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Keywords = metalla-cages

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15 pages, 6741 KiB  
Article
The Effect of Photosensitizer Metalation Incorporated into Arene–Ruthenium Assemblies on Prostate Cancer
by Lucie Paulus, Manuel Gallardo-Villagrán, Claire Carrion, Catherine Ouk, Frédérique Martin, Bruno Therrien, David Yannick Léger and Bertrand Liagre
Int. J. Mol. Sci. 2023, 24(17), 13614; https://doi.org/10.3390/ijms241713614 - 2 Sep 2023
Cited by 6 | Viewed by 1993
Abstract
Prostate cancer is the second most common cancer for men and a major health issue. Despite treatments, a lot of side effects are observed. Photodynamic therapy is a non-invasive method that uses photosensitizers and light to induce cell death through the intramolecular generation [...] Read more.
Prostate cancer is the second most common cancer for men and a major health issue. Despite treatments, a lot of side effects are observed. Photodynamic therapy is a non-invasive method that uses photosensitizers and light to induce cell death through the intramolecular generation of reactive oxygen species, having almost no side effects. However, some of the PSs used in PDT show inherent low solubility in biological media, and accordingly, functionalization or vectorization is needed to ensure internalization. To this end, we have used arene–ruthenium cages in order to deliver PSs to cancer cells. These metalla-assemblies can host PSs inside their cavity or be constructed with PS building blocks. In this study, we wanted to determine if the addition of metals (Mg, Co, Zn) in the center of these PSs plays a role. Our results show that most of the compounds induce cytotoxic effects on DU 145 and PC-3 human prostate cancer cells. Localization by fluorescence confirms the internalization of the assemblies in the cytoplasm. An analysis of apoptotic processes shows a cleavage of pro-caspase-3 and poly-ADP-ribose polymerase, thus leading to a strong induction of DNA fragmentation. Finally, the presence of metals in the PS decreases PDT’s effect and can even annihilate it. Full article
(This article belongs to the Special Issue Molecular Research and Treatment of Urologic Cancer)
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41 pages, 9677 KiB  
Review
Luminescence and Palladium: The Odd Couple
by David Dalmau and Esteban P. Urriolabeitia
Molecules 2023, 28(6), 2663; https://doi.org/10.3390/molecules28062663 - 15 Mar 2023
Cited by 18 | Viewed by 4076
Abstract
The synthesis, photophysical properties, and applications of highly fluorescent and phosphorescent palladium complexes are reviewed, covering the period 2018–2022. Despite the fact that the Pd atom appears closely related with an efficient quenching of the fluorescence of different molecules, different synthetic strategies have [...] Read more.
The synthesis, photophysical properties, and applications of highly fluorescent and phosphorescent palladium complexes are reviewed, covering the period 2018–2022. Despite the fact that the Pd atom appears closely related with an efficient quenching of the fluorescence of different molecules, different synthetic strategies have been recently optimized to achieve the preservation and even the amplification of the luminescent properties of several fluorophores after Pd incorporation. Beyond classical methodologies such as orthopalladation or the use of highly emissive ligands as porphyrins and related systems (for instance, biladiene), new concepts such as AIE (Aggregation Induced Emission) in metallacages or in coordination-driven supramolecular compounds (CDS) by restriction of intramolecular motions (RIM), or complexes showing TADF (Thermally Activated Delayed Fluorescence), are here described and analysed. Without pretending to be comprehensive, selected examples of applications in areas such as the fabrication of lighting devices, biological markers, photodynamic therapy, or oxygen sensing are also here reported. Full article
(This article belongs to the Special Issue Featured Reviews in Organometallic Chemistry)
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12 pages, 1746 KiB  
Article
Macrocycle with Equatorial Coordination Sites Provides New Opportunity for Structure-Diverse Metallacages
by Yibo Zhao, Yunfeng Lu, Ao Liu, Zhi-Yuan Zhang, Chunju Li and Andrew C.-H. Sue
Molecules 2023, 28(6), 2537; https://doi.org/10.3390/molecules28062537 - 10 Mar 2023
Cited by 4 | Viewed by 2773
Abstract
Reported here is the synthesis of a macrocycle with equatorial coordination sites for the construction of self-assembled metallacages. The macrocycle is prepared via a post-modification on the equator of biphen[n]arene. Utilizing this macrocycle as a ligand, three prismatic cages and one [...] Read more.
