Luminescent Lanthanide Research Articles

Lanthanide luminescence nanothermometer with working wavelength beyond 1500 nm for cerebrovascular temperature imaging in vivo

Nanothermometers enable the detection of temperature changes at the microscopic scale, which is crucial for elucidating biological mechanisms and guiding treatment strategies. However, temperature monitoring of micron-scale structures in vivo using luminescent nanothermometers remains challenging, primarily due to the severe scattering effect of biological tissue that compromises the imaging resolution. Herein, a lanthanide luminescence nanothermometer with a working wavelength beyond 1500 nm is developed to achieve high-resolution temperature imaging in vivo. The energy transfer between lanthanide ions (Er3+ and Yb3+) and H2O molecules, called the environment quenching assisted downshifting process, is utilized to establish temperature-sensitive emissions at 1550 and 980 nm. Using an optimized thin active shell doped with Yb3+ ions, the nanothermometer’s thermal sensitivity and the 1550 nm emission intensity are enhanced by modulating the environment quenching assisted downshifting process. Consequently, minimally invasive temperature imaging of the cerebrovascular system in mice with an imaging resolution of nearly 200 μm is achieved using the nanothermometer. This work points to a method for high-resolution temperature imaging of micron-level structures in vivo, potentially giving insights into research in temperature sensing, disease diagnosis, and treatment development.

Current Development of Lanthanide Complexes for Biomedical Applications.

Luminescent molecule-based bioimaging system is widely used for precise localization and distinction of cancer/tumor cells. Luminescent lanthanide (Ln(III)) complexes offer long-lived (sub-millisecond time scale) and sharp (FWHM <10 nm) emission, arising from the forbidden 4f-4f electronic transitions. Luminescent Ln(III) complex-based bioimaging has emerged as a promising option for both in vitro and in vivo visualizations. In this mini-review, the historical development and recent significant progress of luminescent Ln(III) probes for bioapplications are introduced. The recent studies are mainly focused on three points: (i) the structural modifications of Ln(III) complexes in both macrocyclic and small ligands, (ii) the acquirement of high resolution luminescence images of cancer/tumor cells and (iii) the constructions of ratiometric biosensors. Furthermore, our recent study is explained as a new Cancer GPS (cancer grade probing for determining tumor grade through photophysical property analyses of intracellular Eu(III) complex.

Achieving Cross Time-Domain Multiplexed Signal Cascade and Cancer Exosomes Identification by Bridging Long Lifetime Phosphor to NIR-II Lanthanide Energy Transfer.

Designing lanthanide luminescence lifetime sensors in the second near-infrared (NIR-II) window holds great potentials for physiological studies. However, the single lifetime signal is confined to one or two orders of magnitude of signal variation, which limits the sensitivity of lifetime probes. In this study, a lifetime cascade system, i.e., ZGO:Mn, Eu-DNA-1/TCPP-PEI70K@Yb-AptEpCAM, with a variety of signals (τm, τn, τµ, τm/τn and τm/τµ) is constructed for exosome identification using time-domain multiplexing. The sensitized ligand TCPP acts as both target-modulated switch and a bridge for connecting long lifetime ZGO:Mn, Eu-DNA-1 emitter to lanthanide Yb3+. This drives successive dual-path energy transfer and forms two D(donor)-A(acceptor) pairs. The lifetime variation is dominantly modulated by arranging TCPP as energy intermediate relay to covert milliseconds to nanoseconds to microseconds. It enables a broad lifetime range of six orders of magnitude. The presence of exosome specifically recognizes aptamers on TCPP-PEI70K@Yb-AptEpCAM to impede D-A pairs and reverse multiplexed response signals of the lifetime cascade system. The ratio lifetime signals τm/τn and τm/τµ achieve prominent exosome quantification and exosome type differentiation attributed to signal amplification. The cascade system relying on lifetime criteria can realize precise quantization and provide an effective strategy for subsequent physiological study.

