Stimuli Response of Eu<sup>3+</sup>-Based Metallo-Supramolecular Polymers toward Pharmaceutical Amines

Ben‐Shahar, Yuval; Yamin, Tamar Shamai; Marx, Sharon; Karton-Lifshin, Naama; Marciano, Daniele

doi:10.1021/acssensors.2c02491

Cited by 5 publications

(1 citation statement)

References 68 publications

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“…Lanthanides (Ln) are distinguished by their unique photophysical attributes, including prolonged fluorescence decay, sharp emission bands, and extended emission wavelengths. − These characteristics have inspired the synthesis of innovative luminescent lanthanide-based supramolecular assemblies, paving the way for advancements in optical electronic devices, optical sensing, and light-harvesting materials in recent years. − In particular, lanthanide(III) ions exhibit diverse coordination geometries with coordination numbers spanning from 8 to 12. , Such geometries contribute to the generation of supramolecular polymers exhibiting varied morphological features. During supramolecular polymerization, certain kinetically metastable complexes emerge due to these diverse coordination geometries .…”

Section: Introductionmentioning

confidence: 99%

Metallosupramolecular Multiblock Copolymers of Lanthanide Complexes by Seeded Living Polymerization

Lim,

Cho,

Kang

et al. 2024

J. Am. Chem. Soc.

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Supramolecular block copolymers, derived via seeded living polymerization, are increasingly recognized for their rich structural and functional diversity, marking them as cuttingedge materials. The use of metal complexes in supramolecular block copolymerization not only offers a broad range of block copolymers through the structural similarity in the coordination geometry of the central metal ion but also controls spectroscopic properties, such as emission wavelength, emission strength, and fluorescence lifetime. However, the exploration of metallosupramolecular multiblock copolymerization based on metal complexes remains quite limited. In this work, we present a pioneering synthesis of metallosupramolecular multiblock copolymers utilizing Eu 3+ and Tb 3+ complexes as building blocks. This is achieved through the strategic manipulation of nonequilibrium self-assemblies via a living supramolecular polymerization approach. Our comprehensive exploration of both thermodynamically and kinetically regulated metallosupramolecular polymerizations, centered around Eu 3+ and Tb 3+ complexes with bisterpyridine-modified ligands containing R-alanine units and a long alkyl group, has highlighted intriguing behaviors. The monomeric [R-L 1 Eu(NO 3 ) 3 ] complex generates a spherical structure as the kinetic product. In contrast, the monomeric [R-L 1 Eu 2 (NO 3 ) 6 ] complex generates fiber aggregates as a thermodynamic product through intermolecular interactions such as π−π stacking, hydrophobic interaction, and H-bonds. Utilizing the Eu 3+ complex, we successfully conducted seed-induced living polymerization of the monomeric building unit under kinetically regulated conditions. This yielded a metallosupramolecular polymer of precisely controlled length with minimal polydispersity. Moreover, by copolymerizing the kinetically confined Tb 3+ complex state ("A" species) with a seed derived from the Eu 3+ complex ("B" species), we were able to fabricate metallosupramolecular tri-and pentablock copolymers with A−B−A, and B−A−B−A−B types, respectively, through a seed-end chain-growth mechanism.

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Section: Introductionmentioning

confidence: 99%

Metallosupramolecular Multiblock Copolymers of Lanthanide Complexes by Seeded Living Polymerization

Lim,

Cho,

Kang

et al. 2024

J. Am. Chem. Soc.

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High‐Loading L‐Arginine Stabilized in an Oxygen‐Rich Lanthanide Metal–Organic Framework Capable of NO Release and Self‐Quantifying Luminescence Detection

