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1.
Chemphyschem ; 21(10): 1036-1043, 2020 05 18.
Artigo em Inglês | MEDLINE | ID: mdl-32176399

RESUMO

Cationic lanthanide complexes are generally able to spontaneously internalize into living cells. Following our previous works based on a diMe-cyclen framework, a second generation of cationic water-soluble lanthanide complexes based on a constrained cross-bridged cyclam macrocycle functionalized with donor-π-conjugated picolinate antennas was prepared with europium(III) and ytterbium(III). Their spectroscopic properties were thoroughly investigated in various solvents and rationalized with the help of DFT calculations. A significant improvement was observed in the case of the Eu3+ complex, while the Yb3+ analogue conserved photophysical properties in aqueous solvent. Two-photon (2P) microscopy imaging experiments on living T24 human cancer cells confirmed the spontaneous internalization of the probes and images with good signal-to-noise ratio were obtained in the classic NIR-to-visible configuration with the Eu3+ luminescent bioprobe and in the NIR-to-NIR with the Yb3+ one.

2.
Chemistry ; 25(38): 9026-9034, 2019 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-30972809

RESUMO

Two trispicolinate 1,4,7-triazacyclonane (TACN)-based ligands bearing three picolinate biphotonic antennae were synthetized and their Yb3+ and Gd3+ complexes isolated. One series differs from the other by the absence (L1 )/presence (L2 ) of bromine atoms on the antenna backbone, offering respectively improved optical and singlet-oxygen generation properties. Photophysical properties of the ligands, complexes and micellar Pluronic suspensions were investigated. Complexes exhibit high two-photon absorption cross-section combined either with NIR emission (Yb) or excellent 1 O2 generation (Gd). The very large intersystem crossing efficiency induced by the combination of bromine atom and heavy rare-earth element was corroborated with theoretical calculations. The 1 O2 generation properties of L2 Gd micellar suspension under two-photon activation leads to tumour cell death, suggesting the potential of such structures for theranostic applications.

3.
Chem Commun (Camb) ; 53(44): 6005-6008, 2017 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-28516180

RESUMO

An Yb(iii) complex based on a dimethyl cyclen macrocyclic ligand functionalized by charge transfer antennae was prepared. This cationic [YbL3]+ complex is stable and soluble in water and presents interesting photophysical nonlinear properties. It is spontaneously internalized and accumulates in live cells. High quality images have been obtained both in a classical NIR-to-vis configuration and in the more challenging NIR-to-NIR one.


Assuntos
Complexos de Coordenação/química , Corantes Fluorescentes/química , Imagem Óptica , Fótons , Itérbio/química , Cátions/química , Linhagem Celular Tumoral , Sobrevivência Celular , Humanos , Raios Infravermelhos , Conformação Molecular
4.
Chemphyschem ; 17(1): 128-35, 2016 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-26538240

RESUMO

The photophysical and nonlinear optical properties of water-soluble chromophore-functionalised tris-dipicolinate complexes [LnL3](3-) (Ln=Yb and Nd) are thoroughly studied, revealing that only the Yb(III) luminescence can be sensitized by a two-photon excitation process. The stability of the complex in water is strongly enhanced by embedding in dispersible organosilicate nanoparticles (NPs). Finally, the spectroscopic properties of [NBu4]3 [YbL3] are studied in solution and in the solid state. The high brightness of the NPs allows imaging them as single objects using a modified two-photon microscopy setup in a NIR-to-NIR configuration.


Assuntos
Complexos de Coordenação/efeitos da radiação , Microscopia Confocal/métodos , Nanopartículas/efeitos da radiação , Ácidos Picolínicos/efeitos da radiação , Itérbio/química , Complexos de Coordenação/síntese química , Complexos de Coordenação/química , Luz , Nanopartículas/química , Ácidos Picolínicos/síntese química , Ácidos Picolínicos/química , Espectroscopia de Luz Próxima ao Infravermelho
5.
Inorg Chem ; 54(11): 5384-97, 2015 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-25965094

