Multi-stimuli responsive block copolymers as a smart release platform for a polypyridyl ruthenium complex

Appold, Michael; Mari, Cristina; Lederle, Christina; Elbert, Johannes; Schmidt, Claudia; Ott, Ingo; Stühn, Bernd; Gasser, Gilles; Gallei, Markus

doi:10.1039/c6py02026g

Cited by 50 publications

(47 citation statements)

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“…11-20 organotin compounds [20][21][22] or other metallodrugs. 10,23 . This approach has been shown to be highly effective against cancer cell lines.…”

Section: Introductionmentioning

confidence: 99%

Mesoporous silica nanoparticles functionalised with a photoactive ruthenium(ii) complex: exploring the formulation of a metal-based photodynamic therapy photosensitiser

et al. 2019

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A series of nanomaterials based on mesoporous silica have been synthesised and functionalised with a photoactive polypyridyl ruthenium(ii) complex, namely [Ru(bipy)2-dppz-7-hydroxymethyl][PF6]2 (bipy = 2,2'-bipyridine, dppz = dipyrido[3,2-a:2',3'-c]phenazine), by various methods. The functionalisation reactions were based on the covalent binding to different ligands attached to the pores of the mesoporous nanoparticles and a simple physisorption using polyamino-functionalised mesoporous silica nanoparticles. The resulting nanostructured systems have been characterised by XRD, XRF, BET, SEM and TEM, observing the incorporation of the metallodrug onto the nanostructured silica in a different way depending on the synthetic method used in the loading reactions. In our studies, we have also observed that functionalisation with the metallodrug causes changes in the structural and textural features of the materials. The phototherapeutic activity of the ruthenium-functionalised materials in HeLa cervical cancer cells has been tested and the preliminary results are presented herein.

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“…11-20 organotin compounds [20][21][22] or other metallodrugs. 10,23 . This approach has been shown to be highly effective against cancer cell lines.…”

Section: Introductionmentioning

confidence: 99%

Mesoporous silica nanoparticles functionalised with a photoactive ruthenium(ii) complex: exploring the formulation of a metal-based photodynamic therapy photosensitiser

et al. 2019

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“…Furthermore, stimuli‐responsive block copolymers—commonly referred to as smart block copolymers—can be designed to alter conformation, solubility, or even covalent structure, as a function of external triggers. Common stimuli include temperature, pH, light, redox reagents, and electrical fields …”

Section: Introductionmentioning

confidence: 99%

Polyvinylpyridine‐Grafted Block Copolymers by an Iterative All‐Anionic Polymerization Strategy

Appold

Rüttiger

Kuttich

et al. 2017

Macro Chemistry & Physics

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Common stimuli include temperature, pH, light, redox reagents, and electrical fields. [16][17][18][19][20][21][22][23] Block copolymers featuring polyvinylpyridine (PVP) segments have attracted enormous attention due to their ability to undergo microphase separation, metal ion complexation, nanoparticle complexation, as well as participate in hydrogen bonding. [24] Stamm and co-workers have reported extensively on poly(styrene-block-(4-vinylpyridine)) (PS-b-P4VP) as a system. For example, they have reported on the influence of hydrogen bonding for poly(styrene-block-(4-vinylpyridine)) (PS-b-P4VP) for microphase separation, [25] the use of sacrificial PS-b-P4VP networks as carbon precursors, [26] the use of PS-b-P4VP as polymer templates for the preparation of highly ordered arrays of metallic nanodots, [27] and the preparation of P4VP-based block copolymers for helically arranged nanoparticle complexation in cylindrical domains. [28] Besides their structure formation capabilities, PVPs have been used as pH-responsive homopolymers, or as reversibly addressable segments in smart block copolymer architectures featuring protonated pyridinium moieties. [16] For example, Li et al. reported on the pH responsiveness of Au@PVP particles, and their application as pHresponsive bimetallic catalysts. [29] Furthermore, responsive P4VP-based cross-linked films have been used as pH sensors and as surfaces with controllable surface wettability. [30] The group of Eisenberg has also reported on the morphological changes in PS-b-P4VP micelles as a function of pH range. [31] Additionally, multi-stimuli-responsive block copolymers featuring a poly(2-vinylpyridine) (P2VP)-containing block segment were investigated in thin films, [32] as micelles in water, [33,34] and as smart nanocapsules. The latter have been advantageously used for the triggered release of different payloads from the capsules' interior. [21,35] As another impressive example, PSb-P4VP was the first polymer under investigation for creating integral asymmetric membranes with highly uniform pore sizes. [36] The complexation of the P4VP block segments with copper(II) ions was utilized for a stabilization of the PS-b-P4VP micelles in solution and hence a high reproducibility of uniform pore structures was achieved. [37,38] Besides copper(II) salts, other transition metals like nickel(II), cobalt(II), and iron(II) are also capable of influencing the self-organization of Anionic PolymerizationsFunctional block copolymers are a highly relevant material platform for many potential applications in fields of nanolithography, drug delivery, and separation technologies. Here, poly(2-vinylpyridine) (P2VP)-grafted diblock copolymers consisting of polystyrene-block-polyisoprene (PS-b-PI) backbone are synthesized via an iterative anionic grafting-to polymerization strategy. P2VP macro anions having molar masses of 1.1, 3.6, and 9.9 kDa are grafted to PS-b-PI block copolymers featuring 37 mol% 1,2-polyisoprene moieties. Prior to the grafting-to strategy, the PS-b-PI is subjected to pl...

