Materials Science › Materials Chemistry

Lanthanide and Transition Metal Complexes

Works Count: 66597

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This cluster of papers focuses on the use of lanthanide luminescence in biomedical applications, particularly in the development of MRI contrast agents, bioimaging probes, and chemical exchange saturation transfer techniques. It also explores the association between gadolinium deposition and nephrogenic systemic fibrosis. The research covers a wide range of topics including the design of luminescent hybrid materials, europium complexes, and molecular imaging.

Keywords

Lanthanide Luminescence; MRI Contrast Agents; Gadolinium Deposition; Bioimaging Probes; Chemical Exchange Saturation Transfer; Nephrogenic Systemic Fibrosis; Luminescent Hybrid Materials; Europium Complexes; Molecular Imaging; Lanthanide Coordination Complexes

The Chemistry of Contrast Agents in Medical Magnetic Resonance Imaging

2013-02-18

Éva Tóth , André Merbach

Contributors. Preface. Physical Principles of Medical Imaging by Nuclear Magnetic Resonance (S. Mansson and A. Bjornerud). Relaxivity of Gadolinium (III) Complexes: Theory and Mechanism (E. Toth, et al.). Synthesis of … Contributors. Preface. Physical Principles of Medical Imaging by Nuclear Magnetic Resonance (S. Mansson and A. Bjornerud). Relaxivity of Gadolinium (III) Complexes: Theory and Mechanism (E. Toth, et al.). Synthesis of MRI Contrast Agents I: Acyclic Ligands. (P. Anelli and L. Lattuada). Synthesis of MRI Contrast Agents II: Macrocyclic Ligands. (V. Jacques and J. Desreux). Protein--Bound Metal Chelates (S. Aime, et al.). Stability and Toxicity of Contrast Agents (E. Brucher and A. Sherry). Computational Studies Related to Gd(III)--Based Contrast Agents (D. Sulzle, et al.). Structure and Dynamics of Gadolinium--Based Contrast Agents (J. Peters, et al). Multi--Frequency and High--Frequency EPR Methods in Contrast Agent Research: Examples from GdA+ Chelates (R. Clarkson, et al). Particulate Magnetic Contrast Agents (R. Muller, et al). Photophysical Aspects of Lanthanide(III) Complexes (J. Bruce, et al).

Europium as a label in time-resolved immunofluorometric assays

1984-03-01

Ilkka Hemmilä , S. Dakubu , Veli-Matti Mukkala +2 more

Lanthanide-Containing Molecular and Supramolecular Polymetallic Functional Assemblies

2002-05-15

Jean‐Claude G. Bünzli , Claude Piguet

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTLanthanide-Containing Molecular and Supramolecular Polymetallic Functional AssembliesJean-Claude G. Bünzli and Claude PiguetView Author Information Institute of Molecular and Biological Chemistry, Swiss Federal Institute of Technology, BCH 1402, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTLanthanide-Containing Molecular and Supramolecular Polymetallic Functional AssembliesJean-Claude G. Bünzli and Claude PiguetView Author Information Institute of Molecular and Biological Chemistry, Swiss Federal Institute of Technology, BCH 1402, CH-1015 Lausanne, and the Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 quai Ernest Ansermet, CH-1211 Geneva 4, Switzerland Cite this: Chem. Rev. 2002, 102, 6, 1897–1928Publication Date (Web):May 15, 2002Publication History Received21 January 2002Published online15 May 2002Published inissue 1 June 2002https://pubs.acs.org/doi/10.1021/cr010299jhttps://doi.org/10.1021/cr010299jresearch-articleACS PublicationsCopyright © 2002 American Chemical SocietyRequest reuse permissionsArticle Views5970Altmetric-Citations916LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Ions,Lanthanides,Ligands,Luminescence,Metals Get e-Alerts

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Non-radiative deactivation of the excited states of europium, terbium and ytterbium complexes by proximate energy-matched OH, NH and CH oscillators: an improved luminescence method for establishing solution hydration states

1999-01-01

Andrew Beeby , Ian M. Clarkson , Rachel S. Dickins +6 more

The radiative rate constants for depopulation of the excited states of closely-related series of anionic, neutral and cationic europium, terbium and ytterbium complexes have been measured in H2O and D2O. … The radiative rate constants for depopulation of the excited states of closely-related series of anionic, neutral and cationic europium, terbium and ytterbium complexes have been measured in H2O and D2O. With the aid of selective ligand deuteriation, the relative contributions of OH, NH (both amide and amine) and CH oscillators have been measured and critically assessed. Quenching of the Eu 5D0 excited state by amine NH oscillators is more than twice as efficient as OH quenching. The importance of the distance between the excited Ln ion and the XH oscillator is described with recourse to published crystallographic information. The general equation, q = A′(ΔkH2O–kD2O)corr is presented and revised values of A′ for Eu (1.2 ms), Tb (5 ms) and Yb (1 µs) given, which allow for the quenching contribution of closely diffusing OH oscillators. The relevance of such studies to the hydration state of certain gadolinium complexes is described and clear evidence provided for a break in hydration at gadolinium.

Lanthanide ion luminescence probes of the structure of biological macromolecules

1981-12-01

William DeW. Horrocks , Daniel R. Sudnick

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTLanthanide ion luminescence probes of the structure of biological macromoleculesWilliam D. Horrocks, Jr. and Daniel R. SudnickCite this: Acc. Chem. Res. 1981, 14, 12, 384–392Publication Date (Print):December … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTLanthanide ion luminescence probes of the structure of biological macromoleculesWilliam D. Horrocks, Jr. and Daniel R. SudnickCite this: Acc. Chem. Res. 1981, 14, 12, 384–392Publication Date (Print):December 1, 1981Publication History Published online1 May 2002Published inissue 1 December 1981https://doi.org/10.1021/ar00072a004RIGHTS & PERMISSIONSArticle Views2237Altmetric-Citations827LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alertsclose Get e-Alerts

The emission spectrum and the radiative lifetime of Eu3+ in luminescent lanthanide complexes

2002-03-22

Martinus H. V. Werts , Ronald T. F. Jukes , Jan W. Verhoeven

Although luminescent complexes of lanthanide ions and organic ligands have been studied intensively, relatively little attention has been paid to the natural (or 'radiative') lifetime of the lanthanide centered luminescent … Although luminescent complexes of lanthanide ions and organic ligands have been studied intensively, relatively little attention has been paid to the natural (or 'radiative') lifetime of the lanthanide centered luminescent state in these systems. Here, the applicability of the well-known Judd–Ofelt theory to the emissive properties of Eu3+ complexes is investigated. Moreover, it is demonstrated experimentally that the radiative lifetime of the 5D0 excited state of Eu3+ can be calculated directly from its corrected emission spectrum, without using Judd–Ofelt theory. We also discuss briefly the possibility of finding the natural lifetimes of lanthanide ions other than Eu3+.

Intramolecular Energy Transfer The Fluorescence of Complexes of Europium

1942-04-01

S. I. Weissman

The characteristic line fluorescence of trivalent europium is excited in certain organoeuropium compounds by irradiation with light absorbed only by the organic part of the compound. The efficiency of excitation … The characteristic line fluorescence of trivalent europium is excited in certain organoeuropium compounds by irradiation with light absorbed only by the organic part of the compound. The efficiency of excitation varies greatly with the nature of the compound, temperature, and solvent. Under optimum conditions, i.e., solution of a covalent compound at liquid-air temperature, almost unit efficiency has been obtained. The decay time of the fluorescence is independent of quenching; quenching prevents excitation of the europium ion. There seems to be a steady gradation of efficiency of transfer from covalent to ionic compounds.

Design of luminescent lanthanide complexes: From molecules to highly efficient photo-emitting materials

2009-08-11

Lidia Armelao , Silvio Quici , Francesco Barigelletti +4 more

Synthesis and Fluorescence of Some Trivalent Lanthanide Complexes

1964-12-01

L. R. Melby , Norman J. Rose , E. Abramson +1 more

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and Fluorescence of Some Trivalent Lanthanide ComplexesL. R. Melby, N. J. Rose, E. Abramson, and J. C. CarisCite this: J. Am. Chem. Soc. 1964, 86, 23, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and Fluorescence of Some Trivalent Lanthanide ComplexesL. R. Melby, N. J. Rose, E. Abramson, and J. C. CarisCite this: J. Am. Chem. Soc. 1964, 86, 23, 5117–5125Publication Date (Print):December 1, 1964Publication History Published online1 May 2002Published inissue 1 December 1964https://pubs.acs.org/doi/10.1021/ja01077a015https://doi.org/10.1021/ja01077a015research-articleACS PublicationsRequest reuse permissionsArticle Views6857Altmetric-Citations742LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Chemical exchange saturation transfer (CEST): What is in a name and what isn't?

2011-02-17

Peter C.M. van Zijl , Nirbhay N. Yadav

Abstract Chemical exchange saturation transfer (CEST) imaging is a relatively new magnetic resonance imaging contrast approach in which exogenous or endogenous compounds containing either exchangeable protons or exchangeable molecules are … Abstract Chemical exchange saturation transfer (CEST) imaging is a relatively new magnetic resonance imaging contrast approach in which exogenous or endogenous compounds containing either exchangeable protons or exchangeable molecules are selectively saturated and after transfer of this saturation, detected indirectly through the water signal with enhanced sensitivity. The focus of this review is on basic magnetic resonance principles underlying CEST and similarities to and differences with conventional magnetization transfer contrast. In CEST magnetic resonance imaging, transfer of magnetization is studied in mobile compounds instead of semisolids. Similar to magnetization transfer contrast, CEST has contributions of both chemical exchange and dipolar cross‐relaxation, but the latter can often be neglected if exchange is fast. Contrary to magnetization transfer contrast, CEST imaging requires sufficiently slow exchange on the magnetic resonance time scale to allow selective irradiation of the protons of interest. As a consequence, magnetic labeling is not limited to radio‐frequency saturation but can be expanded with slower frequency‐selective approaches such as inversion, gradient dephasing and frequency labeling. The basic theory, design criteria, and experimental issues for exchange transfer imaging are discussed. A new classification for CEST agents based on exchange type is proposed. The potential of this young field is discussed, especially with respect to in vivo application and translation to humans. Magn Reson Med, 2011. © 2011 Wiley‐Liss, Inc.

