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Lanthanide Luminescence: Fundamental Research and Applications

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A special issue of Molecules (ISSN 1420-3049).

Deadline for manuscript submissions: closed (30 September 2017) | Viewed by 36741

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Special Issue Editor

Dr. Svetlana V. Eliseeva

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Guest Editor

Centre de Biophysique Moléculaire, CNRS UPR 4301, F-45071 Orléans, CEDEX 2, France
Interests: visible and near-infrared lanthanide luminescence; lanthanide luminescence sensitization; energy transfer mechanisms; spectroscopy; microscopy; optical imaging; complexes; coordination polymers; dendrimers; nanomaterials

Special Issue Information

Dear Colleagues,

Intriguing emission features of lanthanide(III)-based compounds, i.e., narrow bandwidths of f-f transitions, long luminescence lifetimes, large difference between excitation and emission bands in the case of non-direct sensitization and high photostability, have triggered their diverse applications. Today, lanthanide(III) luminescence is essential for, but not limited to, use in telecommunications, lasers, security marking, lighting, sensing, immunoassays, luminescent thermometry, optical imaging, and biomedicine. Such developments have been accompanied by continuous efforts in the design and synthesis of small molecular complexes, macromolecules (supramolecular assemblies, coordination polymers or dendrimers), and nanomaterials (inorganic, polymer or silica nanoparticles) with improved luminescent and functional properties that would satisfy the demanding field of modern applications. Such progresses would not be also achieved without fundamental and theoretical studies devoted to the sensitization of lanthanide(III) luminescence and corresponding energy transfer mechanisms.

This Special Issue has the goal to gather recent exciting developments covering both fundamental and applied aspects of lanthanide(III) luminescence, to highlight difficulties encountered during design and synthesis of luminescent lanthanide(III)-based compounds, especially when the specific requirements have to be taken into account for a particular application.

Dr. Svetlana V. Eliseeva
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

Lanthanide
Complex
Nanomaterial
Supramolecular assembly
Coordination polymer
Metal-organic framework
Dendrimer
Hybrid material
Ionic liquid
Synthesis
Luminescence
Visible
Near-infrared
Energy transfer
Sensitization mechanism
Antenna effect
Upconversion
Downconversion
Downshifting
Spectroscopy
Optical imaging
Microscopy
Luminescent thermometry
Theranostics
Biomedicine
Immunoassay
Sensing
Phosphor
Lighting
Telecommunication
Laser
Security ink
Solar energy conversion
Scintillator

Published Papers (6 papers)

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Research

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11 pages, 1765 KiB

Open AccessArticle

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

by Yuki Hasegawa, Ayumi Ishii, Yudai Inazuka, Naho Yajima, Shogo Kawaguchi, Kunihisa Sugimoto and Miki Hasegawa

Molecules 2018, 23(2), 55; https://doi.org/10.3390/molecules23020055 - 24 Jan 2018

Cited by 11 | Viewed by 4716

Abstract

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

(This article belongs to the Special Issue Lanthanide Luminescence: Fundamental Research and Applications)

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2855 KiB

Open AccessFeature PaperArticle

Controlled Synthesis of Monodisperse Hexagonal NaYF₄:Yb/Er Nanocrystals with Ultrasmall Size and Enhanced Upconversion Luminescence

by Hui Li, Lei Xu and Guanying Chen

Molecules 2017, 22(12), 2113; https://doi.org/10.3390/molecules22122113 - 01 Dec 2017

Cited by 37 | Viewed by 6827

Abstract

The ability to synthesize upconversion nanocrystals (UCNCs) with tailored upconversion luminescence and controlled size is of great importance for biophotonic applications. However, until now, limited success has been met to prepare bright, ultrasmall, and monodispersed β-NaYF₄:Yb³⁺/Er³⁺ UCNCs. In this work, we report on a synthetic method to produce monodisperse hexagonal NaYF₄:Yb³⁺/Er³⁺ nanocrystals of ultrasmall size (5.4 nm) through a precise control of the reaction temperature and the ratio of Na⁺/Ln³⁺/F⁻. We determined the optimum activator concentration of Er³⁺ to be 6.5 mol % for these UCNCs, yielding about a 5-fold higher upconversion luminescence (UCL) intensity than the commonly used formula of NaYF₄:30% Yb³⁺/2% Er³⁺. Moreover, a thin epitaxial shell (thickness, 1.9 nm) of NaLnF₄ (Ln = Y, Gd, Lu) was grown onto these ultrasmall NaYF₄:Yb³⁺/Er³⁺ NCs, enhancing its UCL by about 85-, 70- and 50-fold, respectively. The achieved sub-10-nm core and core–shell hexagonal NaYF₄:Yb³⁺/Er³⁺ UCNCs with enhanced UCL have strong potential applications in bioapplications such as bioimaging and biosensing. Full article

(This article belongs to the Special Issue Lanthanide Luminescence: Fundamental Research and Applications)

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1682 KiB

Open AccessArticle

Design of Novel, Water Soluble and Highly Luminescent Europium Labels with Potential to Enhance Immunoassay Sensitivities

by Henri Sund, Kaj Blomberg, Niko Meltola and Harri Takalo

Molecules 2017, 22(10), 1807; https://doi.org/10.3390/molecules22101807 - 24 Oct 2017