RESUMO

The reaction between the TTF-fused dipyrido[3,2-a:2',3'-c]phenazine (dppz) ligand (L) and 1 equiv of Ln(hfac)3·2H2O (hfac(-) = 1,1,1,5,5,5-hexafluoroacetyacetonate) or 1 equiv of Ln(tta)3·2H2O (tta(-) = 2-thenoyltrifluoroacetonate) (Ln(III) = Dy(III) or Yb(III)) metallic precursors leads to four mononuclear complexes of formula [Ln(hfac)3(L)]·C6H14 (Ln(III) = Dy(III) (1), Yb(III) (2)) and [Ln(tta)3(L)]·C6H14 (Ln(III) = Dy(III) (3), Yb(III) (4)), respectively. Their X-ray structures reveal that the Ln(III) ion is coordinated to the bischelating nitrogenated coordination site and adopts a D4d coordination environment. The dynamic magnetic measurements show a slow relaxation of the Dy(III) magnetization for 1 and 3 with parameters highlighting a slower relaxation for 3 than for 1 (τ0 = 4.14(±1.36) × 10(-6) and 1.32(±0.07) × 10(-6) s with Δ = 39(±3) and 63.7(±0.7) K). This behavior as well as the orientation of the associated magnetic anisotropy axes have been rationalized on the basis of both crystal field splitting parameters and ab initio SA-CASSCF/RASSI-SO calculations. Irradiation of the lowest-energy HOMO → LUMO ILCT absorption band induces a (2)F5/2 → (2)F7/2 Yb-centered emission for 2 and 4. For these Yb(III) compounds, Stevens operators method has been used to fit the thermal variation of the magnetic susceptibilities, and the resulting MJ splittings have been correlated with the emission lines.

6.
Dalton Trans ; 43(21): 7752-9, 2014 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-24699861

RESUMO

Magnesium spinel (MgAl2O4) powders doped with Yb(3+) ions have been synthesized by a sol-gel method and heat-treated in the range of 700-1000 °C for 3 h. XRD patterns indicated that the powders have a cubic structure with high crystallite dispersion. Nanoparticles in the range of 10-30 nm are obtained as a function of the dopant concentration and sintering temperature. The main Yb(3+) zero-phonon line is located at 976 nm. The spectroscopic properties of the Yb(3+) ions are characterized by broad absorption spectroscopy and emission spectroscopy. Even at low temperature, the spectra reveal a strong distorted spinel lattice due to the high inversion rate between Mg(2+) tetrahedral sites and Al(3+) octahedral sites. The substitution of Mg(2+) ions by Yb(3+) ions favors the creation of Yb(3+) ion pairs which are observed in the cooperative luminescence spectra at around 500 nm. The luminescence decays are influenced by both the Yb(3+) content, the energy transfer between ions and by the presence of pairs and aggregates. Detailed analysis of the observed structural and spectroscopic measurements has been described in this manuscript.

7.
Chemistry ; 20(6): 1569-76, 2014 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-24402683

RESUMO

Herein, we provide some structural evidence of the complexation color-change of murexide solutions in presence of lanthanide, which has been used for decades in complexometric studies. For Ln = Sm to Lu and Y, the compounds crystallize as monomeric [Ln(Murex)3]⋅11 H2O with an N3O6 tricapped square-antiprism environment, which are stable up to 250 °C. Single-ion magnet (SIM) behavior is then observed on the Yb(III) derivative in an original nine-coordinated environment. In-field slow relaxation (Δ = (15.6±1) K; τ0 = 2.73×10(-6) s) is observed with a very narrow distribution of the relaxation time (αmax = 0.09). Magnetic and photophysical properties can be correlated. On one hand the analysis of NIR emission spectrum permits to have access to crystal field parameters and to compare them with those extracted from dc measurements. On the other hand, magnetic measurements permit to identify the nature of the MJ states involved in the (2)F5/2 → (2)F7/2 luminescence spectrum. The gap between the low-lying states is in agreement with the energy barrier obtained from magnetic slow-relaxation measurement.

8.
Opt Express ; 20(23): 25596-602, 2012 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-23187378

RESUMO

We demonstrate a dual-wavelength Nd:YSAG ceramic laser in which the gain volume is structurated into two different regions providing gain at the wavelength of 1061 nm and 1064 nm respectively. We discuss the role of the nonuniform distribution of the temperature in structurating the gain region via the Boltzmann effect. We show that the two laser wavelengths can be switched by adjusting the size of the pump beam or by slightly modifying the geometrical parameters of the laser cavity, either the length of the cavity or the orientation of a mirror. Additionally, we demonstrate that the transverse modes at the two wavelengths are shaped according to the effect of gain filtering caused by the structuration of the gain region.

9.
Opt Express ; 20(12): 12658-65, 2012 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-22714294

RESUMO

In this paper, a broad combined orange-red emission from Eu²âº- and Eu³âº-doped low-silica calcium aluminosilicate (LSCAS) glass is reported. Spectroscopic results demonstrate that it is possible to tune the emission wavelength by changing the excitation wavelength in the UV-Vis region. The color coordinates for the emission spectra were calculated, and using the Commission Internationale de l'Éclairage 1931 and 1976 chromatic diagrams, it is possible to note that they are dependent on the excitation wavelength. In addition, the (u', v') color coordinates for the investigated LSCAS samples are close to the Planckian spectrum in the cold region between 2000 and 2600K. Our results show that the Eu:LSCAS system can be used in a white light phosphor when mixed in aggregate with phosphors using green-yellow luminescent ions.

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