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From Antenna to Assay: Lessons Learned in Lanthanide Luminescence

2009-03-26

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

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 … 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 ∼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 polarized luminescence (CPL) activity. To efficiently sensitize Eu(III) emission, we have used the 1-hydroxypyridin-2-one (1,2-HOPO) chelate to create remarkable ligands that combine excellent photophysical properties and exceptional aqueous stabilities. A more complete understanding of this chromophore has been achieved by combining low-temperature phosphorescence measurements with the same TD-DFT approach used with the IAM system. Eu(III) complexes with strong CPL activity have also been obtained with chiral 1,2-HOPO ligands. We have also undertaken kinetic analysis of radiative and nonradiative decay pathways for a series of Eu(III) complexes; the importance of the metal ion symmetry on the ensuing photophysical properties is clear. Lastly, we describe a Tb(III)-IAM compound—now carried through to commercial availability—that offers improved performance in the common HTRF platform and has the potential to vastly improve sensitivity.

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Lanthanide luminescence for functional materials and bio-sciences

2009-09-11

Svetlana V. Eliseeva , Jean‐Claude G. Bünzli

Recent startling interest for lanthanide luminescence is stimulated by the continuously expanding need for luminescent materials meeting the stringent requirements of telecommunication, lighting, electroluminescent devices, (bio-)analytical sensors and bio-imaging set-ups. … Recent startling interest for lanthanide luminescence is stimulated by the continuously expanding need for luminescent materials meeting the stringent requirements of telecommunication, lighting, electroluminescent devices, (bio-)analytical sensors and bio-imaging set-ups. This critical review describes the latest developments in (i) the sensitization of near-infrared luminescence, (ii) "soft" luminescent materials (liquid crystals, ionic liquids, ionogels), (iii) electroluminescent materials for organic light emitting diodes, with emphasis on white light generation, and (iv) applications in luminescent bio-sensing and bio-imaging based on time-resolved detection and multiphoton excitation (500 references).

Spectroscopic properties and design of highly luminescent lanthanide coordination complexes

2000-01-01

G.F. de Sá , Oscar L. Malta , Celso de Mello Donegá +4 more

Gadolinium(III) Chelates as MRI Contrast Agents: Structure, Dynamics, and Applications

1999-08-20

Peter Caravan , Jeffrey J. Ellison , Thomas J. McMurry +1 more

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTGadolinium(III) Chelates as MRI Contrast Agents: Structure, Dynamics, and ApplicationsPeter Caravan, Jeffrey J. Ellison, Thomas J. McMurry, and Randall B. LaufferView Author Information EPIX Medical, Inc., 71 … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTGadolinium(III) Chelates as MRI Contrast Agents: Structure, Dynamics, and ApplicationsPeter Caravan, Jeffrey J. Ellison, Thomas J. McMurry, and Randall B. LaufferView Author Information EPIX Medical, Inc., 71 Rogers Street, Cambridge, Massachusetts 02142 Cite this: Chem. Rev. 1999, 99, 9, 2293–2352Publication Date (Web):August 20, 1999Publication History Received22 February 1999Revised24 June 1999Published online20 August 1999Published inissue 8 September 1999https://pubs.acs.org/doi/10.1021/cr980440xhttps://doi.org/10.1021/cr980440xresearch-articleACS PublicationsCopyright © 1999 American Chemical SocietyRequest reuse permissionsArticle Views27447Altmetric-Citations3831LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Coordination compounds,Ions,Ligands,Molecular structure,Molecules Get e-Alerts

Luminescent lanthanide complexes as photochemical supramolecular devices

1993-02-01

N. Sabbatini , Massimo Guardigli , Jean‐Maríe Lehn

Graphical Evaluation of Blood-to-Brain Transfer Constants from Multiple-Time Uptake Data. Generalizations

1985-12-01

Clifford S. Patlak , Ronald G. Blasberg

The method of graphical analysis for the evaluation of sequential data (e.g., tissue and blood concentrations over time) in which the test substance is irreversibly trapped in the system has … The method of graphical analysis for the evaluation of sequential data (e.g., tissue and blood concentrations over time) in which the test substance is irreversibly trapped in the system has been expanded. A simpler derivation of the original analysis is presented. General equations are derived that can be used to analyze tissue uptake data when the blood-plasma concentration of the test substance cannot be easily measured. In addition, general equations are derived for situations when trapping of the test substance is incomplete and for a combination of these two conditions. These derivations are independent of the actual configuration of the compartmental system being analyzed and show what information can be obtained for the period when the reversible compartments are in effective steady state with the blood. This approach is also shown to result in equations with at least one less nonlinear term than those derived from direct compartmental analysis. Specific applications of these equations are illustrated for a compartmental system with one reversible region (with or without reversible binding) and one irreversible region.

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Luminescent polynuclear d10 metal complexes

1999-01-01

Vivian Wing‐Wah Yam , Kenneth Kam‐Wing Lo

A number of polynuclear d10 transition metal complexes have been found to exhibit interesting luminescence properties. The photoluminescence properties of polynuclear d10 metal complexes are highly diversified. In the presence … A number of polynuclear d10 transition metal complexes have been found to exhibit interesting luminescence properties. The photoluminescence properties of polynuclear d10 metal complexes are highly diversified. In the presence of a wide range of bridging and ancillary ligands, the excited states of such complexes have been suggested to range from metal-to-ligand charge-transfer, ligand-to-metal charge-transfer, metal-centred to ligand-centred in nature. Recent work on the photophysical and photochemical properties, as well as the applications of this class of luminescent polynuclear d10 metal complexes will be described in this review article.

Nephrogenic Systemic Fibrosis: Risk Factors and Incidence Estimation

2007-02-03

Elizabeth A. Sadowski , Lindsey Bennett , Micah R. Chan +4 more

To retrospectively review data in 13 patients with biopsy-confirmed nephrogenic systemic fibrosis (NSF), assess the associated risk factors, and report the incidence of NSF at the authors' institution.This HIPAA-compliant study … To retrospectively review data in 13 patients with biopsy-confirmed nephrogenic systemic fibrosis (NSF), assess the associated risk factors, and report the incidence of NSF at the authors' institution.This HIPAA-compliant study had institutional review board approval; informed consent was waived. Statistical analysis was performed for all available clinical and laboratory data in patients with biopsy-confirmed NSF. The data from the patients with NSF were compared with data from a control population of patients with renal insufficiency but who did not develop NSF.There were eight male and five female patients, aged 17-69 years, with a diagnosis of NSF. Within 6 months of diagnosis, all 13 patients had been exposed to gadodiamide and one had been exposed to gadobenate dimeglumine in addition to gadodiamide. At the time of contrast material-enhanced magnetic resonance (MR) imaging, all 13 patients had renal insufficiency (estimated glomerular filtration rate [eGFR] < 60 mL/min/1.73 m(2)) and were hospitalized for a proinflammatory event (major surgery, infection, or vascular event). The group with NSF had significantly decreased eGFR (P = .01), more proinflammatory events (P < .001), and more contrast-enhanced MR examinations per patient (P = .002) than did the control group.A combination of factors, including altered kidney function, inflammatory burden, and exposure to gadolinium-based contrast agents may all play a role in development of NSF. Alternative imaging should be considered in patients with these factors. If use of a gadolinium-based agent is clinically indicated, the referring physician and patient should be informed of the potential risk of developing NSF.

Intensities of Crystal Spectra of Rare-Earth Ions

1962-08-01

G. S. Ofelt

Magnetic and electric dipole transitions between levels of the 4fx configuration perturbed by a static crystalline field are treated. The expression obtained for the pure-electronic electric-dipole transition probability involves matrix … Magnetic and electric dipole transitions between levels of the 4fx configuration perturbed by a static crystalline field are treated. The expression obtained for the pure-electronic electric-dipole transition probability involves matrix elements of an even-order unit tensor between the two 4fx states involved in the transition. The contributions to the transition probability from interactions, via the crystalline field, with the nd94fx−1, 4fx−1nd, 4fx−1ng configurations are shown to add linearly, in such a manner as to multiply each odd k crystal-field parameter Akq by a constant. If ``J mixing'' in the 4fx configuration is neglected ΔJ between the upper and lower 4fx levels is restricted to six units or less. If ``L mixing'' is neglected then ΔL is also restricted to six units or less. Application is made to the fluorescence spectra of PrCl3 and EuCl3. Many of the missing and weak transitions are explained.

Phosphorescent heavy-metal complexes for bioimaging

2011-01-01

Qiang Zhao , Chunhui Huang , Fuyou Li

The application of phosphorescent heavy-metal complexes with d6, d8 and d10 electron configurations for bioimaging is a new and promising research field and has been attracting increasing interest. In this … The application of phosphorescent heavy-metal complexes with d6, d8 and d10 electron configurations for bioimaging is a new and promising research field and has been attracting increasing interest. In this critical review, we systematically evaluate the advantages of phosphorescent heavy-metal complexes as bioimaging probes, including their photophysical properties, cytotoxicity and cellular uptake mechanisms. The progress of research into the use of phosphorescent heavy-metal complexes for staining different compartments of cells, monitoring intracellular functional species, providing targeted bioimaging, two-photon bioimaging, small-animal bioimaging, multimodal bioimaging and time-resolved bioimaging is summarized. In addition, several possible future directions in this field are also discussed (133 references).

Characteristics of gadolinium-DTPA complex: a potential NMR contrast agent

1984-03-01

HJ Weinmann , R C Brasch , W. R. Press +1 more

Chelation of the rare-earth element gadolinium (Gd) with diethylenetriaminepentaacetic acid (DTPA) results in a strongly paramagnetic, stable complex that is well tolerated in animals. The strongly paramagnetic gadolinium complex reduces … Chelation of the rare-earth element gadolinium (Gd) with diethylenetriaminepentaacetic acid (DTPA) results in a strongly paramagnetic, stable complex that is well tolerated in animals. The strongly paramagnetic gadolinium complex reduces hydrogen-proton relaxation times even in low concentrations (less than 0.01 mmol/L). The pharmacokinetic behavior of intravenously delivered Gd-DTPA is similar to the well known iodinated contrast agents used in urography and angiography; excretion is predominantly through the kidneys with greater than 90% recovery in 24 hr. The intravenous LD50 of the meglumine salt of Gd-DTPA is 10 mmol/kg for the rat; in vivo there is no evidence of dissociation of the gadolinium ion from the DTPA ligand. The combination of strong proton relaxation, in-vivo stability, rapid urinary excretion, and high tolerance favors the further development and the potential clinical application of gadolinium-DTPA as a contrast enhancer in magnetic resonance imaging.

