun-Bo, E-mail: liuchunbo431@gmail.com [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); Zhang, Xing-Jing [Key Laboratory of Preparation and Applications of Environmental Friendly Materials, Jilin Normal University, Chinese Ministry of Education, Siping 136000 (China)

    2015-05-15

    Four new lanthanide complexes [Ln(O–NCP){sub 2}(NO{sub 3})]{sub n} based on multifunctional N,O-donor ligand 2-(2-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline (O–HNCP) and Ln(NO{sub 3}){sub 3}·6H{sub 2}O (Ln=Nd(1), La(2), Sm(3), Eu(4)) have been achieved under hydrothermal conditions and characterized by elemental analyses, infrared spectra and single crystal X-ray diffraction. Structural analyses revealed that all of these four complexes possess similar two-dimensional layer structures. In addition, thermal stability and luminescent properties of these complexes were also investigated. - Graphical abstract: A series of lanthanide(III) coordination polymers with intriguing structures based on 2-(2-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline ligand have been hydrothermally synthesized. The thermal stabilities and photoluminescence properties of these complexes have been investigated. - Highlights: • Four lanthanide(III) complexes have been hydrothermally synthesized. • The N,O-donor O–HNCP was used as the ligand. • TGA and PL properties of complexes 1–4 have been investigated.

  9. Synthesis and Thermal Behaviour of Lanthanide Complexes of 4′[(Cholesteryloxy)Carbonyl]—Benzo—15—Crown—5

    Institute of Scientific and Technical Information of China (English)

    KoenBinnemans; BilgiCuendogan

    2002-01-01