Modulation of lanthanide luminescence by carbamoylmethylphosphine oxide ligand: A theoretical study

The antenna capacity of Phenacyldiphenylphosphine oxide (Phenac), combining C=O and P=O donor groups was established by theoretical examination of its chromophore properties, binding ability to encapsulate and stabilize lanthanide complexes and potential to sensitize the EuIII and TbIII luminescence in Eu(Phenac)2(NO3)3(H2O) (1), Eu(Phenac)2(NO3)3 (2), Eu(Phenac)3(NO3)3 (3) and Tb(Phenac)2(NO3)3(H2O) (4) complexes in vacuum, solution and solid phase. The ligand-centered singlet and triplet excited state energies, the rates and lifetimes for the rival nonradiative (S1→T1,2 intersystem crossing (ISC)) and radiative and nonradiative S1→S0 and T1→S0 relaxation were predicted by means of DFT/TDDFT/ωB97XD calculations. Similar relaxation paths were found for all complexes. The absorbed energy by Sn > 1(π-π*) states relaxed to T1min by major ISC mechanism S1→T2→T1. The long radiative lifetime of S1→S0 due to n(p(C)(O))π-π*,p(P) character facilitated the forward ISC process. The environment, Phenac's number and LnIII size affect the T1 energy ∼0.1 eV. The calculated (Phenac→EuIII) energy transfer rates suggested the most likely T1 → 5D1/5D0 channels for a population of emitting metal-centered states. The small Φ of EuIII and larger luminescence of TbIII were discussed and explained. The importance of the P=O and C=O groups for the coordination ability and absorption properties of Phenac has been elucidated.

Simultaneously significant transparency enhancement and efficient temperature feedback achieved in AlON ceramic through luminescent rare earth doping

Activator-doped aluminum oxynitride (γ-AlON) could provide an extremely versatile transparent ceramic with photothermal feedback, opening the door to many new applications and devices for use in extreme conditions. However, existing AlON transparent ceramics have failed to achieve temperature-responsive luminescence. To address this, a simple-to-implement luminescent rare-earth doping strategy for fabricating AlON transparent ceramic with efficient temperature feedback is proposed and demonstrated. Luminescent Pr2O3 serves as the illustrative example. Benefiting from the liquid phase formed by Pr2O3 and the thermal coupling between the 3P1 and 3P0 levels of Pr3+, AlON ceramics doped with Pr2O3 exhibit significantly elevated transparency and temperature-responsive luminescence. More importantly, the AlON:Pr ceramic can serve as photothermal feedback windows, which presents attractive performance. This paradigm fills an important gap in the AlON transparent ceramics for temperature feedback windows, and will inspire the controllable design of luminescent rare-earth doped AlON ceramics for use in harsh conditions.

Comprehensive Photophysical and Nonlinear Spectroscopic Study of Thioanisolyl‐Picolinate Triazacyclononane Lanthanide Complexes

AbstractDetailed photophysical studies of luminescent lanthanide complexes are presented and elaborated using a newly developed thioanisolyl‐picolinate antenna and the related tacn macrocyclic ligand. The new ligand proved to sensitise Nd(III), Sm(III), Eu(III) and Yb(III) emission. Eu(III) complex showed complete energy transfer, yielding high quantum yield (44 %) and brightness, while the Tb(III) analogue underwent a thermally activated back‐energy transfer, resulting in a strong oxygen quenching of the triplet excited state. Transient absorption spectroscopy measurements of Gd(III), Tb(III) and Eu(III) compounds confirmed the sensitization processes upon the charge‐transfer antenna excitation. The triplet excited state lifetime of the Tb(III) complex was 5‐times longer than that of the Gd(III) analogue. In contrast, the triplet state was totally quenched by the energy transfer to the 4f‐metal ion in the Eu(III) species. Nonlinear two‐photon absorption highlighted efficient biphotonic sensitization in Eu(III) and Sm(III) complexes. In case of the Nd(III) compound, one‐photon absorption in 4f–4f transitions was predominant, despite the excitation at the antenna two‐photon band. This phenomenon was due to the Nd(III) 4f–4f transitions overlapping with the wavelength‐doubled absorption of the complex.

The research progress of X-ray excited lanthanide-doped nanoparticles

X-rays, renowned for their powerful penetration capabilities, are wildly used in medical diagnostics and material sciences. The distinctive electronic configurations of lanthanide-doped nanoparticles result in their unique luminescent properties. In this review, we first discussed the luminescent mechanism of X-ray-activated lanthanide nanomaterials, including conversion, transport, and luminescence. We then provide a comprehensive summary of the design strategies for lanthanide-doped nanoparticles, the selection of suitable host matrices, choosing the right lanthanide elements, optimizing structural configurations, and employing state-of-the-art synthesis methods. Finally, we highlight the applications of these nanoparticles in fields such as biosensing, photodynamic therapy, optical data storage and time-gated imaging, while also delving into the prospects and challenges associated with these nanoparticles.