Using the amide proton signals of intracellular proteins and peptides to detect pH effects in MRI

2003-07-18

Jinyuan Zhou , Jean‐François Payen , David A. Wilson +2 more

A New Class of Contrast Agents for MRI Based on Proton Chemical Exchange Dependent Saturation Transfer (CEST)

2000-03-01

Kathleen Ward , Anthony H. Aletras , Robert S. Balaban

Polymeric drugs for efficient tumor-targeted drug delivery based on EPR-effect

2008-12-05

Hiroshi Maeda , Gahininath Y. Bharate , Jurstine Daruwalla

NMR-Relaxation Mechanisms of O17 in Aqueous Solutions of Paramagnetic Cations and the Lifetime of Water Molecules in the First Coordination Sphere

1962-07-15

T. J. Swift , Robert E. Connick

An investigation was made of the temperature and frequency dependence of T2 for O17 in aqueous solutions containing Mn2+, Fe2+, Co2+, Ni2+, and Cu2+. This represented an extension of the … An investigation was made of the temperature and frequency dependence of T2 for O17 in aqueous solutions containing Mn2+, Fe2+, Co2+, Ni2+, and Cu2+. This represented an extension of the studies previously performed in this laboratory on these ions. Virtually all of the temperature effects predicted by the modified Bloch equations for a two-species system were verified experimentally. Rates of exchange of water molecules between the bulk of the solution and the first coordination sphere of the paramagnetic cations were determined for all the ions studied. Activation energies for exchange were measured and electronic T1's and coupling constants were determined in some cases. Evidence was found for a tetrahedral Co2+(H2O)4 species in aqueous solutions near 100°C. The data for cupric ion were interpreted in terms of six coordinated water molecules in a distorted octahedron, with a ratio of ∼105 existing for the axial-water-exchange rate over that of the equatorial waters. The rates of exchange were compared with other physical measurements and the nature of the bonding was considered.

Plastic Optical Fiber Lasers and Amplifiers Containing Lanthanide Complexes

2002-05-07

Ken Kuriki , Yasuhiro Koike , Yoshi Okamoto

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPlastic Optical Fiber Lasers and Amplifiers Containing Lanthanide ComplexesKen Kuriki, Yasuhiro Koike, and Yoshi OkamotoView Author Information Faculty of Science and Technology, Keio University, Yokohama, Kanagawa 223-8522, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPlastic Optical Fiber Lasers and Amplifiers Containing Lanthanide ComplexesKen Kuriki, Yasuhiro Koike, and Yoshi OkamotoView Author Information Faculty of Science and Technology, Keio University, Yokohama, Kanagawa 223-8522, Japan, JST ERATO, Koike Photonics Polymer Project, K2 TOWN CAMPUS, 144-8 Ogura, Saiwai-ku, Kawasaki, Kanagawa, 212-0054, Japan Department of Chemistry and Polymer Research Institute, Polytechnic University, 6-Metrotech Center, Brooklyn, New York 11201 Cite this: Chem. Rev. 2002, 102, 6, 2347–2356Publication Date (Web):May 7, 2002Publication History Received8 November 2001Published online7 May 2002Published inissue 1 June 2002https://pubs.acs.org/doi/10.1021/cr010309ghttps://doi.org/10.1021/cr010309gresearch-articleACS PublicationsCopyright © 2002 American Chemical SocietyRequest reuse permissionsArticle Views4181Altmetric-Citations781LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Coordination compounds,Fibers,Fluorescence,Lasers,Plastics Get e-Alerts

Lanthanides in molecular magnetism: old tools in a new field

2011-01-01

Lorenzo Sorace , Cristiano Benelli , Dante Gatteschi

In this tutorial review we discuss some basic aspects concerning the magnetic properties of rare-earth ions, which are currently the subject of a renovated interest in the field of molecular … In this tutorial review we discuss some basic aspects concerning the magnetic properties of rare-earth ions, which are currently the subject of a renovated interest in the field of molecular magnetism, after the discovery that slow relaxation of the magnetization at liquid nitrogen temperature can occur in mononuclear complexes of these ions. Focusing on Dy(III) derivatives a tutorial discussion is given of the relation of the crystal field parameters, which determine the anisotropy of these systems and consequently their interesting magnetic properties, with the geometry of the coordination sphere around the lanthanide centre and with the pattern of f orbitals. The problem of systems of low point symmetry is also addressed by showing how detailed single crystal investigation, coupled to more sophisticated calculation procedures, is an absolute necessity to obtain meaningful structure-property relationships in these systems.

Fluorescence Lifetime Measurements and Biological Imaging

2010-03-31

М. Б. Березин , Samuel Achilefu

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTFluorescence Lifetime Measurements and Biological ImagingMikhail Y. Berezin* and Samuel Achilefu*View Author Information Department of Radiology, Washington University School of Medicine, 4525 Scott Ave, St. Louis, USA* … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTFluorescence Lifetime Measurements and Biological ImagingMikhail Y. Berezin* and Samuel Achilefu*View Author Information Department of Radiology, Washington University School of Medicine, 4525 Scott Ave, St. Louis, USA* To whom correspondence should be addressed. Tel. 314-747-0701 (M.Y.B.); 314-362-8599 (S.A.). Fax: 314-747-5191. E-mail: [email protected] (M.Y.B.); [email protected] (S.A.).Cite this: Chem. Rev. 2010, 110, 5, 2641–2684Publication Date (Web):March 31, 2010Publication History Received19 October 2009Published online31 March 2010Published inissue 12 May 2010https://pubs.acs.org/doi/10.1021/cr900343zhttps://doi.org/10.1021/cr900343zreview-articleACS PublicationsCopyright © 2010 American Chemical SocietyRequest reuse permissionsArticle Views41161Altmetric-Citations1762LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Biological imaging,Dyes and pigments,Fluorescence,Fluorescence imaging,Fluorophores Get e-Alerts

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Correlation between the lowest triplet state energy level of the ligand and lanthanide(III) luminescence quantum yield

1997-09-01

Martti Latva , Harri Takalo , Veli-Matti Mukkala +3 more

The EPR effect for macromolecular drug delivery to solid tumors: Improvement of tumor uptake, lowering of systemic toxicity, and distinct tumor imaging in vivo

2012-10-23

Hiroshi Maeda , Hideaki Nakamura , Jun Fang

Strategies for increasing the sensitivity of gadolinium based MRI contrast agents

2006-01-01

Peter Caravan

Gadolinium(III) complexes are often used in clinical MRI to increase contrast by selectively relaxing the water molecules near the complex. There is a desire to improve the sensitivity (relaxivity) of … Gadolinium(III) complexes are often used in clinical MRI to increase contrast by selectively relaxing the water molecules near the complex. There is a desire to improve the sensitivity (relaxivity) of these contrast agents in order to detect molecular targets. This tutorial review describes the molecular factors that contribute to relaxivity and illustrates with recent examples how these can be optimized. It may be of interest to senior undergraduates and more advanced researchers interested in lanthanide chemistry, biophysics, and/or molecular imaging.

On the design of highly luminescent lanthanide complexes

2014-11-07

Jean‐Claude G. Bünzli

Being Excited by Lanthanide Coordination Complexes: Aqua Species, Chirality, Excited-State Chemistry, and Exchange Dynamics

2002-05-21

David Parker , Rachel S. Dickins , Horst Puschmann +2 more

Lanthanide Luminescence for Biomedical Analyses and Imaging

2010-02-12

Jean‐Claude G. Bünzli

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTLanthanide Luminescence for Biomedical Analyses and ImagingJean-Claude G. Bünzli*View Author Information Laboratory of Lanthanide Supramolecular Chemistry, École Polytechnique Fédérale de Lausanne (EPFL), BCH 1402, CH-1015 Lausanne, Switzerland, … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTLanthanide Luminescence for Biomedical Analyses and ImagingJean-Claude G. Bünzli*View Author Information Laboratory of Lanthanide Supramolecular Chemistry, École Polytechnique Fédérale de Lausanne (EPFL), BCH 1402, CH-1015 Lausanne, Switzerland, and Department of Advanced Materials Chemistry, WCU Center for Next Generation Photovoltaic Systems, Korea University, Sejong Campus, 208 Seochang, Jochiwon, Chung Nam 339-700, Republic of Korea* To whom correspondence should be addressed. E-mail: [email protected]Cite this: Chem. Rev. 2010, 110, 5, 2729–2755Publication Date (Web):February 12, 2010Publication History Received5 November 2009Published online12 February 2010Published inissue 12 May 2010https://pubs.acs.org/doi/10.1021/cr900362ehttps://doi.org/10.1021/cr900362ereview-articleACS PublicationsCopyright © 2010 American Chemical SocietyRequest reuse permissionsArticle Views28225Altmetric-Citations2256LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Coordination compounds,Ions,Lanthanides,Luminescence,Probes Get e-Alerts

Hypersensitive pseudoquadrupole transitions in lanthanides

1964-01-01

Chr. Klixbüll Jørgensen , B. R. Judd

It is pointed out that the absorption lines of the lanthanides that are peculiarly sensitive to changes in the ligands are consistent with the selection rules for quadrupole radiation within … It is pointed out that the absorption lines of the lanthanides that are peculiarly sensitive to changes in the ligands are consistent with the selection rules for quadrupole radiation within the 4f shell. A number of sources for this sensitivity are examined, and it is concluded that it owes its origin to the inhomogeneity of the dielectric. According to this mechanism, there is an asymmetrical distribution of the dipoles induced by the electromagnetic field in the medium surrounding a lanthanide ion. The variation across the lanthanide ion of the electric vector is very much greater than for the case of a homogeneous dielectric, and the intensities of quadrupole transitions are enormously enhanced.

