Search Results (24)

We successfully synthesized millimeter-sized single crystals of the molecular erbium(III) complex Er(acac)₃(cphen), where acac = acetylacetonate and cphen = 5-chloro-1,10-phenanthroline. The novelty of this work stems from the exhaustive examination of the polar and electronic properties of the obtained samples at the macro-, micro-, and nanoscale levels. The single crystal X-ray diffraction method demonstrates the monoclinic (noncentrosymmetric space group P2₁) crystallographic structure of the synthesized samples and scanning electron microscopy exhibits the terrace–ledge morphology of the surface in erbium(III) crystals. By using the piezoelectric force microscopy mode, the origin of the polar properties and the hyperpolarizability in the synthesized samples were assigned to the internal domain structure framed by the characteristic terrace–ledge topography. The direct piezoelectric coefficient (~d33) was found to be intensely dependent on the local area and was measured in the range of 4–8 pm/V. A nanoscale study using the kelvin probe force and capacitance force (dC/dz) microscopy modes exposed the effect of the Er ions clustering in the erbium(III) complex. The PFM method applied solely to the Er ion revealed the corresponding direct piezoelectric coefficient (~d33) of about 4 pm/V. Given the maximum piezoelectric coefficient in the erbium(III) complex at 8 pm/V, we highlight the significant importance of the spatial coordination between the lanthanide ion and the ligands. The polar coordination between the lanthanide ion and the nitrogen and oxygen atoms was also corroborated by Raman spectroscopy supported by the density functional theory calculations. The obtained results can be of paramount importance for the application of molecular erbium(III) complex crystals in low-magnitude magnetic or electric field devices, which would reduce the energy consumption and speed up the processing switching in nonvolatile memory devices. Full article

The study provides novel insights into the crystal–chemical and optical characteristics of frankamenite. Frankamenite belongs to a special group (canasite group) of the complex alkaline Ca-(K)-(Na) silicates, and it was found in charoitites from the only known location, Murun Massif, Eastern Siberia, Russia. The crystal–chemical, vibrational, and optical properties of frankamenite were investigated by combining electron probe microanalysis (EPMA), single-crystal X-ray diffraction (SCXRD), infrared (IR) absorption, Raman, UV-Visible absorption, and electron spin resonance (ESR) spectroscopy. The behavior of the peaks in the IR spectra was also studied using ab initio calculations. Detailed characteristics of the internal composition and structure of the mineral species were described, and vibrational and optical properties based on these peculiarities were interpreted. The thermally stimulated reorientation of the H₂O molecules and OH⁻ groups was studied by thermo-Raman spectroscopy. Octahedral cationic positions can be readily doped with transition metal and lanthanide ions that provide a promising opportunity to adjust the Ce³⁺ luminescence. Hence, frankamenite is a potential material for ion exchange, novel phosphors, and luminophores. Full article

A new probe based on the complex of 1,2 dihydro-2-oxoquinoloine-4-carboxylic acid (DOCA) as a ligand with Europium (III) ion was developed for the quantitation of Moxifloxacin HCl (Moxi.HCl) in pharmaceuticals and human plasma using a luminescence method. The metal to ligand ratio of the complex is 1:2 as determined by a Job plot. The determination of Moxi.HCl is based on static quenching of the luminescence of the probe upon coordination of Moxi.HCl. The negative value for ΔG proves that this reaction is spontaneous. The calibration curve was constructed based on a Stern–Volmer equation and the quantitation range was 0.05–80 µg mL⁻¹. This is low enough to determine the drug in blood plasma, even hours after administration, which is not feasible with the methods published so far. The LOD was 15 ng mL⁻¹. The accuracy of the method was demonstrated by good recoveries of spiking experiments in tablets, ophthalmic eyedrops and human blood plasma, where the mean recovery was 99% with RSDs below 5%. The method was validated by closely matching concentrations of the drug found in all these real samples by HPLC. Additionally, Moxi.HCl can be assessed semi-quantitatively by eye vision upon excitation with a UV lamp at 365 nm by a gradual color shift from red to blue with increasing concentrations of Moxi.HCl. Full article

A desirable lanthanide-based ratiometric fluorescence probe was designed as a multifunctional nanoplatform for the determination of dipicolinic acid (DPA), a unique bacterial endospore biomarker, with high selectivity and sensitivity. The carbon dots (CDs) with blue emission wavelengths at 470 nm are developed with europium ion (Eu³⁺) to form Eu³⁺/CDs fluorescent probes. DPA can specifically combine with Eu³⁺ and then transfer energy from DPA to Eu³⁺ sequentially through the antenna effect, resulting in a distinct increase in the red fluorescence emission peak at 615 nm. The fluorescence intensity ratio of Eu³⁺/CDs (fluorescence intensity at 615 nm/fluorescence intensity at 470 nm) showed good linearity and low detection limit. The developed ratiometric nanoplatform possesses great potential for application in complex matrices owing to its specificity for DPA. In addition, the integration of a smartphone with the Color Picker APP installed enabled point-of-care testing (POCT) with quantitative measurement capabilities, confirming the great potential of the as-prepared measurement platform for on-site testing. Full article

