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Special Issue "Lanthanides: New Trends and Applications"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Photochemistry".

Deadline for manuscript submissions: 31 August 2019

Special Issue Editor

Guest Editor
Dr. Lianshe Fu

CICECO-Aveiro Institute of Materials, University of Aveiro, Portugal
Website | E-Mail
Interests: lanthanide; photoluminescence; organic-inorganic hybrid; white light-emitting diode; luminescent solar concentrator; sol-gel method; computational chemistry

Special Issue Information

Dear Colleagues,

Lanthanide (Ln) compounds have been widely applied to display, solid-state lighting, integrated optics and optical telecommunications fields due to their intrinsic luminescent features, such as high emission quantum yield, narrow bandwidth, long lifetimes and ligand-dependent luminescence sensitization. In recent years, Ln-based organic-inorganic hybrids, metal-organic frameworks, gels (hydrogels and organogels) as monoliths, thin films or nanomaterials have been synthesized and show new trends in molecular thermometers, chemical sensing, luminescent solar concentrators, white light-emitting diodes, anticounterfeiting, quick response code and biomedical (biosensing, imaging and theranostics) applications. These materials can also be tailored for multifunctional applications owing to the diverse emission profiles and color tunablilities.

The aim of this Special Issue is to collect the contributions from researchers and experts to study all application aspects of Ln-based materials. I would like to cordially invite you to submit an article to this Special Issue. Full papers, short communications and reviews are all welcome.

Dr. Lianshe Fu
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 papers will be 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 1800 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
  • Phosphor
  • Organic-inorganic hybrid
  • Coordination polymer
  • Metal-organic framework
  • Ionic liquid
  • Sol-gel method
  • Luminescence
  • Downconversion
  • Downshifting
  • Upconversion
  • Sensing
  • Lighting
  • Optical imaging
  • Luminescent solar concentrator
  • White light-emitting diode
  • Luminescent thermometry
  • Biomedical application
  • Telecommunication
  • Logic gate

Published Papers (6 papers)