High-nuclearity Luminescent Lanthanide Nanocages for Tumor Drug Delivery.

There is an unmet need for easy-to-visualize drug carriers that can deliver therapeutic cargoes deep into solid tumors. Herein, we report the preparation of ultrasmall luminescent imine-based lanthanide nanocages, Eu60 and Tb60 (collectively Ln60 ), designed to encapsulate anticancer chemotherapeutics for tumor therapy. The as-prepared nanocages possess large cavities suitable for the encapsulation of doxorubicin (DOX), yielding DOX@Ln60 nanocages with diameters around 5 nm. DOX@Ln60 are efficiently internalized by breast cancer cells, allowing the cells to be visualized via the intrinsic luminescent property of Ln(III). Once internalized, the acidic intracellular microenvironment promotes imine bond cleavage and the release of the loaded DOX. DOX@Ln60 inhibits DNA replication and triggers tumor cell apoptosis. In a murine triple negative breast cancer (TNBC) model, DOX@Ln60 was found to inhibit tumor growth with negligible side effects on normal tissues. It proved more effective than various controls, including DOX and Ln60 . The present nanocages thus point the way to the development of precise nanomedicines for tumor imaging and therapy.

Comprehensive performance of polycarbonate films doped with Tb(III) and Eu(III) complexes

AbstractIn order to expand the application of biobased polycarbonate in optical components, a series of isosorbide polycarbonate (PICC)/rare earth ion complex fluorescent composites were prepared by using PICC as a macromolecular ligand and Eu3+ and Tb3+ as rare earth luminescence centers. The coordination system between rare earth ions and PICC was investigated by Fourier transform infrared spectroscopy, DSC and TGA. On adjusting the ratio of Eu3+ and Tb3+, a PICC/rare earth ion composite with adjustable fluorescence color was obtained. Also, the thermal, mechanical and optical properties of a series of PICC/rare earth ion fluorescent films with different ratios were tested. A transparent fluorescent composite material with excellent mechanical properties and tunable fluorescent colors has been prepared. © 2024 Society of Industrial Chemistry.

Construction of Multifunctional Luminescent Lanthanide MOFs for Luminescent Sensing of Temperature, Trifluoroacetic Acid Vapor and Explosives.

Metal-organic frameworks (MOFs) with multifunctional and tunable optical properties have unique advantages in the field of sensing, and the structure and properties of MOFs are significantly influenced by the ligands. In this study, a Y-type tricarboxylic acid ligand containing amide bonds was synthesized through functional guidance, and three isomorphic and heterogeneous three-dimensional MOFs (Eu-MOF, Tb-MOF, and Gd-MOF) were obtained by solvothermal reaction. Further studies revealed that both the Tb-MOF and Eu-MOF could selectively detect picric acid (PA). The luminescence quenching of the two MOFs by PA was attributed to competing absorption and photoelectron energy transfer mechanisms. In addition, due to the energy transfer between Tb and Rhodamine B, Rhodamine B was encapsulated into Tb-MOF. The obtained material exhibited a linear relationship between the temperature parameters I544/I584 and temperature within the range of 280-400 K, the correlation coefficient (R2) reached an impressive value of 0.999, and the absolute sensitivity of the sample used for temperature sensing was 1.534% K-1. What is more, the material exhibited a good response to trifluoroacetic acid vapor, which suggests the potential of the material for temperature sensing and detection of trifluoroacetic acid vapor. The designed and investigated strategy can also serve as a reference for further research on excellent multifunctional sensors.