Reported here is the synthesis of a macrocycle with equatorial coordination sites for the construction of self-assembled metallacages. The macrocycle is prepared via a post-modification on the equator of biphen[n]arene. Utilizing this macrocycle as a ligand, three prismatic cages and one octahedral cage were synthesized by regulating the geometric structures and coordination number of metal acceptors. The multi-cavity configuration of prismatic cage was revealed by single-crystal structure. We prove that a macrocycle with equatorial coordination sites can be an excellent building block for synthesizing structure-diverse metallacages. Our results provide a typical example and a general method for the design and synthesis of metallacages. Full article
(This article belongs to the Collection Heterocyclic Compounds)
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21 pages, 5621 KiB  
Review
The Applications of Metallacycles and Metallacages
by Changfeng Yin, Jiaxing Du, Bogdan Olenyuk, Peter J. Stang and Yan Sun
Inorganics 2023, 11(2), 54; https://doi.org/10.3390/inorganics11020054 - 22 Jan 2023
Cited by 14 | Viewed by 3887
Abstract
Metallacycles and metallacages constitute a class of coordination compounds composed of metal ions and organic ligands. Because of their precise stoichiometry, the flexibility and viability of design, metallacycles and metallacages have attracted considerable attention as supramolecular assemblies. Various two-dimensional polygons, three-dimensional polyhedra, and [...] Read more.
Metallacycles and metallacages constitute a class of coordination compounds composed of metal ions and organic ligands. Because of their precise stoichiometry, the flexibility and viability of design, metallacycles and metallacages have attracted considerable attention as supramolecular assemblies. Various two-dimensional polygons, three-dimensional polyhedra, and other nanoscale materials have been constructed and applied. The highly diverse structures, sizes, and shapes endow metallacycles and metallacages with unique physical and chemical properties and make them suitable for various applications such as encapsulation, separation, catalysis, and biological science. Herein, we review the recent developments in various metallacycles and metallacages in different fields. The text highlights biomedical applications involving molecular recognition and binding, antibacterial activity, and especially cancer diagnosis and treatment, including imaging, chemotherapy, PDT, and PTT. Full article
(This article belongs to the Special Issue Metallamacrocycles and Metallacages: Foundations and Applications)
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11 pages, 3062 KiB  
Article
Controlling Chiral Self-Sorting in Truxene-Based Self-Assembled Cages
by Amina Benchohra, Simon Séjourné, Antoine Labrunie, Liam Miller, Enzo Charbonneau, Vincent Carré, Frédéric Aubriet, Magali Allain, Marc Sallé and Sébastien Goeb
Inorganics 2022, 10(7), 103; https://doi.org/10.3390/inorganics10070103 - 19 Jul 2022
Cited by 3 | Viewed by 2952
Abstract
Coordination driven self-assembly of achiral components, i.e., hexa-alkylated truxene ligands (L) with bis-metallic complexes (M2), afforded three chiral face-rotating stereoisomer polyhedra (M6L2). By tuning the length of the alkyl chains as well as the distance between both [...] Read more.
Coordination driven self-assembly of achiral components, i.e., hexa-alkylated truxene ligands (L) with bis-metallic complexes (M2), afforded three chiral face-rotating stereoisomer polyhedra (M6L2). By tuning the length of the alkyl chains as well as the distance between both ligands facing each other in the self-assemblies (M6L2), one can control the diastereomeric distribution between the expected homo- and hetero-chiral structures. Full article
(This article belongs to the Special Issue Metallamacrocycles and Metallacages: Foundations and Applications)
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18 pages, 5928 KiB  
Review
Anthracene-Containing Metallacycles and Metallacages: Structures, Properties, and Applications
by Jian-Hong Tang and Yu-Wu Zhong
Inorganics 2022, 10(7), 88; https://doi.org/10.3390/inorganics10070088 - 22 Jun 2022
Cited by 8 | Viewed by 4002
Abstract
Due to its highly conjugated panel-like structure and unique photophysical and chemical features, anthracene has been widely used for fabricating attractive and functional supramolecular assemblies, including two-dimensional metallacycles and three-dimensional metallacages. The embedded anthracenes in these assemblies often show synergistic effects on enhancing [...] Read more.