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Research

Open AccessArticle
Bio-mining of Lanthanides from Red Mud by Green Microalgae
Molecules 2019, 24(7), 1356; https://doi.org/10.3390/molecules24071356
Received: 15 March 2019 / Revised: 3 April 2019 / Accepted: 4 April 2019 / Published: 6 April 2019
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Abstract
Red mud is a by-product of alumina production containing lanthanides. Growth of green microalgae on red mud and the intracellular accumulation of lanthanides was tested. The best growing species was Desmodesmus quadricauda (2.71 cell number doublings/day), which accumulated lanthanides to the highest level [...] Read more.
Red mud is a by-product of alumina production containing lanthanides. Growth of green microalgae on red mud and the intracellular accumulation of lanthanides was tested. The best growing species was Desmodesmus quadricauda (2.71 cell number doublings/day), which accumulated lanthanides to the highest level (27.3 mg/kg/day), if compared with Chlamydomonas reinhardtii and Parachlorella kessleri (2.50, 2.37 cell number doublings and 24.5, 12.5 mg/kg per day, respectively). With increasing concentrations of red mud, the growth rate decreased (2.71, 2.62, 2.43 cell number doublings/day) due to increased shadowing of cells by undissolved red mud particles. The accumulated lanthanide content, however, increased in the most efficient alga Desmodesmus quadricauda within 2 days from zero in red-mud free culture to 12.4, 39.0, 54.5 mg/kg of dry mass at red mud concentrations of 0.03, 0.05 and 0.1%, respectively. Red mud alleviated the metal starvation caused by cultivation in incomplete nutrient medium without added microelements. Moreover, the proportion of lanthanides in algae grown in red mud were about 250, 138, 117% higher than in culture grown in complete nutrient medium at red mud concentrations of 0.03, 0.05, 0.1%. Thus, green algae are prospective vehicles for bio-mining or bio-leaching of lanthanides from red mud. Full article
(This article belongs to the Special Issue Lanthanides: New Trends and Applications)
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Open AccessArticle
Formation, Photophysics, and Photochemistry of Anionic Lanthanide(III) Mono- and Bisporphyrins
Molecules 2019, 24(7), 1309; https://doi.org/10.3390/molecules24071309
Received: 28 February 2019 / Revised: 29 March 2019 / Accepted: 31 March 2019 / Published: 3 April 2019
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Abstract
Since water-soluble porphyrin complexes of lanthanides(III) have proved to be promising for medical applications (e.g., luminescence imaging, photodynamic therapy, and theranostics), the investigation of the formation, photophysical, and photochemical properties of such coordination compounds provides useful pieces of information for their potential usage. [...] Read more.
Since water-soluble porphyrin complexes of lanthanides(III) have proved to be promising for medical applications (e.g., luminescence imaging, photodynamic therapy, and theranostics), the investigation of the formation, photophysical, and photochemical properties of such coordination compounds provides useful pieces of information for their potential usage. Steady-state and time-resolved fluorometry, UV–Vis absorption spectroscopy, and continuous-wave photolysis were utilized for this purpose. 5,10,15,20-Tetrakis(4-sulfonatophenyl)porphyrin formed mono- and bisporphyrin complexes with samarium(III), europium(III), and gadolinium(III) as representatives in the middle of the lanthanide series. The special photoinduced behavior of these compounds was mostly determined by the position of the metal center, which was located out of the ligand plane, thus distorting it. Besides, the photochemical and, especially, photophysical features of the corresponding mono- and bisporphyrin complexes were similar because, in the latter species, two monoporphyrins were connected by a weak metal bridge between the peripheral sulfonato substituents (tail-to-tail dimerization). The formation of these coordination compounds and the transformation reactions between the mono- and bisporphyrins were rather slow in the dark at room temperature. These processes were accelerated by visible irradiation. However, dissociation and, especially, redox degradation were the main photoreactions in these systems, although with low quantum yields. Additionally, depending on the excitation wavelength, new types of photoproducts were also detected. Full article
(This article belongs to the Special Issue Lanthanides: New Trends and Applications)
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Open AccessArticle
Synthesis and Near Infrared Luminescence Properties of a Series of Lanthanide Complexes with POSS Modified Ligands
Molecules 2019, 24(7), 1253; https://doi.org/10.3390/molecules24071253
Received: 17 January 2019 / Revised: 25 March 2019 / Accepted: 27 March 2019 / Published: 30 March 2019
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Abstract
A polyhedral oligomeric silsesquioxanes (POSS) modified 8-hydroxyquinoline derivative (denoted as Q-POSS) was synthesized and used as a ligand to coordinate with lanthanide ions to obtain a series of lanthanide complexes Ln(Q-POSS)3 (Ln = Er3+, Yb3+, Nd3+). [...] Read more.
A polyhedral oligomeric silsesquioxanes (POSS) modified 8-hydroxyquinoline derivative (denoted as Q-POSS) was synthesized and used as a ligand to coordinate with lanthanide ions to obtain a series of lanthanide complexes Ln(Q-POSS)3 (Ln = Er3+, Yb3+, Nd3+). The as-prepared lanthanide complexes have been characterized by FT-IR, UV–Vis, and elemental analysis. All these complexes showed the characteristic near-infrared (NIR) luminescence originated from the corresponding lanthanide ions under excitation. Compared with the unmodified counterparts LnQ3 (HQ = 8-hydroxyquinoline), the Ln(Q-POSS)3 complexes showed obviously increased emission intensity, which was ascribed mainly to the steric-hindrance effects of the POSS moiety in the ligands. It is believed that the POSS group could suppress undesired excimer formation and intermolecular aggregation, thus decreasing the concentration quenching effect of the corresponding lanthanide complexes. Full article
(This article belongs to the Special Issue Lanthanides: New Trends and Applications)
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Open AccessArticle
Catalytic Asymmetric Fluorination of Alkyl 1-indanone-2-carboxylates Ruled by Pybox-Eu(III) Combination
Molecules 2019, 24(6), 1141; https://doi.org/10.3390/molecules24061141
Received: 7 March 2019 / Revised: 19 March 2019 / Accepted: 20 March 2019 / Published: 22 March 2019
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Abstract
A highly enantioselective catalytic method for the synthesis of quaternary α-fluoro derivatives of 3-oxo esters is described. The reaction uses europium (III) triflate and commercially available chiral pybox-type C2-symmetric ligand. Excellent results in terms of yields and enantioselectivities were assured using the electrophilic [...] Read more.
A highly enantioselective catalytic method for the synthesis of quaternary α-fluoro derivatives of 3-oxo esters is described. The reaction uses europium (III) triflate and commercially available chiral pybox-type C2-symmetric ligand. Excellent results in terms of yields and enantioselectivities were assured using the electrophilic NFSI reagent under mild reaction conditions. Full article
(This article belongs to the Special Issue Lanthanides: New Trends and Applications)
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Graphical abstract