Ultrastarke Elektron‐Phonon‐Kopplung in Uran‐organischen Gerüstverbindungen führt zu einer inversen Temperaturabhängigkeit der Lumineszenz

AbstractElektron‐Phonon‐Wechselwirkungen, die in kondensierter Materie von entscheidender Bedeutung sind, werden in metallorganischen Gerüstverbindungen (MOFs) selten beobachtet. In Lanthanoid‐ oder Actinoid‐basierten Verbindungen gelingt der Nachweis dieser Wechselwirkungen typischerweise über die Analyse der Lumineszenz. Frühere Studien zu Ln‐ und Ac‐basierten MOFs bei hohen Temperaturen ergaben zusätzliche Lumineszenzsignale, die jedoch zu schwach für eine gründliche Analyse waren. Im Rahmen unserer Untersuchungen haben wir mithilfe eines Schicht‐für‐Schicht‐Verfahrens eine hochgeordnete, kristalline uranbasierte MOF‐Dünnschicht (KIT‐U‐1) hergestellt. Unter UV‐Licht zeigte diese Schicht zwei ausgeprägte „heiße Banden“, die auf eine starke Elektron‐Phonon‐Wechselwirkung hinweisen. Während bei 77 K keine Emissionsbanden sichtbar waren, erschien bei 300 K eine Emissionsbande mit der halben Intensität der Hauptbande. Überraschenderweise tauchte oberhalb von 320 K eine zweite, sogenannte heiße Bande auf, die von früheren Ergebnissen aus Seltenerd‐Verbindungen abweicht. Wir haben eine detaillierte ab initio‐Analyse mithilfe der zeitabhängigen Dichtefunktionaltheorie durchgeführt, um dieses ungewöhnliche Verhalten zu verstehen und die für die starke Elektron‐Phonon‐Kopplung verantwortliche Gitterschwingung zu identifizieren. Die heißen Emissionsbanden der KIT‐U‐1‐Schicht wurden dann dazu genutzt, ein hochempfindliches optisches Einkomponenten‐Thermometer zu entwickeln. Diese Ergebnisse belegen das Potenzial hochwertiger MOF‐Dünnschichten bei der Nutzung der einzigartigen Lumineszenz von Lanthanoiden und Actinoiden für neuartige Anwendungen.

Ultrastrong Electron-Phonon Coupling in Uranium-Organic Frameworks Leading to Inverse Luminescence Temperature Dependence.

Electron-phonon interactions, crucial in condensed matter, are rarely seen in Metal-Organic Frameworks (MOFs). Detecting these interactions typically involves analyzing luminescence in lanthanide- or actinide-based compounds. Prior studies on Ln- and Ac-based MOFs at high temperatures revealed additional peaks, but these were too faint for thorough analysis. In our research, we fabricated a high-quality, crystalline uranium-based MOF (KIT-U-1) thin film using a layer-by-layer method. Under UV light, this film showed two distinct "hot bands," indicating a strong electron-phonon interaction. At 77 K, these bands were absent, but at 300 K, a new emission band appeared with half the intensity of the main luminescence. Surprisingly, a second hot band emerged above 320 K, deviating from previous findings in rare-earth compounds. We conducted a detailed ab-initio analysis employing time-dependent density functional theory to understand this unusual behaviour and to identify the lattice vibration responsible for the strong electron-phonon coupling. The KIT-U-1 film's hot-band emission was then utilized to create a highly sensitive, single-compound optical thermometer. This underscores the potential of high-quality MOF thin films in exploiting the unique luminescence of lanthanides and actinides for advanced applications.

Ultrasensitive Eu-Based MOF Luminescence Sensor for Clenbuterol Visible Recognition.

Clenbuterol (CLB) as an illegal feed additive may cause a great security risk to food safety. However, convenient and efficient detection means for CLB in practical application remain a formidable challenge. Herein, a stable Eu-based organic framework {[H2N(CH3)2]2[Eu2(ttca)2]·H2O}n (compound 1) (H4ttca = [1,1':2',1″-terphenyl]-4,4',4″,5'-tetracarboxylic acid) has been harvested, exhibiting excellent chemical stability and thermal stability. Luminescence investigation reveals that compound 1 can sensitively and selectively detect CLB without being affected by different components from simulated serum and urine (limit detection: 22.7 nM). Furthermore, sensor 1 can also be applicable to CLB recognition in real swine feeds, presenting excellent anti-interference performance. The good cyclicity of compound 1 endows CLB determination with many advantages: low cost, high stability, and simplicity. Importantly, in view of the indication of the luminescence color (red to blue), test membranes were fabricated and employed for convenient and fast CLB detection, providing a valuable scheme for the visual monitoring of CLB in meat products. This work enriches rare earth metal compounds and luminescence sensor portfolios and breaks the concentration record (nM) for detecting CLB compared with reported complex materials, providing an effective monitoring platform for CLB visually.