Strategies towards single molecule magnets based on lanthanide ions

2008-12-26

Roberta Sessoli , Annie K. Powell

Lanthanide‐Containing Light‐Emitting Organic–Inorganic Hybrids: A Bet on the Future

2008-12-12

Luís D. Carlos , Rute A. S. Ferreira , V. de Zea Bermudez +1 more

Interest in lanthanide-containing organic-inorganic hybrids has grown considerably during the last decade, with the concomitant fabrication of materials with tunable attributes offering modulated properties. The potential of these materials relies … Interest in lanthanide-containing organic-inorganic hybrids has grown considerably during the last decade, with the concomitant fabrication of materials with tunable attributes offering modulated properties. The potential of these materials relies on exploiting the synergy between the intrinsic characteristics of sol-gel derived hosts (highly controlled purity, versatile shaping and patterning, excellent optical quality, easy control of the refractive index, photosensitivity, encapsulation of large amounts of isolated emitting centers protected by the host) and the luminescence features of trivalent lanthanide ions (high luminescence quantum yield, narrow bandwidth, long-lived emission, large Stokes shifts, ligand-dependent luminescence sensitization). Promising applications may be envisaged, such as light-emitting devices, active waveguides in the visible and near-IR spectral regions, active coatings, and bio-medical actuators and sensors, opening up exciting directions in materials science and related technologies with significant implications in the integration, miniaturization, and multifunctionalization of devices. This review provides an overview of the latest advances in Ln(3+)-containing siloxane-based hybrids, with emphasis on the different possible synthetic strategies, photoluminescence features, empirical determination.

Thresholds in cerebral ischemia - the ischemic penumbra.

1981-11-01

Jens Astrup , Bo K. Siesjö , L. Symon

Benefiting from the Unique Properties of Lanthanide Ions

2005-12-17

Jean‐Claude G. Bünzli

The recent upsurge of interest in contrast agents for magnetic resonance imaging, of luminescent chemosensors for medical diagnostic, and lately, for optical imaging of cells has generated an impressive momentum … The recent upsurge of interest in contrast agents for magnetic resonance imaging, of luminescent chemosensors for medical diagnostic, and lately, for optical imaging of cells has generated an impressive momentum for the coordination and supramolecular chemistry of trivalent lanthanide ions. We shortly review the synthetic methods allowing the introduction of these spherical ions with fascinating optical and magnetic properties into elaborate mono- and polymetallic edifices. We then illustrate these methods by selected examples describing the use of (i) a coronand to produce luminescent liquid crystals, (ii) derivatized calixarenes for 4f−5f element separation, (iii) podates for the production of nanoparticles with high relaxivity and for sensitizing the near-infrared (NIR) emission, and (iv) self-assembly processes for producing functional bimetallic edifices.

Verfahren zur Darstellung der Graphitsäure

1898-05-01

L. Staudenmaier

erhalteueine Flussigkeit, welche bei 240-2430 siedet und in Wssser loslich ist.Die Salze desselben krystallisiren schlecht; uur ist es gelungrii, schiine Krystalle des Chloropl;ttinats zu gewinnen.Die Doppelverbindung des Chlorliydrntes rnit Quecksilberchlorid … erhalteueine Flussigkeit, welche bei 240-2430 siedet und in Wssser loslich ist.Die Salze desselben krystallisiren schlecht; uur ist es gelungrii, schiine Krystalle des Chloropl;ttinats zu gewinnen.Die Doppelverbindung des Chlorliydrntes rnit Quecksilberchlorid hildet einen weissen kryatnllinischeo Niederschlag.Die Reaction nwischen dem Chlorhydrnt und Kaliumnitrit ver- lauft ziemlich stiirrnisch, wobei sich eine neiitrnle Verbindung mit menthonahnlichem,

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Gadolinium – a specific trigger for the development of nephrogenic fibrosing dermopathy and nephrogenic systemic fibrosis?

2006-01-23

Thomas Grobner

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Taking advantage of luminescent lanthanide ions

2005-01-01

Jean‐Claude G. Bünzli , Claude Piguet

Lanthanide ions possess fascinating optical properties and their discovery, first industrial uses and present high technological applications are largely governed by their interaction with light. Lighting devices (economical luminescent lamps, … Lanthanide ions possess fascinating optical properties and their discovery, first industrial uses and present high technological applications are largely governed by their interaction with light. Lighting devices (economical luminescent lamps, light emitting diodes), television and computer displays, optical fibres, optical amplifiers, lasers, as well as responsive luminescent stains for biomedical analysis, medical diagnosis, and cell imaging rely heavily on lanthanide ions. This critical review has been tailored for a broad audience of chemists, biochemists and materials scientists; the basics of lanthanide photophysics are highlighted together with the synthetic strategies used to insert these ions into mono- and polymetallic molecular edifices. Recent advances in NIR-emitting materials, including liquid crystals, and in the control of luminescent properties in polymetallic assemblies are also presented. (210 references.)

Superparamagnetic iron oxide: pharmacokinetics and toxicity

1989-01-01

Ralph Weissleder , DD Stark , BL Engelstad +5 more

The pharmacokinetics (distribution, metabolism, bioavailability, excretion) and toxicity (acute and subacute toxicity, mutagenicity) of a superparamagnetic iron oxide preparation (AMI-25), currently used in clinical trials, were evaluated by 59Fe radiotracer … The pharmacokinetics (distribution, metabolism, bioavailability, excretion) and toxicity (acute and subacute toxicity, mutagenicity) of a superparamagnetic iron oxide preparation (AMI-25), currently used in clinical trials, were evaluated by 59Fe radiotracer studies, measurements of relaxation times, the ability to reverse iron deficiency anemia, histologic examination, and laboratory parameters. One hour after administration of AMI-25 to rats (18 mumol Fe/kg; 1 mg Fe/kg), 82.6 +/- 0.3% of the administered dose was sequestered in the liver and 6.2 +/- 7.6% in the spleen. Peak concentrations of 59Fe were found in liver after 2 hr and in the spleen after 4 hr. 59Fe slowly cleared from liver (half-life, 3 days) and spleen (half-life, 4 days) and was incorporated into hemoglobin of erythrocytes in a time-dependent fashion. The half-time of the T2 effect on liver and spleen (24-48 hr) was shorter than the 59Fe clearance, indicating metabolism of AMI-25 into other forms of iron. IV administration of AMI-25 (30 mg Fe/kg) corrected iron-deficiency anemia and showed bioavailability similar to that of commercially available IV iron preparations within 7 days. No acute or subacute toxic effects were detected by histologic or serologic studies in rats or beagle dogs who received a total of 3000 mumol Fe/kg, 150 times the dose proposed for MR imaging of the liver. Our results indicate that AMI-25 is a fully biocompatible potential contrast agent for MR.

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Gadolinium-based Contrast Agent Accumulates in the Brain Even in Subjects without Severe Renal Dysfunction: Evaluation of Autopsy Brain Specimens with Inductively Coupled Plasma Mass Spectroscopy

2015-05-05

Tomonori Kanda , Toshio Fukusato , Megumi Matsuda +6 more

To use inductively coupled plasma mass spectroscopy (ICP-MS) to evaluate gadolinium accumulation in brain tissues, including the dentate nucleus (DN) and globus pallidus (GP), in subjects who received a gadolinium-based … To use inductively coupled plasma mass spectroscopy (ICP-MS) to evaluate gadolinium accumulation in brain tissues, including the dentate nucleus (DN) and globus pallidus (GP), in subjects who received a gadolinium-based contrast agent (GBCA).Institutional review board approval was obtained for this study. Written informed consent for postmortem investigation was obtained either from the subject prior to his or her death or afterward from the subject's relatives. Brain tissues obtained at autopsy in five subjects who received a linear GBCA (GBCA group) and five subjects with no history of GBCA administration (non-GBCA group) were examined with ICP-MS. Formalin-fixed DN tissue, the inner segment of the GP, cerebellar white matter, the frontal lobe cortex, and frontal lobe white matter were obtained, and their gadolinium concentrations were measured. None of the subjects had received a diagnosis of severely compromised renal function (estimated glomerular filtration rate <45 mL/min/1.73 m(2)) or acute renal failure. Fisher permutation test was used to compare gadolinium concentrations between the two groups and among brain regions.Gadolinium was detected in all specimens in the GBCA agent group (mean, 0.25 µg per gram of brain tissue ± 0.44 [standard deviation]), with significantly higher concentrations in each region (P = .004 vs the non-GBCA group for all regions). In the GBCA group, the DN and GP showed significantly higher gadolinium concentrations (mean, 0.44 µg/g ± 0.63) than other regions (0.12 µg/g ± 0.16) (P = .029).Even in subjects without severe renal dysfunction, GBCA administration causes gadolinium accumulation in the brain, especially in the DN and GP.

Nephrogenic Systemic Fibrosis

2006-08-03

Peter Marckmann , Lone Skov , Kristian Rossen +4 more

Nephrogenic systemic fibrosis is a new, rare disease of unknown cause that affects patients with renal failure. Single cases led to the suspicion of a causative role of gadodiamide that … Nephrogenic systemic fibrosis is a new, rare disease of unknown cause that affects patients with renal failure. Single cases led to the suspicion of a causative role of gadodiamide that is used for magnetic resonance imaging. This study therefore reviewed all of the authors' confirmed cases of nephrogenic systemic fibrosis (n = 13) with respect to clinical characteristics, gadodiamide exposure, and subsequent clinical course. It was found that all had been exposed to gadodiamide before the development of nephrogenic systemic fibrosis. The delay from exposure to first sign of the disease was 2 to 75 d (median 25 d). Odds ratio for acquiring the disease when gadodiamide exposed was 32.5 (95% confidence interval 1.9 to 549.2; P < 0.0001). Seven (54%) patients became severely disabled, and one died 21 mo after exposure. No other exposure/event than gadodiamide that was common to more than a minority of the patients could be identified. These findings indicate that gadodiamide plays a causative role in nephrogenic systemic fibrosis.