Xu,

Wang,

et al. 2024

Advanced Optical Materials

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Exogenous supplementation of L‐arginine (L‐Arg) facilitates the release of nitric oxide (NO) for gas therapy applications in tumor microenvironments rich in H2O2. However, direct administration inevitably leads to the premature release of hydrophilic L‐Arg in the bloodstream, potentially resulting in unstable plasma L‐Arg concentrations and subsequent adverse reactions. Therefore, it is crucial to identify efficient and stable high‐dose L‐Arg delivery carriers, albeit challenging. Here, the study has achieved high (≈94 mg g−1) and stable L‐Arg loading within a 12‐coordinated Yb‐based lanthanide metal‐organic framework (named Yb‐DOBDC, where DOBDC is 2,5‐dihydroxyterephthalic acid). Yb‐DOBDC features size‐matched apertures and oxygen‐rich pore microenvironments, securely entrapping L‐Arg through electrostatic interactions and conjugation effects, thereby enhancing the biostability of the drug during delivery. In vitro experiments demonstrate that L‐Arg‐loaded Yb‐DOBDC (L‐Arg@Yb‐DOBDC) promotes NO release upon H2O2 stimulation, and the Yb‐DOBDC framework exhibits good biocompatibility within cells. More interestingly, the near‐infrared‐luminescence‐emitting Yb‐DOBDC exhibits a “turn‐off” behavior upon gradual loading of L‐Arg, enabling self‐quantifying luminescence detection during the encapsulation process. Consequently, the L‐Arg@Yb‐DOBDC system designed in this work, with its high/stable loading capacity and self‐quantifying luminescence detection capability, holds theoretical research value and potential practical application prospects.

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Sterisch erlaubte Supramolekulare Polymerisationen des H‐Typs

Manha Veedu,

Niemeyer,

Bäumer

et al. 2023

Angewandte Chemie

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The functionalization of pi‐conjugated scaffolds with sterically demanding substituents is a widely used tactic to suppress cofacial (H‐type) stacking interactions, which may even inhibit self‐assembly. Contrary to expectations, we demonstrate herein that increasing steric effects can result in an enhanced thermodynamic stability of H‐type supramolecular polymers. In our approach, we have investigated two boron dipyrromethene (BODIPY) dyes with bulky phenyl (2) and mesityl (3) meso‐substituents and compared their self‐assembly in nonpolar media with that of a parent meso‐methyl BODIPY 1 lacking bulky groups. While the enhanced steric demand induces pathway complexity, the superior thermodynamic stability of the H‐type pathways can be rationalized in terms of additional enthalpic gain arising from intermolecular C‐H···F‐B interactions of the orthogonally arranged aromatic substituents, which overrule their inherent steric demand. Our findings underline the importance of balancing competing non‐covalent interactions in self‐assembly.

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Stimuli Response of Eu³⁺-Based Metallo-Supramolecular Polymers toward Pharmaceutical Amines

Cited by 5 publications

References 68 publications

Metallosupramolecular Multiblock Copolymers of Lanthanide Complexes by Seeded Living Polymerization

Metallosupramolecular Multiblock Copolymers of Lanthanide Complexes by Seeded Living Polymerization

High‐Loading L‐Arginine Stabilized in an Oxygen‐Rich Lanthanide Metal–Organic Framework Capable of NO Release and Self‐Quantifying Luminescence Detection

Sterisch erlaubte Supramolekulare Polymerisationen des H‐Typs

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Stimuli Response of Eu3+-Based Metallo-Supramolecular Polymers toward Pharmaceutical Amines

Cited by 5 publications

References 68 publications

Metallosupramolecular Multiblock Copolymers of Lanthanide Complexes by Seeded Living Polymerization

Metallosupramolecular Multiblock Copolymers of Lanthanide Complexes by Seeded Living Polymerization

High‐Loading L‐Arginine Stabilized in an Oxygen‐Rich Lanthanide Metal–Organic Framework Capable of NO Release and Self‐Quantifying Luminescence Detection

Sterisch erlaubte Supramolekulare Polymerisationen des H‐Typs

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Product

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Stimuli Response of Eu³⁺-Based Metallo-Supramolecular Polymers toward Pharmaceutical Amines