Time-gated fluorescence measurement (TGFM) using long-life fluorescence probes is a highly sensitive fluorescence-measurement technology due to the inherently high signal-to-background ratio. Although many probes for TGFM such as luminescent-metal-complex probes and lanthanide-doped nanoparticles are in development, they generally need sophisticated/expensive instruments for biosensing/imaging applications. Probes possessing high brightness, low-energy (visible light) excitation, and long lifetimes up to milliseconds of luminescence, are highly desired in order to simplify the optical and electronic design of time-gated instruments (e.g., adopting non-UV-grade optics or low-speed electronics), lower the instrument complexity and cost, and facilitate broader applications of TGFM. In this work, we developed Mn-doped CuGa(In)S-ZnS nanocrystals (NCs) using simple and standard synthetic steps to achieve all the desired optical features in order to investigate how the optical properties (fluorescence/absorption spectra, brightness, and lifetimes) of the Mn-doped NCs are affected by different host NCs and Mn concentrations in host NCs. With optimal synthetic conditions, a library of Mn-doped NCs was achieved that possessed high brightness (up to 47% quantum yield), low-energy excitation (by 405 nm visible light), and long lifetimes (up to 3.67 ms). Additionally, the time-domain fluorescence characteristics of optimal Mn-doped NCs were measured under pulsed 405 nm laser excitation and bandpass-filter-based emission collection. The measurement results indicate the feasibility of these optimal Mn-doped NCs in TGFM-based biosensing/imaging. Full article

Tetracycline (TC) and oxytetracycline (OTC) are the most widely used broad-spectrum antimicrobial agents in tetracycline drugs, and their structures and properties are very similar, so it is a great challenge to distinguish and detect these two antibiotics with a single probe at the same time. Herein, a dual-channel fluorescence probe (SiCDs@mMIPs-cit-Eu) was developed by integrating two independent reaction sites with SiCDs-doped mesoporous silica molecular imprinting group and europium complex group into a nanomaterial. The synergistic influence of inner filter effect and “antenna effect” can be guaranteed to solve the distinction between TC and OTC. Moreover, this novel strategy can also sequentially detect TC and OTC in buffer solution and real samples with high sensitivity and selectivity. This method revealed good responses to TC and OTC ranging from 0 to 5.5 μM with a detection limit of 5 and 16 nM, respectively. Combined with the smartphone color-scanning application, the portable and cheap paper-based sensor was designed to realize the multi-color visual on-site detection of TC and OTC. In addition, the logic gate device was constructed according to the fluorescence color change of the probe for TC and OTC, which provided the application possibility for the intelligent detection of the probe. Full article

Europium (III) luminescent chelates possess intrinsic photophysical properties that are extremely useful in a wide range of applications. The lack of examples of coumarin-based lanthanide complexes is mainly due to poor photo-sensitization attempts. However, with the appeal of using such a versatile scaffold as antenna, especially in the development of responsive molecular probes, it is worth the effort to research new structural motifs. In this work, we present a series of two new tris coumarin-dipicolinate europium (III) complexes, specifically tailored to be either a mono or a dual emitter, tuning their properties with a simple chemical modification. We also encountered a rich chemical speciation in solution, studied in detail by means of paramagnetic NMR and emission spectroscopy. Full article