Energy transfer process, luminescence optimizing and various applications of lanthanide complexes

Modulating the spectroscopic overlap between the emission bands of donors and the absorption spectra of acceptors by various simulations, it is possible to systematically investigate the emission behaviors of lanthanide complexes under different conditions. To establish the relationships between emission behaviors and various external simulations, it is necessary to study the energy transfer rate and efficiency between the donor and acceptor under different conditions to clarify the luminescent mechanism of the complexes, providing a theoretical basis for high-performance smart materials. This review focuses on the recent progress of luminescence performance of lanthanide complexes, including energy transfer mechanisms, emission color modulation, the strategies for optimizing lanthanide luminescence, and finally, various applications based on luminescence performance of lanthanide complexes and lanthanide metal-organic frameworks.

Multicolor Fluorescent Inks Based on Lanthanide Hybrid Organogels for Anticounterfeiting and Logic Circuit Design.

With the rapid development of information technology, the encrypted storage of information is becoming increasingly important for human life. The luminescent materials with a color-changed response under physical or chemical stimuli are crucial for information coding and anticounterfeiting. However, traditional fluorescent materials usually face problems such as a lack of tunable fluorescence, insufficient surface-adaptive adhesion, and strict synthesis conditions, hindering their practical applications. Herein, a series of luminescent lanthanide hybrid organogels (Ln-MOGs) were rapidly synthesized using a simple method at room temperature through the coordination between lanthanide ions and 2,6-pyridinedicarboxylic acid and 5-aminoisophthalic acid. And the multicolor fluorescent inks were also prepared based on the Ln-MOG and hyaluronic acid, with the advantages of being easy to write, color-adjustable, and water-responsive discoloration, which has been applied to paper-based anticounterfeiting technology. Inspired by the responsiveness of the fluorescent inks to water, we designed a logic system that can realize single-input logic operations (NOT and PASS1) and double-input logic operations (NAND, AND, OR, NOR, XOR). The encryption of a binary code can be actualized utilizing different luminescent response modes based on the logic circuit system. By adjusting the energy sensitization and luminescence mechanism of lanthanide ions in the gel structure, the information reading and writing ability of the fluorescent inks were verified, which has great potential in the field of multicolor pattern anticounterfeiting and information encryption.

Portable and Recyclable Luminescent Lanthanide Coordination Polymer Film Sensors for Adenosine Triphosphate in Urine.

Adenosine triphosphate (ATP) is a small molecule that is released to the urine from bladder urothelial cells and the bladder mucosal band of the human body. In certain cases, ATP can serve as a biomarker in bladder disease. For the practical applicability of luminescent sensors for ATP in urine, it is significant to find a new strategy for making the detection progress simple and available for in-field urine analysis. Here, a novel luminescent lanthanide coordination polymer (Tb-BPA) was designed and synthesized for quick and sensitive detection of ATP through luminescence quenching with a quenching constant of 4.90 × 103 M-1 and a detection limit of 0.55 × 10-6 M. Besides, Tb-BPA has excellent anti-interference ability and can detect ATP in simulated urine with a small relative standard deviation (<4%). Moreover, the luminescent polyacrylonitrile nanofiber films modified by Tb-BPA were prepared by electrospinning and were used for ATP visual detection. Notably, this film is easy to recover and reuse, and maintains good detection performance after at least 7 cycles.

Reversible Multimode Luminescence Modulations in Photochromic-Translucent Yb3+/Eu3+ Codoped K0.5Na0.5NbO3 Ceramics.

Luminescent tunable materials have promising application potential in optical switches, optical information storage, and so on. Although europium (Eu) is a good downconversion red luminescent rare earth element, there are few studies on the upconversion luminescence and photochromism of Eu-doped potassium sodium niobate (KNN) ferroelectrics. In this paper, Eu3+ and Yb3+ codoped KNN translucent ferroelectric ceramics were synthesized and the effect of Yb3+ content on the luminescence and photochromism is studied. Both the up- and downconversion luminescence intensity and decay rate before and after photochromism can be well controlled by Yb3+ content. That is, an upconversion luminescent translucent ceramic that can be completely discolored by 405 nm light illumination for 10 s was obtained. The luminescence modulations are closely related to the evolution of oxygen vacancy and crystal field around the luminescence center, which can be verified by the illumination-induced electron paramagnetic resonance (EPR) signal and local piezoresponse switching behavior variation as well as the discovery of energy level splitting and spectral line shift. We believe that this work shows a paradigm for designing high-performance reversible multimode luminescence modulation ferroelectric ceramics.