Intracranial Gadolinium Deposition after Contrast-enhanced MR Imaging

2015-03-05

Robert J. McDonald , Jennifer S. McDonald , David F. Kallmes +5 more

To determine if repeated intravenous exposures to gadolinium-based contrast agents (GBCAs) are associated with neuronal tissue deposition.In this institutional review board-approved single-center study, signal intensities from T1-weighted magnetic resonance (MR) … To determine if repeated intravenous exposures to gadolinium-based contrast agents (GBCAs) are associated with neuronal tissue deposition.In this institutional review board-approved single-center study, signal intensities from T1-weighted magnetic resonance (MR) images and postmortem neuronal tissue samples from 13 patients who underwent at least four GBCA-enhanced brain MR examinations between 2000 and 2014 (contrast group) were compared with those from 10 patients who did not receive GBCA (control group). Antemortem consent was obtained from all study participants. Neuronal tissues from the dentate nuclei, pons, globus pallidus, and thalamus of these 23 deceased patients were harvested and analyzed with inductively coupled plasma mass spectrometry (ICP-MS), transmission electron microscopy, and light microscopy to quantify, localize, and assess the effects of gadolinium deposition. Associations between cumulative gadolinium dose, changes in T1-weighted MR signal intensity, and ICP-MS-derived tissue gadolinium concentrations were examined by using the Spearman rank correlation coefficient (ρ).Compared with neuronal tissues of control patients, all of which demonstrated undetectable levels of gadolinium, neuronal tissues of patients from the contrast group contained 0.1-58.8 μg gadolinium per gram of tissue, in a significant dose-dependent relationship that correlated with signal intensity changes on precontrast T1-weighted MR images (ρ = 0.49-0.93). All patients in the contrast group had relatively normal renal function at the time of MR examination. Gadolinium deposition in the capillary endothelium and neural interstitium was observed only in the contrast group.Intravenous GBCA exposure is associated with neuronal tissue deposition in the setting of relatively normal renal function. Additional studies are needed to investigate the clinical significance of these findings and the generalizability to other GBCAs. Online supplemental material is available for this article.

Interpretation of europium(III) spectra

2015-02-24

Koen Binnemans

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Lanthanide Probes for Bioresponsive Imaging

2013-12-13

Marie C. Heffern , Lauren M. Matosziuk , Thomas J. Meade

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTLanthanide Probes for Bioresponsive ImagingMarie C. Heffern, Lauren M. Matosziuk, and Thomas J. Meade*View Author Information Department of Chemistry, Molecular Biosciences, Neurobiology, Biomedical Engineering, and Radiology, Northwestern … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTLanthanide Probes for Bioresponsive ImagingMarie C. Heffern, Lauren M. Matosziuk, and Thomas J. Meade*View Author Information Department of Chemistry, Molecular Biosciences, Neurobiology, Biomedical Engineering, and Radiology, Northwestern University, Evanston, Illinois 60208-3113, United States*Phone: 847-491-2841. Fax: 847-491-3832. E-mail: [email protected]Cite this: Chem. Rev. 2014, 114, 8, 4496–4539Publication Date (Web):December 13, 2013Publication History Received30 August 2013Published online13 December 2013Published inissue 23 April 2014https://pubs.acs.org/doi/10.1021/cr400477thttps://doi.org/10.1021/cr400477treview-articleACS PublicationsCopyright © 2013 American Chemical SocietyRequest reuse permissionsArticle Views16228Altmetric-Citations971LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Antennas,Coordination compounds,Lanthanides,Luminescence,Probes Get e-Alerts

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Chemistry of MRI Contrast Agents: Current Challenges and New Frontiers

2018-10-16

Jessica Wahsner , Eric M. Gale , Aurora Rodríguez‐Rodríguez +1 more

Tens of millions of contrast-enhanced magnetic resonance imaging (MRI) exams are performed annually around the world. The contrast agents, which improve diagnostic accuracy, are almost exclusively small, hydrophilic gadolinium(III) based … Tens of millions of contrast-enhanced magnetic resonance imaging (MRI) exams are performed annually around the world. The contrast agents, which improve diagnostic accuracy, are almost exclusively small, hydrophilic gadolinium(III) based chelates. In recent years concerns have arisen surrounding the long-term safety of these compounds, and this has spurred research into alternatives. There has also been a push to develop new molecularly targeted contrast agents or agents that can sense pathological changes in the local environment. This comprehensive review describes the state of the art of clinically approved contrast agents, their mechanism of action, and factors influencing their safety. From there we describe different mechanisms of generating MR image contrast such as relaxation, chemical exchange saturation transfer, and direct detection and the types of molecules that are effective for these purposes. Next we describe efforts to make safer contrast agents either by increasing relaxivity, increasing resistance to metal ion release, or by moving to gadolinium(III)-free alternatives. Finally we survey approaches to make contrast agents more specific for pathology either by direct biochemical targeting or by the design of responsive or activatable contrast agents.

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The intensities of lanthanide f ↔ f transitions

2007-12-13

Robert D. Peacock

Broadband transient full-Stokes luminescence spectroscopy

2025-06-25

Antti‐Pekka M. Reponen , Mark Mattes , Zachary A. VanOrman +3 more | Nature

Abstract Materials emitting circularly polarized light (CPL) are highly sought after for applications ranging from efficient displays to quantum information technologies 1–7 . However, established methods for time-resolved CPL (TRCPL) … Abstract Materials emitting circularly polarized light (CPL) are highly sought after for applications ranging from efficient displays to quantum information technologies 1–7 . However, established methods for time-resolved CPL (TRCPL) characterization have notable limitations 8–17 , generally requiring a compromise between sensitivity, accessible timescales and spectral information. This has limited the acquisition of in-depth photophysical insight necessary for materials development. Here we demonstrate a high-sensitivity (noise level of the order of 10 −4 ), broadband (about 400–900 nm), transient (nanosecond resolution, millisecond range) full-Stokes (CPL and linear polarizations) spectroscopy setup. The achieved combination of high-sensitivity, broad wavelength response and flexible time ranges represents a substantial advancement over previous TRCPL approaches. As a result, TRCPL measurements are shown to be applicable to hitherto inaccessible material systems and photophysical processes, including systems with low (10 −3 ) dissymmetry factors and luminescence pathways spanning nanosecond to millisecond time ranges. Finally, full-Stokes measurements allow tracking the temporal evolution of linear polarization components, of interest by themselves, but especially relevant in the context of controlling for associated CPL artefacts 18,19 in the time domain.

A Unique Trinuclear, Triangular Ni(II) Complex Composed of Two tri-Anionic bis-Oxamates and Capping Nitroxyl Radicals

2025-06-25

Vitaly Morozov , Denis G. Samsonenko⧫ , Kira E. Vostrikova | Inorganics

Phenylene-based bis-oxamate polydentate ligands offer a unique opportunity for creating a large variety of coordination compounds, in which paramagnetic metal ions are strongly magnetically coupled. The employment of imino nitroxyl … Phenylene-based bis-oxamate polydentate ligands offer a unique opportunity for creating a large variety of coordination compounds, in which paramagnetic metal ions are strongly magnetically coupled. The employment of imino nitroxyl (IN) radicals as supplementary ligands confers numerous benefits, including the strong ferromagnetic interaction between Ni and IN. Furthermore, the chelating IN can act as a capping ligand, thereby impeding the formation of coordination polymers. In this study, we present the molecular and crystal structure and experimental and theoretical magnetic behavior of an exceptional neutral trinuclear complex [Ni(L3−)2(IN)3]∙5CH3OH (1) (L is N,N′-1,3-phenylenebis-oxamic acid; IN is [4,4,5,5-tetramethyl-2-(6-methylpyridin-2-yl)-4,5-dihydro-1H-imidazol-1-yl]oxidanyl radical) with a cyclic triangular arrangement. Moreover, in this compound three Ni2+ ions are linked by the two bis-oxamate ligands playing a rare tritopic function due to an unprecedented triple deprotonation of the related meta-phenylene-bis(oxamic acid). The main evidence of such a deprotonation of the ligand is the neutrality of the cluster, since there are no anions or cations compensating for its charge in the crystals of the compound. Despite the presence of six possible magnetic couplings in the trinuclear cluster 1, its behavior was reproduced with a high degree of accuracy using a three-J model and ZFS, under the assumption that the three different Ni-IN interactions are equal to each other, whereas only two equivalent-in-value Ni-Ni interactions were taken into account, with the third one being equated to zero. Our study indicates the presence of two opposite-in-nature types of magnetic interactions within the triangular core. DFT and CASSCF/NEVPT2 calculations were completed to support the experimental magnetic data simulation.

Single-Ion Magnetism in Pseudo-D5h Symmetric Complexes of Less Explored Lanthanides Built from a Bulky Phosphonamide

2025-06-24

Aheli Ghatak , Ramaswamy Murugavel | Crystal Growth & Design

Recent advances in the synthetic methodologies, crystallographic studies, and luminescent properties of europium β-diketonate complexes

2025-06-24

Asif Manzoor , Faisal Jamil , Haris Nadeem +7 more | Journal of Coordination Chemistry

Magnetic Properties of Prolate Lanthanide Complexes: Synergy between Axial and Equatorial Ligands

2025-06-24

Leonardo Tacconi , Anna Schannong Manvell , Arianna Lanza +6 more | Inorganic Chemistry

The chemical design of single-molecule magnets is a vibrant field of research. Huge efforts in determining the key factors to slow down the relaxation time of the magnetization led to … The chemical design of single-molecule magnets is a vibrant field of research. Huge efforts in determining the key factors to slow down the relaxation time of the magnetization led to massive improvements in the blocking temperature. Even though several lanthanides are excellent magnetic anisotropy building blocks, the current literature is dominated by (pseudo)-axial Dy3+ complexes. Prolate ions such as Er3+ and Yb3+ exhibit on average relatively modest barriers and fast relaxation times. In this paper, we pinpoint how the combination of symmetry and ligand charge distribution affects the slow relaxation of prolate ions. In this paper, we synthesized and characterized two new lanthanide complexes, namely, [LnDOTA][CoF2(py)4] (Ln = Er3+ or Yb3+, DOTA = tetraazacyclododecane-N,N',N″,N‴-tetraacetate, py = pyridine). Such complexes were used to provide a proof of concept that apical ligands, typically considered detrimental in prolate ion complexes, can be exploited in combination with the other ligands' geometry to improve the performances of the system.