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“…62 As examples, selenium [63][64][65] , silver 66 , gold [67][68][69] and silicon [70][71][72][73][74] nanoparticles as well as upconverting nanoparticles [75][76][77] were successfully loaded with Ru(II) polypyridine complexes, forming a drug delivery vehicle. Further, the physical encapsulation of Ru(II) polypyridine complexes into polymeric partciles [78][79][80][81][82][83][84][85][86] , micelles [87][88][89] , dendrimers 90 or liposomes [91][92] was reported. Recent studies have also shown the conjugation of Ru(II) polypyridine complexes to carbon nanotubes [93][94][95] as well as metal-organic frameworks 96-97 as a delivery system.…”

Section: Introductionmentioning

confidence: 99%

Polymeric Encapsulation of a Ruthenium Polypyridine Complex for Tumor Targeted 1- and 2-Photon Photodynamic Therapy

Karges¹,

Li²,

Zeng³

et al. 2020

Preprint

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Photodynamic therapy is a medical technique, which is gaining increasing attention to treat various types of cancer. Among the investigated classes of photosensitizers, the use of Ru(II) polypyridine complexes is gaining momentum. However, the currently investigated compounds generally show poor cancer cell selectivity. As a consequence, high drug doses are needed, which can cause side effects. To overcome this limitation, there is a need for the development of a suitable drug delivery system to increase the amount of PS delivered to the tumor. Herein, we report on the encapsulation of a promising Ru(II) polypyridyl complex into polymeric nanoparticles with terminal biotin groups. Thanks to this design, the particles showed much higher selectivity for cancer cells in comparison to non-cancerous cells in a 2D monolayer and 3D multicellular tumor spheroid model. As a highlight, upon intravenous injection of an identical amount of the Ru(II) polypyridine complex, an improved accumulation inside an adenocarcinomic human alveolar basal epithelial tumor of a mouse by a factor of 8.7 compared to the Ru complex itself was determined. The nanoparticles were found to have a high phototoxic effect upon 1-photon (500 nm) or 2-photon (800 nm) excitation with an eradication of an adenocarcinomic human alveolar basal epithelial tumor inside a mouse. Overall, this work describes, to the best of our knowledge, the first <i>in vivo</i> study demonstrating the cancer cell selectivity of a very promising Ru(II)-based PDT photosensitizer encapsulated into polymeric nanoparticles with terminal biotin groups.

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Multi-stimuli responsive block copolymers as a smart release platform for a polypyridyl ruthenium complex

Abstract: An efficient protocol for the preparation of poly(N,N-dimethylaminoethyl methacrylate)(PDMAEMA)-based multi-stimuli responsive block copolymers (BCPs) with poly(methyl methacrylate) (PMMA)viaanionic polymerization protocols is presented.

Cited by 50 publications

References 63 publications

Mesoporous silica nanoparticles functionalised with a photoactive ruthenium(ii) complex: exploring the formulation of a metal-based photodynamic therapy photosensitiser

Mesoporous silica nanoparticles functionalised with a photoactive ruthenium(ii) complex: exploring the formulation of a metal-based photodynamic therapy photosensitiser

Polyvinylpyridine‐Grafted Block Copolymers by an Iterative All‐Anionic Polymerization Strategy

Polymeric Encapsulation of a Ruthenium Polypyridine Complex for Tumor Targeted 1- and 2-Photon Photodynamic Therapy

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