Construction of Highly Luminescent Lanthanide Coordination Polymers and Their Visualization for Luminescence Sensing.

NaH2SIP was selected as an organic ligand (NaH2SIP = 5-sulfoisophthalic acid monosodium salt). We successfully constructed a new class of lanthanide coordination polymers Ln-HS ([Ln(SIP)(DMF)(H2O)4]DMF·H2O; Ln = Eu, Tb, Sm, and Dy) by a simple solvothermal synthesis method. They exhibited excellent photoluminescence properties for Ln3+ ions, where Eu-HS and Tb-HS exhibited high quantum yields of 13.70 and 42.38%, respectively. The codoped lanthanide coordination polymers obtained by doping with different ratios of Eu3+/Tb3+ serve as excellent ratiometric thermometers with high sensitivities in the physiological temperature range, with values of 16.8, 7.0, and 14.5%·K-1, respectively. The luminescent colors of Tb0.95Eu0.05-HS and Tb0.94Eu0.06-HS exhibit variations from green to yellow to orange, achieving visualized luminescence in a narrow temperature range. The composite film material Tb0.94Eu0.06-HS@PMMA demonstrates this color variation. Next, Tb0.5Sm0.5-HS obtained by Tb3+/Sm3+ codoping was investigated. The difference in the luminescence colors visible to the naked eye at different excitation wavelengths and the change in luminescence colors occur in a very narrow temperature range. All of them show the great value of the visualized luminescence in practical anticounterfeiting, with double anticounterfeiting function and high security.

Contrasting impact of coordination polyhedra and site symmetry on the electronic energy levels in nine-coordinated Eu(III) and Sm(III) crystals structures determined from single crystal luminescence spectra.

Lanthanide luminescence is characterised by "forbidden" 4f-4f transitions and a complicated electronic structure. Our understanding of trivalent lanthanide(III) ion luminescence is centered on Eu3+ because absorbing and emitting transitions in Eu3+ occur from a single electronic energy level. In Sm3+ both absorbing and emitting multiplets have a larger multiplicity. A band arising in transitions from the first emitting state multiplet to the ground state multiplet will have nine lines for a Sm3+ complex. In this study, high-resolution emission and excitation spectra were used to determine the electronic energy levels for the lowest multiplet and first emitting multiplet in four Sm3+ compounds with either tricapped trigonal prismatic TTP or capped square antiprismatic cSAP coordination polyhedra but different site symmetry. This was achieved by the use of Boltzmann distribution population analysis and experimentally determined transition probabilities from emission and excitation spectra. Using this analysis it was possible to show the effect of changing three oxygen atoms with three nitrogen atoms in the donor set for two compounds with the same coordination polyhedra and site symmetry. This work celebrates the 40th anniversary of Kirby and Richardson's first report of [Eu(ODA)3]3- luminescence.

Step-wise changes in the excited state lifetime of [Eu(D2O)9]3+ and [Eu(DOTA)(D2O)]- as a function of the number of inner-sphere O-H oscillators.

Lanthanide luminescence is dominated by quenching by high-energy oscillators in the chemical environment. The rate of non-radiative energy transfer to a single H2O molecule coordinated to a Eu3+ ion exceeds the usual rates of emission by an order of magnitude. We know these rates, but the details of these energy transfer processes are yet to be established. In this work, we study the quenching rates of [Eu(D2O)9]3+ and [Eu(DOTA)(D2O)]- in H2O/D2O mixtures by sequentially exchanging the deuterons with protons. Flash freezing the solutions allows us to identify species with various D/H contents in solution and thus to quantify the energy transfer processes to individual OH-oscillators. This is not possible in solution due to fast exchange in the ensembles present at room temperature. We conclude that the energy transfer processes are accurately described, predicted, and simulated using a step-wise addition of the rates of quenching by each O-H oscillator. This documents the sequential increase in the rate of the energy transfer processes in the quenching of lanthanide luminescence, and further provides a methodology to identify isotopic impurities in deuterated lanthanide systems in solution.