Open AccessFeature PaperArticle
Luminescent κ-Carrageenan-Based Electrolytes Containing Neodymium Triflate
Molecules 2019, 24(6), 1020; https://doi.org/10.3390/molecules24061020
Received: 13 February 2019 / Revised: 6 March 2019 / Accepted: 8 March 2019 / Published: 14 March 2019
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Abstract
In recent years, the synthesis of polymer electrolyte systems derived from biopolymers for the development of sustainable green electrochemical devices has attracted great attention. Here electrolytes based on the red seaweeds-derived polysaccharide κ-carrageenan (κ-Cg) doped with neodymium triflate (NdTrif3) and glycerol [...] Read more.
In recent years, the synthesis of polymer electrolyte systems derived from biopolymers for the development of sustainable green electrochemical devices has attracted great attention. Here electrolytes based on the red seaweeds-derived polysaccharide κ-carrageenan (κ-Cg) doped with neodymium triflate (NdTrif3) and glycerol (Gly) were obtained by means of a simple, clean, fast, and low-cost procedure. The aim was to produce near-infrared (NIR)-emitting materials with improved thermal and mechanical properties, and enhanced ionic conductivity. Cg has a particular interest, due to the fact that it is a renewable, cost-effective natural polymer and has the ability of gelling in the presence of certain alkali- and alkaline-earth metal cations, being good candidates as host matrices for accommodating guest cations. The as-synthesised κ-Cg-based membranes are semi-crystalline, reveal essentially a homogeneous texture, and exhibit ionic conductivity values 1–2 orders of magnitude higher than those of the κ-Cg matrix. A maximum ionic conductivity was achieved for 50 wt.% Gly/κ-Cg and 20 wt.% NdTrif3/κ-Cg (1.03 × 10−4, 3.03 × 10−4, and 1.69 × 10−4 S cm−1 at 30, 60, and 97 °C, respectively). The NdTrif-based κ-Cg membranes are multi-wavelength emitters from the ultraviolet (UV)/visible to the NIR regions, due to the κ-Cg intrinsic emission and to Nd3+, 4F3/24I11/2-9/2. Full article
(This article belongs to the Special Issue Lanthanides: New Trends and Applications)
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Graphical abstract

Open AccessFeature PaperArticle
Ammonia-Responsive Luminescence of Ln3+-β-diketonate Complex Encapsulated within Zeolite Y
Molecules 2019, 24(4), 685; https://doi.org/10.3390/molecules24040685
Received: 22 January 2019 / Revised: 7 February 2019 / Accepted: 12 February 2019 / Published: 14 February 2019
Cited by 1 | PDF Full-text (4149 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Assembling Ln3+(HPBAn) (Ln = Eu or Tb, HPBA = N-(2-pyridinyl)benzoylacetamide) in the cavities of zeolite Y (ZY) via the “ship-in-a-bottle” strategy leads to the formation of novel luminescent composite, Ln(HPBAn)@ZY, whose luminescence can be easily modulated by [...] Read more.
Assembling Ln3+(HPBAn) (Ln = Eu or Tb, HPBA = N-(2-pyridinyl)benzoylacetamide) in the cavities of zeolite Y (ZY) via the “ship-in-a-bottle” strategy leads to the formation of novel luminescent composite, Ln(HPBAn)@ZY, whose luminescence can be easily modulated by ammonia on the basis of the energy level variation of HPBA after deprotonation process. Additionally the bimetallic complex doping sample, Eu0.5Tb0.5(HPBAn)@ZY, show great potential as self-referencing luminescent sensor for detecting low ammonia concentration of 10−12–0.25 wt%. Full article
(This article belongs to the Special Issue Lanthanides: New Trends and Applications)
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Graphical abstract

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