<scp>LUMPAC</scp> 2.0—Bridging Theory and Experiment in the Study of Luminescent Systems

2025-06-23

José Diogo L. Dutra , Willyan F. Oliveira , Gustavo S. Silva +2 more | Journal of Computational Chemistry

ABSTRACT There is no doubt about the relevance that lanthanide‐based luminescent systems have gained in recent decades. These systems have applications in various technological fields, and the development of these … ABSTRACT There is no doubt about the relevance that lanthanide‐based luminescent systems have gained in recent decades. These systems have applications in various technological fields, and the development of these materials has been of great scientific interest since the 1970s. We made the first version of the LUMPAC software available 10 years ago. In our publication, we highlighted the scarcity of studies concerning the use of theoretical computational methods to design new luminescent systems and to explain laboratory‐observed phenomena involving such systems. In this work, we present the LUMPAC 2.0 software. We show how the first version contributed to increasing the number of studies involving theoretical computational methods, and we evaluate its use since its launch. This second version introduces highly relevant features and implementations and will undoubtedly be an important tool in new studies that will be carried out over the next few years.

Gadolinium-Conjugated Lipoic Acid Hydrogels for Magnetic Resonance Imaging

2025-06-23

Andrew R. Brotherton , Bennett Phillips-Sorich , Naedum DomNwachukwu +5 more | ACS Applied Bio Materials

A gadolinium-based contrast agent (GBCA) disulfide homodimer (Gd3+SS) has been incorporated into a lipoic acid (LA)-based hydrogel (Gd3+Gel) for enhanced magnetic resonance imaging (MRI). This study evaluates the magnetic properties … A gadolinium-based contrast agent (GBCA) disulfide homodimer (Gd3+SS) has been incorporated into a lipoic acid (LA)-based hydrogel (Gd3+Gel) for enhanced magnetic resonance imaging (MRI). This study evaluates the magnetic properties and in vitro behavior of Gd3+Gel for potential applications in tracking internal injuries. Results indicate a direct shortening in the relaxation rate with greater magnitude of LA polymerization and a 2.8-fold enhancement in relaxivity (r1) at 1.4 T when Gd3+SS was conjugated into the hydrogel. This effect is attributed to a significant increase in the rotational correlation time (τr) from 0.22 ± 0.05 ns (Gd3+SS) to 6 ± 1 ns (Gd3+Gel). Retention studies confirm that Gd3+SS remains covalently within the hydrogel, with retention of 64.7 ± 1.9% for Gd3+SS and 14.0 ± 1.4% for noncovalent binding gadoterate. The hydrogel relaxation rate (1/T1) increases from 1.1 to 3.5 s-1 at 7 T from blank gel to Gd3+Gel (0.24 mM Gd3+). Cell studies show that PC3-PIP and RAW 264.7 cells maintain high viability with Gd3+SS but exhibit reduced viability with Gd3+Gel, consistent with known lipoic acid effects on immortalized cell lines. Cellular uptake studies using ICP-MS and confocal fluorescence microscopy confirm that monomeric Gd3+SS is readily internalized, whereas Gd3+Gel significantly limits diffusion and uptake. Rheology was conducted to determine the zero-shear viscosity of the LA hydrogel at various concentrations of LA. These findings suggest that the LA hydrogel scaffold enhances MRI contrast, minimizes leaching, and is easily injectable. Gd3+Gel is a promising tool for potential targeted imaging and controlled uptake during healing processes.

X-ray Scintillating Lanthanide-Based Coordination Polymers

2025-06-23

Elizabeth A. Decoteau , Claire T. Belatti , Huong Giang T. Nguyen +3 more | Crystal Growth & Design

Double‐Step R1rho‐Based Lorentzian Fitting (DROF): A New CEST Analysis Approach and Its Comparison With Existing Methods

2025-06-22

Huabin Zhang , Shihao Zeng , Jiawen Wang +5 more | NMR in Biomedicine

At 3-T MRI, reliable quantification of CEST contrast is challenged by peak overlap and broad background contamination. Because of this limitation, some previous studies employ four-pool Lorentzian fitting (i.e., amide, … At 3-T MRI, reliable quantification of CEST contrast is challenged by peak overlap and broad background contamination. Because of this limitation, some previous studies employ four-pool Lorentzian fitting (i.e., amide, direct water saturation, magnetization transfer, and relayed nuclear Overhauser enhancement) for CEST analysis at 3 T, where the multiple CEST contrasts at positive frequency offsets are treated as a single pool. In addition, for fitting-based methods, the fitting accuracy can be readily affected by initial values and boundary conditions. To address these problems, a new CEST analysis approach, named double-step R1rho-based Lorentzian fitting (DROF), with initial value randomization, was developed in this study for extracting five-pool (additional CEST@2 ppm pool) Lorentzian fitting parameters at 3 T. Moreover, a comprehensive evaluation framework including three metrics was proposed to assess the performance of CEST analysis methods. The accuracy and robustness of DROF were evaluated using both simulation and in vivo human data at 3 T, and its performance was compared with existing methods. Results demonstrate that DROF offers improved specificity and stability, suggesting its potential to enhance CEST applicability at 3 T.

Paramagnetic and Luminescent Properties of Gd(III)/Eu(III) Ascorbate Coordination Polymers

2025-06-21

Marco Ricci , Fabio Carniato | Molecules

Gadolinium-based contrast agents (GBCAs) are the gold standard as MRI probes but are nowadays facing medical limitations and environmental concerns. To address these issues, novel strategies focus on the optimization … Gadolinium-based contrast agents (GBCAs) are the gold standard as MRI probes but are nowadays facing medical limitations and environmental concerns. To address these issues, novel strategies focus on the optimization of Gd(III)-based probes. One promising approach involves incorporating Gd(III) into nanoparticles, particularly coordination polymers, which offer improved relaxivity. In this study, we explore the self-assembly of Gd(III) ions with ascorbate ligand, forming extended coordination polymer architectures. Our investigation focuses on understanding the impact of nanoparticles’ growth and aggregation on their relaxivity properties. Notably, the controlled aggregation process leads to a different distribution of the Gd(III) in the surface and in the bulk of the nanoparticles, mainly responsible for their longitudinal relaxivity. Additionally, the introduction of Eu(III) into the network enables the development of a dual-modal probe with paramagnetic and optical features.

Unveiling Iron(III) Complex: Structural Elucidation, DFT Insights, Hirshfeld Surface Analysis, and Cytotoxic Activity

2025-06-21

Sudipta Pathak , Aparup Paul , Chandan Bodhak +4 more | Russian Journal of Inorganic Chemistry

Gadolinium and Its Effects on Nutritional Status, Microscopy and Microanalytical Outcomes: Quantification by ICP‐MS and Incidence on Reproductive Tract and Liver of Wistar Rats

2025-06-20

Samira Maghraoui , Adrian Florea , Leila Tekaya | Microscopy Research and Technique

ABSTRACT The behavior and incidence of the gadolinium (Gd) in the organism, has been carried out because of its increasing industrial and medical uses. Gadolinium was intraperitoneally administered to adult … ABSTRACT The behavior and incidence of the gadolinium (Gd) in the organism, has been carried out because of its increasing industrial and medical uses. Gadolinium was intraperitoneally administered to adult male Wistar rats, allowing access to organs via the blood. First, the nutritional status was daily determined using body weight and food intake of animals. Second, testicles, seminal vesicles, epididymides and their caudae, as well as liver, kidneys and brain weights were recorded. Third, treated and control organs were prepared for ultrastructural and microanalytical observations and were used for Gd quantification by ICP‐MS technique. Seminal vesicles and the kidneys of treated rats showed significant increase in absolute weight. The ICP‐MS showed that Gd was found in very important amounts in liver, testicle and urines collected over 24 h. The ultrastructural and microanalytical techniques showed that Gd was found in the lysosomes of Sertoli, Leydig and hepatic cells in the form of electron‐dense grains associated with phosphorus. Ultrastructural alterations were also noticed in those cells. These original results showed that the lysosome was certainly exceeded since Gd was highly detected in many organs like liver and testicles. The presence of Gd in the rat organism seemed to cause toxicity and alteration in testicular cell organelles leading very probably to disruption in the reproductive tract functions. In this case, the organism seemed to activate elimination of Gd via hepatic biliary ducts and kidney excretion confirmed by the presence of Gd in the different analyzed liver territories and in the collected urines.

Fe(III)-Based Nanomicelles for Magnetic Resonance Imaging of Colorectal Cancer with Hepatic Metastasis

2025-06-20

Tianlun Shen , Kangle Lv , Zhenyan Chen +6 more | Journal of Functional Biomaterials

Colorectal cancer (CRC) is a leading global malignancy with a poor prognosis in advanced stages. Early and accurate diagnosis remains challenging due to the overlapping of clinical manifestations between early-stage … Colorectal cancer (CRC) is a leading global malignancy with a poor prognosis in advanced stages. Early and accurate diagnosis remains challenging due to the overlapping of clinical manifestations between early-stage CRC and inflammatory bowel diseases. Although dynamic contrast-enhanced MRI (DCE-MRI) is a critical imaging modality for the diagnosis of CRC and colorectal cancer liver metastasis (CRLM), conventional gadolinium-based contrast agents (GBCAs) have the limitations of rapid clearance and potential toxicity risks. In this study, we report a gadolinium-free T1-weighted nanocontrast agent based on Fe(III)-coordinated poly(α-amino acid)s (Fe@POS) nanomicelles. Fe@POS nanomicelles exhibit a high longitudinal relaxivity (r1 = 5.56 mM−1s−1) and prolonged blood circulation time with selective CRC tumor accumulation via enhanced permeability and retention (EPR) effect. In vivo MRI studies revealed long-period MRI of CRC. In CRLM lesions, normal hepatic tissue demonstrates greater Fe@POS uptake compared to tumor tissue, which enables clear delineation of tumor margins on MRI. Histological and biochemical analysis confirmed the biocompatibility of Fe@POS nanomicelles, with no acute toxicity observed, highlighting their potential as alternatives to GBCAs for clinical diagnostic applications.