The development of synthetic lanthanide luminescent probes for selective sensing or binding anions in aqueous medium requires an understanding of how these anions interact with synthetic lanthanide probes. Synthetic lanthanide probes designed to differentiate anions in aqueous medium could underpin exciting new sensing tools for biomedical research and drug discovery. In this direction, we present three mononuclear lanthanide-based complexes, EuLCl₃ (1), SmLCl₃ (2), and TbLCl₃ (3), incorporating a hexadentate aminomethylpiperidine-based nitrogen-rich heterocyclic ligand L for sensing anion and establishing mechanistic insight on their binding activities in aqueous medium. All these complexes are meticulously studied for their preferential selectivities towards different anions such as HPO₄²⁻, SO₄²⁻, CH₃COO⁻, I⁻, Br⁻, Cl⁻, F⁻, NO₃⁻, CO₃²⁻/HCO₃⁻, and HSO₄⁻ at pH 7.4 in aqueous HEPES (2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid) buffer. Among the anions scanned, HPO₄²⁻ showed an excellent luminescence change with all three complexes. Job’s plot and ESI-MS support the 1:2 association between the receptors and HPO₄²⁻. Systematic spectrophotometric titrations of 1–3 against HPO₄²⁻ demonstrates that the emission intensities of 1 and 2 were enhanced slightly upon the addition of HPO₄²⁻ in the range 0.01–1 equiv and 0.01–2 equiv., respectively. Among the three complexes, complex 3 showed a steady quenching of luminescence throughout the titration of hydrogen phosphate. The lower and higher detection limits of HPO₄²⁻ by complexes 1 and 2 were determined as 0.1–4 mM and 0.4–3.2 mM, respectively, while complex 3 covered 0.2–100 μM. This concludes that all complexes demonstrated a high degree of sensitivity and selectivity towards HPO₄²⁻. Full article

The development of lanthanide-based luminescent probes with a long emission lifetime has the potential to revolutionize imaging-based diagnostic techniques. By a rational design strategy taking advantage of computational predictions, a novel, water-soluble Eu³⁺ complex from a cyclen-based ligand bearing 1,3-disubstituted benzo[h]isoquinoline arms was realized. The ligand has been obtained overcoming the lack of reactivity of position 3 of the isoquinoline moiety. Notably, steric hindrance of the heteroaromatic chromophore allowed selective and stoichiometry-controlled insertion of two or three antennas on the cyclen platform without any protection strategy. The complex bears a fourth heptanoic arm for easy conjugation to biomolecules. This new chromophore allowed the sensitization of the metal center either with one or two photons excitation. The suitability as a luminescent bioprobe was validated by imaging BMI1 oncomarker in lung carcinoma cells following an established immunofluorescence approach. The use of a conventional epifluorescence microscope equipped with a linear structured illumination module disclosed a simple and inexpensive way to image confocally Ln-bioprobes by single photon excitation in the 350–400 nm window, where ordinary confocal systems have no excitation sources. Full article

Luminescent organic-inorganic hybrids containing lanthanides (Ln³⁺) have been prominent for applications such as luminescent bio-probes in biological assays. In this sense, a luminescent hybrid based on dense silica (SiO₂) nanospheres decorated with Eu³⁺ β–diketonate complexes using dibenzoylmethane (Hdbm) as a luminescent antenna was developed by using a hierarchical organization in four steps: (i) anchoring of 3-aminopropyltriethoxysilane (APTES) organosilane on the SiO₂ surface, (ii) formation of a carboxylic acid ligand, (iii) coordination of Eu³⁺ to the carboxylate groups and (iv) coordination of dbm⁻ to Eu³⁺. The hybrid structure was elucidated through the correlation of thermogravimetry, silicon nuclear magnetic resonance and photoluminescence. Results indicate that the carboxylic acid-Eu³⁺-dbm hybrid was formed on the surface of the particles with no detectable changes on their size or shape after all the four steps (average size of 32 ± 7 nm). A surface charge of −27.8 mV was achieved for the hybrid, assuring a stable suspension in aqueous media. The Eu³⁺ complex provides intense red luminescence, characteristic of Eu³⁺⁵D₀→⁷F_J electronic transitions, with an intrinsic emission quantum yield of 38%, even in an aqueous suspension. Therefore, the correlation of luminescence, structure, particle morphology and fluorescence microscopy images make the hybrid promising for application in bioimaging. Full article

Zinc and copper are essential cations involved in numerous biological processes, and variations in their concentrations can cause diseases such as neurodegenerative diseases, diabetes and cancers. Hence, detection and quantification of these cations are of utmost importance for the early diagnosis of disease. Magnetic resonance imaging (MRI) responsive contrast agents (mainly Lanthanide(+III) complexes), relying on a change in the state of the MRI active part upon interaction with the cation of interest, e.g., switch ON/OFF or vice versa, have been successfully utilized to detect Zn²⁺ and are now being developed to detect Cu²⁺. These paramagnetic probes mainly exploit the relaxation-based properties (T₁-based contrast agents), but also the paramagnetic induced hyperfine shift properties (paraCEST and parashift probes) of the contrast agents. The challenges encountered going from Zn²⁺ to Cu²⁺ detection will be stressed and discussed herein, mainly involving the selectivity of the probes for the cation to detect and their responsivity at physiologically relevant concentrations. Depending on the response mechanism, the use of fast-field cycling MRI seems promising to increase the detection field while keeping a good response. In vivo applications of cation responsive MRI probes are only in their infancy and the recent developments will be described, along with the associated quantification problems. In the case of relaxation agents, the presence of another method of local quantification, e.g., synchrotron X-Ray fluorescence, single-photon emission computed tomography (SPECT) or positron emission tomography (PET) techniques, or ¹⁹F MRI is required, each of which has its own advantages and disadvantages. Full article

