A Porphyrin Dimer–GdDOTA Conjugate as a Theranostic Agent for One- and Two-Photon Photodynamic Therapy and MRI

Schmitt, Julie; Jenni, Sébastien; Sour, Angélique; Heitz, Valérie; Bolze, Frédéric; Pallier, Agnès; Bonnet, Célia S.; Tóth, Éva; Ventura, Barbara

doi:10.1021/acs.bioconjchem.8b00634

Cited by 43 publications

(50 citation statements)

References 77 publications

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“…For all these compounds, the n-butyl chains at the nine positions of fluorenyl groups are clearly identified by four multiplets between 0 and 2 ppm corresponding to Ha, Hb, Hc, and Hd, and the OH proton appears as a large singlet peak at about 5 ppm (Figure 4, bottom). The various fluorene precursors (3)(4)(5)(6)(7)(8)(9), as well as the phthalonitriles Pn1-4, were conveniently characterized by 1 H-NMR (Figures S1-S13, Supplementary Materials). This spectroscopy can even be used to monitor the various reactions using diagnostic signals.…”

Section: K 2 Co /Dmf 50°cmentioning

confidence: 99%

“…The chemistry of porphyrins and phthalocyanines involving new structural motifs and subunits, either within the central macrocycle or in its periphery, is in full development, in particular for photonic applications related to cancer therapy [1][2][3][4], such as photodynamic therapy (PDT) [2,5,6]. In this context, given the well-known oxygen photosensitizing properties of these macrocycles [7][8][9], Thus, in spite of its remarkably high fluorescence quantum yield (ΦF = 88%) [30], H2OFPc ( Figure 2) suffers from a poorly efficient energy transfer (ET) from the fluorenyl-based antennae toward the central macrocycle, possibly due to the unfavorable conformations adopted by the peripheral antennae relative to the central phthalocyanine core, these conformations being likely induced by steric strain.…”

Section: Introductionmentioning

confidence: 99%

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Phthalocyanine-Cored Fluorophores with Fluorene-Containing Peripheral Two-Photon Antennae as Photosensitizers for Singlet Oxygen Generation

et al. 2020

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A series of free base and Zn(II) phthalocyanines featuring fluorenyl antennae linked by methoxy or oxo bridges to the phthalocyanine core (Pc) were synthesized and characterized. Selected linear and nonlinear (two-photon absorption) optical properties of these new compounds were subsequently studied. As previously observed for related porphyrin dendrimers bearing 2-fluorenyl peripheral dendrons, an efficient energy transfer occurs from the peripheral antennae to the central phthalocyanine core following excitation in the fluorenyl-based π-π* absorption band of these chromophores. Once excited, these compounds relax to the ground state, mostly by emitting intense red light or by undergoing intersystem crossing. As a result, the tetrafunctionalized Zn(II) phthalocyanines are fluorescent, but can also efficiently photosensitize molecular oxygen in tetrahydrofurane (THF), forming singlet oxygen with nearly comparable yields to bare Zn(II) phthalocyanine (ZnPc). In comparison with the latter complex, the positive role of the fluorenyl-containing antennae on one-and two-photon brightness (2PA) is presently demonstrated when appended in peripheral (β) position to the phthalocyanine core. Furthermore, when compared to known porphyrin analogues, the interest in replacing the porphyrin by a phthalocyanine as the central core to obtain more fluorescent two-photon oxygen photosensitizers is clearly established. As such, this contribution paves the way for the future development of innovative biphotonic photosensitizers usable in theranostics.Molecules 2020, 25, 239 2 of 30 studying new porphyrin-or phthalocyanine-based molecular assemblies that might efficiently undergo two-photon excitation [10-13] while presenting a significant luminescence, constitutes an appealing goal for researchers interested in developing new photosensitizers for theranostic applications [4,5,[14][15][16]. Along these lines, some of us [17,18] and others [19], independently reported that fluorenyl units, when appended at the meso positions of porphyrins, were particularly suited to enhance the fluorescence quantum yields of this macrocyclic core, most likely by limiting the rate of non-radiative decay via internal conversion [20]. Thus, tetrafluorenylporphyrin (H 2 TFP) [21] features a quantum yield of 24% compared to that tetraphenylporphyrin (H 2 TPP; Φ F = 12%) taken as a reference compound (Figure 1) [18]. Subsequent photophysical studies with tetra(fluorenylmethoxyphenyl)porphyrin (H 2 TOFP), octa(fluorenylmethoxy)tetraphenylporphyrin (H 2 OOFP), or hexadeca(fluorenylmethoxy)tetra-phenylporphyrin (H 2 SOFP) featuring four, eight [22] and sixteen peripheral fluorenyl groups [23], respectively, evidenced that 2-fluorenyl units were also able to enhance the luminescence quantum yield of the central tetraphenylporphyrin (TPP) core when appended by methoxy bridges to the meso-phenyl rings of a central H 2 TPP core (Figure 1). In these molecular assemblies, the fluorene groups play the role of light-harvesting "antennae". Once photoexcited in their fi...