Determining Molecular Structure, Coordination Geometry, and Molecular Symmetry

2025-06-19

Thomas Just Sørensen , Villads R. M. Nielsen | Research Square (Research Square)

<title>Abstract</title> Chemists have a strong language describing and defining idealized polyhedra <bold>P</bold> and symmetry point groups <bold>G</bold>, but no efficient measure to correlate these to real molecular structures <bold>Q</bold>. Symmetry … <title>Abstract</title> Chemists have a strong language describing and defining idealized polyhedra <bold>P</bold> and symmetry point groups <bold>G</bold>, but no efficient measure to correlate these to real molecular structures <bold>Q</bold>. Symmetry and structure have been ascribed through experience, but this approach is error-prone and provides no measure that can correlate molecular structure to molecular properties. Quantification of molecular structure and symmetry is crucial, and this requires two tools: a tool that orients a molecular structure to a symmetry axis, and a tool that measures the deviation of the molecular structure from symmetry. The first approach developed was the Continuous Symmetry Measure (CSM), which does both tasks and is exact across all symmetries as well as mathematically elegant. Unfortunately as a tool the CSM is close to impossible to implement. This led to the development of the Continuous Shape Measure (CShM) that measures how close a molecular structure <bold>Q</bold> is to a set of selected structures <bold>P</bold>’. The CShM tool have severe limitations, and we suggest that the Continuous Symmetry operation Measure (CSoM) should be the preferred tool. The CSoM tool can quantify the symmetry of any structure that can be described as a list of points in space. Here, we describe the CSM, CShM, and CSoM approaches and demonstrate how these can be used as tools to determine molecular structure, coordination geometry, and symmetry of water, organic molecules, transition metal complexes, and lanthanide compounds.

Effect of the Compartmentalization Into Liposome's Cavity on the Relaxation Times of F− and PF6− Anions

2025-06-19

Diana Costanzo , Francesca Garello , Silvio Aime +1 more | NMR in Biomedicine

ABSTRACT The entrapment of fluoride (F − ) and hexafluorophosphate (PF 6 − ) anions within liposome inner cavities significantly alters their magnetic resonance properties, offering potential advancements in imaging … ABSTRACT The entrapment of fluoride (F − ) and hexafluorophosphate (PF 6 − ) anions within liposome inner cavities significantly alters their magnetic resonance properties, offering potential advancements in imaging technologies. This study addresses the need for improved MRI contrast agents, particularly those enabling precise monitoring of drug delivery systems. By leveraging the unique interaction between these anions and the liposomal membrane, we investigate their effects on nuclear magnetic relaxation. Specifically, we observe that both longitudinal (T 1 ) and transverse (T 2 ) relaxation times of the nuclei associated with the encapsulated anions are substantially shortened. This relaxation enhancement is dependent on vesicle size, being more pronounced for smaller liposomes, and varies with anion type and concentration. Notably, PF 6 − induces a greater reduction in T 1 and T 2 relaxation times compared to F − . The observed effects are attributed to the dynamic interactions between the anions and the liposomal bilayer, which are modulated by the vesicle's physicochemical properties. The results reveal a striking two‐order magnitude decrease in the 19 F T 1 of liposomes loaded with PF 6 − , demonstrating their potential utility as sensitive MRI reporters. This work underscores the broader implications of tailoring liposome compositions for specific biomedical applications. The study not only advances the understanding of liposome‐anion interactions but also establishes a pathway for the development of novel contrast agents with high sensitivity and specificity, bridging the gap between material science and clinical imaging innovations.

Designing Luminescent Eu(III) Complexes with Heteroligands: A Comprehensive Spectroscopic, DFT and Judd-Ofelt Study

2025-06-18

Sonia Redhu , Devender Singh , Sofia Malik +5 more | Journal of Luminescence

A Polyaromatic Metallotube with a Dual Multi‐Functionalization Ability

2025-06-17

Koki Tagai , Yuya Tanaka , Michio Yamada +1 more | Angewandte Chemie

Post‐functionalization is an advanced, key synthetic method in supramolecular systems, whereas the previous method relies heavily on the substitution on the organic frameworks. Here we report a polyaromatic metallotube capable … Post‐functionalization is an advanced, key synthetic method in supramolecular systems, whereas the previous method relies heavily on the substitution on the organic frameworks. Here we report a polyaromatic metallotube capable of dually multi‐functionalizing the metal sites in an efficient post‐assembly fashion. The Pt(II)‐linked tube with tetrachloro groups is prepared from two PtCl2 hinges and two bent bispyridine ligands in high yield. The new metallotube efficiently converts to tetra‐substituted tubes by the first multiple functionalization, through the replacement of the chloro groups with various alkynyl groups. The tubular structures before/after the functionalization are unequivocally confirmed by X‐ray crystallographic analysis. A resultant tetraammonium‐attached Pt(II)tube exhibits high water solubility and uptake abilities toward spherical and rod‐like compounds. The metallotube strongly binds one molecule of fullerene C60 in the polyaromatic cavity yet releases it through the second multi‐functionalization by tetrabromination of the metal hinges in a quantitative and reversible manner. Even after Bingel reaction within the tube, sterically demanding bis‐substituted fullerenes (>~80% selectivity) are readily released by the second functionalization. The present method, i.e., the use of simple PtCl2 hinges, will be applicable to wide‐ranging metallo‐supramolecules to enhance their structural and functional versatilities via post‐multifunctionalizations.

Eu-Tb-Doped Y-BTC MOF: A Step Towards Optimization of an Energy Conversion System

2025-06-17

Francesca Lo Presti , Anna Lucia Pellegrino , Francesca Loschi +3 more | Crystals

Lanthanide-based metal–organic frameworks (Ln-MOFs) represent a key material in various optical applications. Thus, they offer the possibility of fine-tuning their functional properties by adjusting the composition, stoichiometry, and ligand nature. … Lanthanide-based metal–organic frameworks (Ln-MOFs) represent a key material in various optical applications. Thus, they offer the possibility of fine-tuning their functional properties by adjusting the composition, stoichiometry, and ligand nature. This work reports for the first time the environmentally friendly one-pot synthesis of Eu-Tb-doped yttrium-1,3,5-benzenetricarboxylate MOF, i.e., Y-BTC: Eu (10%), Tb (10%), under mild conditions of temperature and pressure. Structural and morphological investigations were conducted through ATR-IR, XRD, and FE-SEM characterization. The doping percentage was analyzed by EDX spectroscopy. The luminescence properties confirm the down-shifting behavior of the MOF, paving the way for using this Eu-Tb-doped Y-BTC system in photovoltaic technology.

Dual‐Antenna Trimetallic Lanthanide Complexes for Enhanced Near‐Infrared Luminescence

2025-06-17

Krishanu Bandyopadhyay , Abhineet Verma , Satyen Saha | Chemistry - An Asian Journal

Abstract Lanthanide [Ln(III)] ions are known for their unique near‐infrared (NIR) luminescence, typically achieved through indirect excitation via the antenna effect. Organic ligands, such as N , N ‐bis(3‐methoxysalicylidene)‐1,4‐diamino butane … Abstract Lanthanide [Ln(III)] ions are known for their unique near‐infrared (NIR) luminescence, typically achieved through indirect excitation via the antenna effect. Organic ligands, such as N , N ‐bis(3‐methoxysalicylidene)‐1,4‐diamino butane ( L ), in combination with Zn, have previously demonstrated their effectiveness in enhancing lanthanide NIR emission, as seen in bimetallic [ L‐Zn‐Ln ] complexes, which employs a single antenna. In this study, we present a new series of trimetallic Zn–Ln complexes, [ (L‐Zn)₂‐Ln ], featuring two compartmental ligand‐Zn complexes, acting as antennas, aimed at further improving energy transfer efficiency to the lanthanide centers. Comprehensive characterization using SCXRD, PXRD, FT‐IR, and CHN analyses confirmed the structural integrity of these complexes. Notably, SCXRD and XPS revealed significant structural differences between the bimetallic and trimetallic systems. The impact of the additional antenna, replacing nitrate and methanol—known contributors to nonradiative relaxation in the bimetallic [ L‐Zn‐Ln ] complexes—was thoroughly examined. Photophysical studies across both visible and NIR regions demonstrated substantial enhancements in luminescence, particularly in the NIR region, attributed to the inclusion of the second antenna, highlighting its role in improving the overall energy transfer process.

Synthesis, Structure, and Property of Tris(biphenyldiyl)yttrium(III) Tris(binaphthyldiyl)yttrium(III) and Tris(binaphthyldiyl)erbium(III) Complexes

2025-06-16

Masaki Hara , Gabriela Handzlik , Mirosław Arczyński +3 more | Inorganic Chemistry

In the recent development of homoleptic σ-hydrocarbyl rare-earth metal complexes focusing on reactivity and catalytic activity, rare-earth metal complexes with a variety of alkyl ligands have been synthesized, and the … In the recent development of homoleptic σ-hydrocarbyl rare-earth metal complexes focusing on reactivity and catalytic activity, rare-earth metal complexes with a variety of alkyl ligands have been synthesized, and the principle for designing thermally stable σ-hydrocarbyl rare-earth metal complexes has been established. Nevertheless, there has been no report of homoleptic rare-earth metal complexes comprising only identical bidentate σ-hydrocarbyl ligands. Herein, we present homoleptic σ-hydrocarbyl rare-earth metal complexes possessing bidentate biaryldiyl ligands, tris(biphenyl-2,2'-diyl)yttrium(III) complex 1, tris(1,1'-binaphthyl-2,2'-diyl)yttrium(III) complex 2, and tris(1,1'-binaphthyl-2,2'-diyl)erbium(III) complex 3. Single-crystal X-ray crystallography revealed the trigonal prismatic geometry of 1, along with the trigonal antiprismatic geometry of 2 and 3, each constructed through three-centered two-electron bonds among the rare-earth metal, ipso-carbon, and lithium. The static and dynamic magnetic properties of 3 were investigated in the solid state, showing a slow magnetic relaxation typical of single-molecule magnets. The fitting of the magnetic behavior of 3 and the ab initio theoretical calculations indicated that the magnetic relaxation of 3 occurs primarily through a Raman relaxation process.