Cited by 7 | Viewed by 4567

Abstract

To meet the continual demands of more-sensitive immunoassays, the synthesis of novel luminescent Eu(III) chelate labels having similar substituted 4-(phenylethynyl)pyridine chromophores in three different chelate structure classes are reported. Significantly enhanced luminescence intensities were obtained, evidently caused by the intra-ligand charge transfer (ILCT) mediated sensitization, but the alternative ligands triplet state process cannot be ruled out. Based on the present study, even quite small changes on the chelate structure, and, especially, on the substituents’ donor/acceptor strength on both ends of 4-(phenylethynyl)pyridine subunits have an unpredictable effect on the luminescence. The highest observed brightness was 16,400 M⁻¹cm⁻¹ in solution and 69,500 M⁻¹cm⁻¹ on dry surface, being 3.4 and 8.7 fold higher compared to the reference chelate. The new label chelates provide solutions for improved assay sensitivity up-to tenfold from the present concepts. Full article

(This article belongs to the Special Issue Lanthanide Luminescence: Fundamental Research and Applications)

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2671 KiB

Open AccessArticle

Synthesis of Europium-Doped Fluorapatite Nanorods and Their Biomedical Applications in Drug Delivery

by Haifeng Zeng, Xiyu Li, Muyang Sun, Sufan Wu and Haifeng Chen

Molecules 2017, 22(5), 753; https://doi.org/10.3390/molecules22050753 - 06 May 2017

Cited by 22 | Viewed by 6098

Abstract

Europium (Eu)-doped fluorapatite (FA) nanorods have a biocompatibility similar to that of hydroxyapatite (HA) for use as cell imaging biomaterials due to their luminescent property. Here, we discuss the new application of europium-doped fluorapatite (Eu-FA) nanorods as an anticancer drug carrier. The Eu-FA nanorods were prepared by using a hydrothermal method. The morphology, crystal structure, fluorescence, and composition were investigated. The specific crystal structure enables the effective loading of drug molecules. Doxorubicin (DOX), which was used as a model anticancer drug, effectively loaded onto the surface of the nanorods. The DOX release was pH-dependent and occurred more rapidly at pH 5.5 than at pH 7.4. The intracellular penetration of the DOX-loaded Eu-FA nanorods (Eu-FA/DOX) can be imaged in situ due to the self-fluorescence property. Treatment of melanoma A375 cells with Eu-FA/DOX elicited a more effective apoptosis rate than direct DOX treatment. Overall, Eu-FA exhibits potential for tracking and treating tumors and may be potentially useful as a multifunctional carrier system to effectively load and sustainably deliver drugs. Full article

(This article belongs to the Special Issue Lanthanide Luminescence: Fundamental Research and Applications)

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Review

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4761 KiB

Open AccessReview

Upconversion Luminescence Sensitized pH-Nanoprobes

by Manoj Kumar Mahata, Hyeongyu Bae and Kang Taek Lee

Molecules 2017, 22(12), 2064; https://doi.org/10.3390/molecules22122064 - 25 Nov 2017

Cited by 40 | Viewed by 7523

Abstract

Photon upconversion materials, featuring excellent photophysical properties, are promising for bio-medical research due to their low autofluorescence, non-cytotoxicity, low photobleaching and high photostability. Upconversion based pH-nanoprobes are attracting considerable interest due to their superiority over pH-sensitive molecular indicators and metal nanoparticles. Herein, we review the advances in upconversion based pH-nanoprobes, the first time in the seven years since their discovery in 2009. With a brief discussion on the upconversion materials and upconversion processes, the progress in this field has been overviewed, along with the toxicity and biodistribution of upconversion materials for intracellular application. We strongly believe that this survey will encourage the further pursuit of intense research for designing molecular pH-sensors. Full article

(This article belongs to the Special Issue Lanthanide Luminescence: Fundamental Research and Applications)

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11469 KiB

Open AccessReview

Lanthanide Photoluminescence in Heterometallic Polycyanidometallate-Based Coordination Networks

by Szymon Chorazy, Maciej Wyczesany and Barbara Sieklucka

Molecules 2017, 22(11), 1902; https://doi.org/10.3390/molecules22111902 - 04 Nov 2017

Cited by 54 | Viewed by 6196

Abstract

Solid-state functional luminescent materials arouse an enormous scientific interest due to their diverse applications in lighting, display devices, photonics, optical communication, low energy scintillation, optical storage, light conversion, or photovoltaics. Among all types of solid luminophors, the emissive coordination polymers, especially those based on luminescent trivalent lanthanide ions, exhibit a particularly large scope of light-emitting functionalities, fruitfully investigated in the aspects of chemical sensing, display devices, and bioimaging. Here, we present the complete overview of one of the promising families of photoluminescent coordination compounds, that are heterometallic d–f cyanido-bridged networks composed of lanthanide(3+) ions connected through cyanide bridges with polycyanidometallates of d-block metal ions. We are showing that the combination of cationic lanthanide complexes of selected inorganic and organic ligands with anionic homoligand [M(CN)x]ⁿ⁻ (x = 2, 4, 6 and 8) or heteroligand [M(L)(CN)4]²⁻ (L = bidentate organic ligand, M = transition metal ions) anions is the efficient route towards the emissive coordination networks revealing important optical properties, including 4f-metal-centred visible and near-infrared emission sensitized through metal-to-metal and/or ligand-to-metal energy transfer processes, and multi-coloured photoluminescence switchable by external stimuli such as excitation wavelength, temperature, or pressure. Full article

(This article belongs to the Special Issue Lanthanide Luminescence: Fundamental Research and Applications)

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