Due to its highly conjugated panel-like structure and unique photophysical and chemical features, anthracene has been widely used for fabricating attractive and functional supramolecular assemblies, including two-dimensional metallacycles and three-dimensional metallacages. The embedded anthracenes in these assemblies often show synergistic effects on enhancing the desired supramolecular and luminescent properties. This review focuses on the metallasupramolecular architectures with anthracene-containing building blocks, as well as their applications in host-guest chemistry, stimulus response, molecular sensing, light harvesting, and biomedical science. Full article
(This article belongs to the Special Issue Metallamacrocycles and Metallacages: Foundations and Applications)
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16 pages, 2722 KiB  
Article
Evaluation of Ruthenium-Based Assemblies as Carriers of Photosensitizers to Treat Rheumatoid Arthritis by Photodynamic Therapy
by Manuel Gallardo-Villagrán, Lucie Paulus, Jean-Louis Charissoux, Sylvain Sutour, Pascale Vergne-Salle, David Yannick Leger, Bertrand Liagre and Bruno Therrien
Pharmaceutics 2021, 13(12), 2104; https://doi.org/10.3390/pharmaceutics13122104 - 7 Dec 2021
Cited by 16 | Viewed by 3421
Abstract
For the first time, ruthenium-based assemblies have been used as carriers for photosensitizers in the treatment of rheumatoid arthritis by photodynamic therapy (PDT). These metallacages are totally soluble in physiological media and can transport photosensitizers (PS) in their cavity. After an incubation period, [...] Read more.
For the first time, ruthenium-based assemblies have been used as carriers for photosensitizers in the treatment of rheumatoid arthritis by photodynamic therapy (PDT). These metallacages are totally soluble in physiological media and can transport photosensitizers (PS) in their cavity. After an incubation period, the PS is released in the cytoplasm and irradiation can take place. This strategy allows photosensitizers with low or null solubility in biological media to be evaluated as PDT agents in rheumatoid arthritis. The systems in which 21H,23H-porphine and 29H,31H-phthalocyanine are encapsulated show excellent photocytotoxicity and no toxicity in the dark. On the other hand, systems in which metalated derivatives such as Mg(II)-porphine and Zn(II)-phthalocyanine are used show good photocytotoxicity, but to a lesser extent than the previous two. Furthermore, the presence of Zn(II)-phthalocyanine significantly increases the toxicity of the system. Overall, fifteen different host–guest systems have been evaluated, and based on the results obtained, they show high potential for treating rheumatoid arthritis by PDT. Full article
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12 pages, 2453 KiB  
Communication
Chiral Self-Sorting in Truxene-Based Metallacages
by Simon Séjourné, Antoine Labrunie, Clément Dalinot, Amina Benchohra, Vincent Carré, Frédéric Aubriet, Magali Allain, Marc Sallé and Sébastien Goeb
Inorganics 2020, 8(1), 1; https://doi.org/10.3390/inorganics8010001 - 20 Dec 2019
Cited by 10 | Viewed by 4776
Abstract
Two chiral face-rotating metalla-assembled polyhedra were constructed upon self-assembling achiral components, i.e., a tritopic ligand based on a truxene core (10,15-dihydro-5H-diindeno[1,2-a;1′,2′-c]fluorene) and two different hydroxyquinonato–bridged diruthenium complexes. Both polyhedra were characterized in solution as well as in the solid state by X-ray crystallography. [...] Read more.
Two chiral face-rotating metalla-assembled polyhedra were constructed upon self-assembling achiral components, i.e., a tritopic ligand based on a truxene core (10,15-dihydro-5H-diindeno[1,2-a;1′,2′-c]fluorene) and two different hydroxyquinonato–bridged diruthenium complexes. Both polyhedra were characterized in solution as well as in the solid state by X-ray crystallography. In both cases, the self-sorting process leading to only two homo-chiral enantiomers was governed by non-covalent interactions between both truxene units that faced each other. Full article
(This article belongs to the Special Issue Recent Advances in Coordination Rings and Cages)
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12 pages, 876 KiB  
Article
A Self-Assembled Electro-Active M8L4 Cage Based on Tetrathiafulvalene Ligands
by Sébastien Goeb, Sébastien Bivaud, Vincent Croué, Vaishali Vajpayee, Magali Allain and Marc Sallé
Materials 2014, 7(1), 611-622; https://doi.org/10.3390/ma7010611 - 22 Jan 2014
Cited by 30 | Viewed by 7907
Abstract
Two self-assembled redox-active cages are presented. They are obtained by coordination-driven self-assembly of a tetra-pyridile tetrathiafulvalene ligand with cis-M(dppf)(OTf)2 (M = Pd or Pt; dppf = 1,1′-bis(diphenylphosphino)ferrocene; OTf = trifluoromethane-sulfonate) complexes. Both species are fully characterized and are constituted of 12 [...] Read more.
Two self-assembled redox-active cages are presented. They are obtained by coordination-driven self-assembly of a tetra-pyridile tetrathiafulvalene ligand with cis-M(dppf)(OTf)2 (M = Pd or Pt; dppf = 1,1′-bis(diphenylphosphino)ferrocene; OTf = trifluoromethane-sulfonate) complexes. Both species are fully characterized and are constituted of 12 electro-active subunits that can be reversibly oxidized. Full article
(This article belongs to the Special Issue Supramolecular Cage Complexes)
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