Bridged polymacrocyclic ligands featured by structurally different cages offer the possibility of coordinating multiple trivalent lanthanide ions, giving rise to the exploitation of their different physicochemical properties, e.g., multimodal detection for molecular imaging purposes. Intrigued by the complementary properties of optical and MR-based image capturing modalities, we report the synthesis and characterization of the polymetallic Ln(III)-based chelate comprised of two DOTA-amide-based ligands (DOTA—1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) bridged via 1,10-diaza-18-crown-6 (DA18C6) motif. The DOTA-amide moieties and the DA18C6 were used to chelate two Eu(III) ions and one Tb(III) ion, respectively, resulting in a multinuclear heterometallic complex Eu₂LTb. The bimetallic complex without Tb(III), Eu₂L, displayed a strong paramagnetic chemical exchange saturation transfer (paraCEST) effect. Notably, the luminescence spectra of Eu₂LTb featured mixed emission including the characteristic bands of Eu(III) and Tb(III). The advantageous features of the complex Eu₂LTb opens new possibilities for the future design of bimodal probes and their potential applicability in CEST MR and optical imaging. Full article

Europium, terbium, dysprosium, and samarium are the main trivalent lanthanide ions emitting in the visible spectrum. In this work, the potential of these ions for colorimetric applications and colour reproduction was studied. The conversion of spectral data to colour coordinates was undertaken for three sets of Ln complexes composed of different ligands. We showed that Eu is the most sensitive of the visible Ln ions, regarding ligand-induced colour shifts, due to its hypersensitive transition. Further investigation on the spectral bandwidth of the emission detector, on the wavelengths’ accuracy, on the instrumental correction function, and on the use of incorrect intensity units confirm that the instrumental correction function is the most important spectrophotometric parameter to take into account in order to produce accurate colour values. Finally, we established and discussed the entire colour range (gamut) that can be generated by combining a red-emitting Eu complex with a green-emitting Tb complex and a blue fluorescent compound. The importance of choosing a proper white point is demonstrated. The potential of using different sets of complexes with different spectral fingerprints in order to obtain metameric colours suitable for anti-counterfeiting is also highlighted. This work answers many questions that could arise during a colorimetric analysis of luminescent probes. Full article

Tunable photoluminescent-functionalized carbon quantum dots CQDs@Ln (TFA)₃ (Ln = Eu, Tb; TFA: trifluoroacetylacetone) were designed and synthesized by introducing lanthanide complexes into the modified CQDs surface through the carboxyl group. The as-prepared CQDs@Ln (TFA)₃ emit strong blue–green light with the peak at 435 nm and simultaneously show the characteristic emission of Ln³⁺ under irradiation of 365 nm light in aqueous solution. Moreover, these functionalized CQDs exhibit excellent photoluminescence properties. In addition, a white luminescent solution CQDs@Eu/Tb (TFA)₃ was obtained by adjusting the ratio of Eu³⁺/Tb³⁺ and the excitation wavelengths. Moreover, CQDs@Tb (TFA)₃ can be utilized as a fluorescent probe for the sensitive and selective detection of MnO₄⁻ without interference from other ions in aqueous solution. These results provide the meaningful data for the multicomponent assembly and the photoluminescent-functionalized materials based on the modified CQDs and lanthanide, which can be expected to have potential application in photocatalytic or sensors. Full article

Redox biology is still looking for tools to monitor redox potential in cellular biology and, despite a large and sustained effort, reliable molecular probes have yet to emerge. In contrast, molecular probes for reactive oxygen and nitrogen have been widely explored. In this manuscript, three kinetically inert lanthanide complexes that selectively react with hypochlorous acid are prepared and characterized. The design is based on 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) and 1,4,7,10-tetraazacyclododecane-1,7-diacetic acid (DO2A) ligands appended with one or two redox active hydroquinone derived arms, thereby forming octadentate ligands ideally suited to complex trivalent lanthanide ions. The three complexes are found to react selectively with hypochlorous acid to form highly symmetric lanthanide(III) 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacedic acid (DOTA) complexes. The conversion of the probe to [Ln.DOTA]⁻ is followed by luminescence, absorption, and NMR spectroscopy in a model system comprised of a Triton-X modified HEPES buffer. It was concluded that the design principle works, and that simple caging units like hydroquinones can work well in conjugation with lanthanide(III) complexes. Full article