Luminescent probes based on water-soluble, dual-emissive lanthanide complexes: metal ion-induced modulation of near-IR emission
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Responsive lanthanide complexes demonstrate differentiated modulated luminescence output upon exposure to metal di-cations in aqueous solution.Keywords:
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We report the synthesis, structures, magnetic, and luminescence properties of a new series of tetranuclear lanthanide-based germsesquioxanes [NEt4]2[(Ph4Ge4O8)2(Ln4)(NO3)6(EtOH)2(MeCN)2]·n(CH3CN) (where Ln = Eu3+ (1), Tb3+ (2), Tb3+/Eu3+ (3), Dy3+/Y3+ (4), and Dy3+ (5)). These paramagnetic compounds exhibit characteristic Ln3+-based emission in solid state at room and liquid nitrogen temperature. Temperature-dependent luminescence investigated between 293 and 373 K reveals that mixed Tb3+/Eu3+ (3) compound works as a self-referenced ratiometric optical thermometer with a maximum relative sensitivity of 0.87%·°C–1 achieved at 57.6 °C.
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Abstract Since the pioneering report by Selvin, we have been fascinated by the potential of using lanthanide luminescence in bioimaging. The uniquely narrow emission lines and long luminescence lifetimes both provide the potential for background free images together with full certainty of probe localization. General use of lanthanide based bioimaging was first challenged by low brightness, and later by the need of UV (<405 nm) excitation sources not present in commercial microscopes. Here, we designed three lanthanide‐based imaging probes based on a known motif to investigate the limitations of 405 nm excitation. These were synthesized, characterized, investigated on dedicated as well as commercial microscopes, and the photophysics was explored in detail. It was proven without doubt that the lanthanide complexes enter the cells and luminesce internally. Even so, no lanthanide luminescence were recovered on the commercial microscopes. Thus, we returned to the photophysical properties that afforded the conclusion that – despite the advances in light sources and photodetectors – we need new designs that can give us brighter lanthanide complexes before bioimaging with lanthanide luminescence becomes something that is readily done.
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Lanthanide-sensitized luminescence is very attractive because the intramolecular energy transfers between the absorbing ligand and the luminescent ion results in strong narrow-band fluorescence with a large Stokes' shift and long decay times. We will report about several sensor systems based either on sol-gel materials or lanthanide chelates for monitoring and controlling water parameters, such as heavy metals, amines, phosphates.
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Luminescence spectroscopy has been used to monitor the selective and reversible binding of pH sensitive, macrocyclic lanthanide complexes,[LnL1] , to the serum protein α1-AGP, whose concentration can vary significantly in response to inflammatory processes.
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Abstract An overview of recent work dealing with luminescence properties in solution of complexes of the lanthanide(3+) ions Nd 3+ , Eu 3+ , Tb 3+ , Er 3+ and Yb 3+ in which an organic chromophore is attached to the metal centre as a sensitizer is given. The various factors that influence the metal‐centred luminescence lifetime and intensity are discussed and illustrated with own results and recent literature examples. The VIS emitting metal ions Eu 3+ and Tb 3+ require sensitizers that absorb light in the UV or near UV range whereas VIS absorbing sensitizers can be used for the NIR emitting ions Nd 3+ , Er 3+ and Yb 3+ . The latter type of complexes is currently of great interest because of potential applications as luminescent markers in biological systems. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
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A new luminescent lanthanide metal–organic framework was successfully synthesized, featuring rare 1D chiral helical channels and a highly selective luminescence quenching response to Fe3+ ions.
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Luminescent lanthanide complexes (Tb(3+), Eu(3+), etc.) have excellent properties for biological applications, including extraordinarily long lifetimes and large Stokes shifts. However, there have been few reports of lanthanide-based functional probes, because of the difficulty in designing suitable complexes with a luminescent on/off switch. Here, we have synthesized a series of complexes which consist of three moieties: a lanthanide chelate, an antenna, and a luminescence off/on switch. The antenna is an aromatic ring which absorbs light and transmits its energy to the metal, and the switch is a benzene derivative with a different HOMO level. If the HOMO level is higher than a certain threshold, the complex emits no luminescence at all, which indicates that the lanthanide luminescence can be modulated by photoinduced electron transfer (PeT) from the switch to the sensitizer. This approach to control lanthanide luminescence makes possible the rational design of functional lanthanide complexes, in which the luminescence property is altered by a biological reaction. To exemplify the utility of our approach to the design of lanthanide complexes with a switch, we have developed a novel protease probe, which undergoes a significant change in luminescence intensity upon enzymatic cleavage of the substrate peptide. This probe, combined with time-resolved measurements, was confirmed in model experiments to be useful for the screening of inhibitors, as well as for clinical diagnosis.
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Abstract Luminescent nanomaterials have attracted great attention in luminescence‐based bioanalysis due to their abundant optical and tunable surface physicochemical properties. However, luminescent nanomaterials often suffer from serious autofluorescence and light scattering interference when applied to complex biological samples. Time‐resolved luminescence methodology can efficiently eliminate autofluorescence and light scattering interference by collecting the luminescence signal of a long‐lived probe after the background signals decays completely. Lanthanides have a unique [Xe]4f N electronic configuration and ladder‐like energy states, which endow lanthanide‐doped nanoparticles with many desirable optical properties, such as long luminescence lifetimes, large Stokes/anti‐Stokes shifts, and sharp emission bands. Due to their long luminescence lifetimes, lanthanide‐doped nanoparticles are widely used for high‐sensitive biosensing and high‐contrast bioimaging via time‐resolved luminescence methodology. In this review, recent progress in the development of lanthanide‐doped nanoparticles and their application in time‐resolved biosensing and bioimaging are summarized. At the end of this review, the current challenges and perspectives of lanthanide‐doped nanoparticles for time‐resolved bioapplications are discussed.
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Since the pioneering report by Selvin, we have been fascinated by the potential of using lanthanide lu-minescence in bioimaging. The uniquely narrow emission lines and long luminescence lifetimes both provide the potential for background free images together with full certainty of probe localization. General use of lanthanide based bioimaging was first challenged by low brightness, and later by the need of UV (<405 nm) excitation sources not present in commercial microscopes. Here, three lantha-nide-based imaging probes were synthesized, characterized, and used in bioimaging on dedicated as well as commercial microscopes. It was proven without doubt that the lanthanide complexes enter the cells and luminesce internally. Even so, no lanthanide luminescence were recovered on the commercial microscopes. Thus, it was concluded that even though the commercial microscopes are capable of single photon detection, lanthanide luminescence based bioimaging still requires dedicated hardware.
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