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Section: K 2 Co /Dmf 50°cmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Phthalocyanine-Cored Fluorophores with Fluorene-Containing Peripheral Two-Photon Antennae as Photosensitizers for Singlet Oxygen Generation

et al. 2020

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“…This presence appears to increase the relaxation times. Although many zinc(II) responsive probes have been reported since 2001 [31], to the best of our knowledge, only two heteronuclear Zn-Gd complexes has been tested as potential contrast agents until now as T1 agents, but not as potential negative contrasts [61,62]. Accordingly, the findings of this work could suppose an incipient contribution in the search for new CAs: the potential use of heteronuclear Zn-Gd complexes as T2 contrast agents.…”

Section: Mri Studiesmentioning

confidence: 91%

Filling Tricompartmental Ligands with GdIII and ZnII Ions: Some Structural and MRI Studies

et al. 2018

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Here we report the synthesis and characterization of a mononuclear gadolinium complex (Gd) and two heteronuclear Zn-Gd complexes (ZnGd and Zn2Gd), which contain two similar three-armed ligands that display an external compartment suitable for lanthanoid ions, and two internal compartments adequate for zinc (II) ions [H3L′ = (2-(3-formyl-2-hydroxy-5-methyl phenyl)-1,3-bis[4 -(3-formyl-2-hydroxy-5-methylphenyl)-3-azabut-3-enyl]-1,3-imidazolidine; H3L = 2-(5-bromo-2-hydroxy-3-methoxyphenyl)-1,3-bis[4-(5-bromo-2-hydroxy-3-methoxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine]. The synthetic methods used were varied, but the use of a metalloligand, [Zn2(L)AcO], as starting material was the key factor to obtain the heterotrinuclear complex Zn2Gd. The structure of the precursor dinuclear zinc complex is mostly preserved in this complex, since it is based on a compact [Zn2Ln(L)(OH)(H2O)]3+ residue, with a µ3-OH bridge between the three metal centers, which are almost forming an isosceles triangle. The asymmetric spatial arrangement of other ancillary ligands leads to chirality, what contrasts with the totally symmetric mononuclear gadolinium complex Gd. These features were confirmed by the crystal structures of both complexes. Despite the presence of the bulky compartmental Schiff base ligand, the chiral heterotrinuclear complex forms an intricate network which is predominately expanded in two dimensions, through varied H-bonds that connect not only the ancillary ligands, but also the nitrate counterions and some solvated molecules. In addition, some preliminary magnetic resonance imaging (MRI) studies have been made to determine the relaxivities of the three gadolinium complexes, with apparently improved T1 and T2 relaxivities with increasing zinc nuclearity, since both transversal and longitudinal relaxivities appear to enhance in the sequence Gd < ZnGd < Zn2Gd.

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“…A theranostic agent containing a PS with high one-and two-photon absorption capacity in the near infrared region and two stable contrast agents for MR imaging has been studied. [55] The structure of this agent consists of a Zn-porphyrin dimer (ZnP-ZnP) linked to two GdDOTA complexes (Figure 6a). High relaxivity values have been obtained with a maximum of r1 = 14.4 mM −1 •s −1 (at 40 MHz in water containing 2% of pyridine to ensure complete water solubility).…”

Section: Molecular Theranostic Agents With Combined Pdt and Mri Studiesmentioning

confidence: 99%

Molecular Theranostic Agents for Photodynamic Therapy (PDT) and Magnetic Resonance Imaging (MRI)

Jenni

Sour

2019

Inorganics

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Magnetic resonance imaging (MRI) is a powerful non-invasive diagnostic tool that can provide important insights for medical treatment monitoring and optimization. Photodynamic therapy (PDT), a minimally invasive treatment for various types of tumors, is drawing increasing interest thanks to its temporal and spatial selectivity. The combination of MRI and PDT offers real-time monitoring of treatment and can give significant information for drug-uptake and light-delivery parameters optimization. In this review we will give an overview of molecular theranostic agents that have been designed for their potential application in MRI and PDT.

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A Porphyrin Dimer–GdDOTA Conjugate as a Theranostic Agent for One- and Two-Photon Photodynamic Therapy and MRI

Cited by 43 publications

References 77 publications

Phthalocyanine-Cored Fluorophores with Fluorene-Containing Peripheral Two-Photon Antennae as Photosensitizers for Singlet Oxygen Generation

Phthalocyanine-Cored Fluorophores with Fluorene-Containing Peripheral Two-Photon Antennae as Photosensitizers for Singlet Oxygen Generation

Filling Tricompartmental Ligands with GdIII and ZnII Ions: Some Structural and MRI Studies

Molecular Theranostic Agents for Photodynamic Therapy (PDT) and Magnetic Resonance Imaging (MRI)

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