A Hexagonal Bipyramidal Uranyl(V) Single-Ion Magnet Showing Finger-Type Photoluminescence

2025-06-16

Pei‐Yu Liao , Haoran Xing , Yi-Ling Zhong +7 more | Journal of the American Chemical Society

The occurrence of uranyl(V) compounds in nuclear fuel cycles and radioactive waste necessitates a deep understanding of the electronic structure of these 5f1 species. Characteristic properties of pentavalent uranium can … The occurrence of uranyl(V) compounds in nuclear fuel cycles and radioactive waste necessitates a deep understanding of the electronic structure of these 5f1 species. Characteristic properties of pentavalent uranium can include single-molecule magnet (SMM) behavior and finger-like luminescence. However, both properties have not previously been observed in the same uranyl(V) complex. Here, we show that one-electron reduction of the hexagonal bipyramidal uranyl(VI) compound [UO2(LN6)][BPh4]2 (1-U) gives the uranyl(V) congener [UO2(LN6)][BPh4] (2-U) (LN6 is a hexadentate N-donor with two connected bis(imino)pyridine groups). In addition to field-induced slow magnetic relaxation, 2-U displays photoluminescence upon excitation at 440 nm, the first time that both phenomena are observed in one uranyl(V) complex. The emission from 2-U is characterized by five well-resolved bands in the region 510-586 nm, in contrast to the broad emission observed for 1-U centered on 650 nm. The relationship between the electronic structure of 1-U and 2-U is emphasized by the photochromic behavior of 1-U, which, upon irradiation at 365 nm, adopts a stable photoexcited state 1-U* following a ligand-to-metal electron transfer, with the magnetic and spectroscopic properties of 1-U* being similar to those of 2-U. A computational study of 1-U and 2-U explains their contrasting emission profiles in terms of the uranyl oxo ligands participating in the key transitions for 2-U but not for 1-U, with the stretching vibrations of the LN6 ligand also contributing to the fine structure.

Dual-Responsive fluorinated glycopolymers Targeting GLUT1 for enhanced BBB penetration and Activatable 19F MRI imaging

2025-06-13

Xuan Liu , Feng Liu , Yuan Lü +7 more | European Polymer Journal

Europium(II) Coordination Polymers with Bipyrimidine Linkers: Structural, Spectroscopic, and Magnetic Studies

2025-06-13

Nithin Suryadevara , Marcus J. Giansiracusa , Robert W. Gable +1 more | Crystal Growth & Design

Isolated carbon(I) species featuring a carbone cation radical

2025-06-13

Yi‐Chen Chan , He-Xin Xiao , Lei Qin +7 more | Nature Synthesis

Regioisomerism Induced Circularly Polarized Luminescence Switching in Natural (+)-Camphor-Based Bis(pyrazolyl)pyridine Europium(III) Complexes

2025-06-13

Justin Cado , Alexandre Abhervé , Maxime Grasser +5 more | Inorganic Chemistry

Chiral 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligands containing camphor units have been used in their enantiopure, racemic, and meso forms to prepare luminescent europium(III) complexes. The bpp ligands have been fully characterized by … Chiral 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligands containing camphor units have been used in their enantiopure, racemic, and meso forms to prepare luminescent europium(III) complexes. The bpp ligands have been fully characterized by single-crystal X-ray diffraction and chiroptical spectroscopy. For one of the enantiopure ligands, namely bis(4S,7R)camphor-2,2-bpp, the regioisomer bis(4S,7R)camphor-1,2-bpp, containing one pyrazole connected through the N1 nitrogen atom, has been obtained and used to coordinate the europium(III) ion. Ancillary hexafluoroacetylacetonato ligands were used to complete the coordination sphere of the lanthanide. The complexes with the 2,2-bpp ligands have been structurally characterized by single-crystal X-ray diffraction. They are isostructural in spite of the noncentrosymmetric monoclinic P21 space group for the enantiopure compounds and the centrosymmetric monoclinic P21/n space group for the meso and the racemic ones. The metal center is ennea-coordinated within slightly distorted Muffin-type geometry. The three enantiopure complexes show strong circularly polarized luminescence activity, with anisotropy factors glum reaching up ±0.2 for the 7F1 ← 5D0 magnetic dipole sensitive transition. Most remarkably, the polarization of the emission is inverted for the two complexes bearing the regioisomeric bis(4S,7R)camphor-2,2-bpp and bis(4S,7R)camphor-1,2-bpp ligands, yet having the same absolute configuration of the camphor units, thus allowing an unprecedented possibility of CPL switching.

Impact of ancillary ligands with varied conjugated structures on the NIR luminescence of β-diketone Nd(III) compounds

2025-06-13

Yanping Dong , Xiqiang Tian , Xiaobo Bai +3 more | Inorganic Chemistry Communications

Strontium Tris(cyclopentadienyl) Complexes: Isostructural f0/d0 Analogues of Divalent Lanthanides

2025-06-13

Samuel B. Zlotnikov , Nicholas Katzer , Patrick W. Smith +3 more | Inorganic Chemistry

Isostructural, diamagnetic diluents are commonly used in magnetic investigations to eliminate interactions between neighboring electron spins. For divalent lanthanides, these diluents are currently limited to closed-shell ytterbium(II) complexes; ytterbium(II), however, … Isostructural, diamagnetic diluents are commonly used in magnetic investigations to eliminate interactions between neighboring electron spins. For divalent lanthanides, these diluents are currently limited to closed-shell ytterbium(II) complexes; ytterbium(II), however, is a poor size-match for the large early- and mid-lanthanides, precluding access to certain ligand frameworks. To aid in the study of lanthanide(II) complexes with unconventional electronic structures and magnetic properties, three strontium tris-cyclopentadienyl complexes, [K(2.2.2-cryptand)][SrCpR3], with common substituted cyclopentadienyl ligands, CpR = C5Me4H (Cptet), C5H4(SiMe3) (Cp'), and C5H3(SiMe3)2 (Cp″) were synthesized, characterized, and examined as diamagnetic diluents. En route to their synthesis, two new Sr metallocenes, [SrCpR2] CpR = Cptet, Cp', were also prepared. [K(2.2.2-cryptand)][SrCptet3] was used to dilute the new complex [K(2.2.2-cryptand)][EuIICptet3], and the EPR spectra of the diluted material shows narrower linewidths than those of pure [K(2.2.2-cryptand)][EuIICptet3], suggesting an increase in the spin-spin relaxation time that enables determination of the europium hyperfine coupling constant.

A Shape‐Complementarity Approach to Inducing Short Au(III)···Au(III) Contacts in Tetracyanoaurate(III) Salts

2025-06-12

Thomas E. Karpiuk , Robby Y. Williams‐Sekiguchi , Samyadeb Mahato +2 more | Chemistry - A European Journal

Abstract Six sets of tetracyanoaurate(III) salts were synthesized and structurally characterized using the metal‐ligand complex cations [RE(bipyO 2 ) 4 ] 3+ (RE = Sc, Y, La; bipyO 2 = … Abstract Six sets of tetracyanoaurate(III) salts were synthesized and structurally characterized using the metal‐ligand complex cations [RE(bipyO 2 ) 4 ] 3+ (RE = Sc, Y, La; bipyO 2 = 2,2′‐bipyridine‐ N , N ’‐dioxide), [Fe(bipyO 2 ) 3 ] 3+ , [Ln(dmbipyO 2 ) 4 ] 3+ (Ln = Ce, Eu, Yb; dmbipyO 2 = 4,4′‐dimethyl‐2,2′‐bipyridine‐ N , N ’‐dioxide), [Ca(tcmc)] 2+ (tcmc = 1,4,7,10‐tetrakis‐(carbamoylmethyl)‐1,4,7,10‐tetraazacyclododecane), and [Ca(12‐crown‐4) 2 ] 2+ . Noncovalent assembly of the [Au(CN) 4 ] − anions tended to occur via Au···N cyano interactions; however, rare Au(III)···Au(III) contacts between the [Au(CN) 4 ] − groups — suggesting aurophilicity — could be induced when certain cation shape requirements were met. Specifically, cations with shape, size, and symmetry that allowed for packing in a complementary fashion with Au(III)···Au(III) aligned [Au(CN) 4 ] − dimers or trimers — providing efficiently close‐packed layers — were found to be sufficient for manifesting Au(III)···Au(III) contacts. Modifying the [RE(bipyO 2 ) 4 ] 3+ cation with peripheral methyl groups (the [Ln(dmbipyO 2 ) 4 ] 3+ cation) caused isoreticular replacement of a {[Au(CN) 4 ] 3 } 3− trimer with a dumbbell‐shaped {[Au(CN) 4 ] 2 Cl} 3− tri‐anion featuring an unusual Au···Cl···Au bridge — illustrating that the assembly of the anionic groups will adapt to conserve the same close packing. Au(III) aurophilicity between the [Au(CN) 4 ] − groups was studied using computational methods, crystal packing of the structures was probed using Hirshfeld surface analysis, and the emission properties of compounds containing the [Eu(dmbipyO 2 ) 4 ] 3+ luminophore were investigated, showing high quantum yields of ca . 50%.

Tb2(DPA)2(HDPA)2 Green Emitter Coordination Compound: Photometric Analysis and Temperature‐Dependence Luminescence

2025-06-10

Ch. J. Salas‐Juárez , I. Garduño‐Wilches , Gerardo Chávez-Esquivel +7 more | Applied Organometallic Chemistry

ABSTRACT Lanthanide‐based coordination compounds are attractive materials for developing light‐emitting systems and optical sensors due to their sharp emissions and long‐lived excited states. In this work, we report the synthesis, … ABSTRACT Lanthanide‐based coordination compounds are attractive materials for developing light‐emitting systems and optical sensors due to their sharp emissions and long‐lived excited states. In this work, we report the synthesis, characterization, and luminescent performance of a novel terbium‐based coordination compound, Tb 2 (DPA) 2 (HDPA) 2 , obtained through a low‐temperature reaction between terbium (III) nitrate and dipicolinic acid (H 2 DPA) in methanol. FTIR, TGA, and PXRD analyses confirmed the coordination of H 2 DPA to Tb 3+ through both singly (HDPA − ) and fully deprotonated (DPA 2− ) forms, resulting in a 2:2:2 stoichiometry. The compound exhibits strong green photoluminescence dominated by the 5 D 4 → 7 F 5 transition, with a lifetime of 1.5 ms and an absolute quantum yield of 50% under λ exc = 330 nm. Photometric characterization revealed CIE 1931 chromaticity coordinates of x = 0.33, y = 0.56 very close to the green standard phosphor European Broadcasting Union illuminant green ( x = 0.29, y = 0.60) and a color purity of 70%. For the 5 D 4 → 7 F 5 transition, a purity of 99.9% was calculated, confirming its potential for solid‐state lighting applications. Temperature‐dependent luminescence studies (30°C–150°C) presented a 90% loss in emission intensity at 100°C, rendering the material visually inactive beyond this point. This behavior supports its application as a thermal on/off indicator in areas such as electronics, industrial processing, and safety labeling.