Self-catalysed folding of single chain nanoparticles (SCNPs) by NHC-mediated intramolecular benzoin condensation

Garmendia, Sofiem; Dove, Andrew P.; Taton, Daniel; O’Reilly, Rachel K.

doi:10.1039/c9py00149b

Cited by 6 publications

(4 citation statements)

References 46 publications

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“…Highly efficient thermoresponsive organocatalytic SCNPs towards tetrahydropyranilation of methanol were reported by Rumyantsev and colleagues [37]. Recently, a variety of N-heterocyclic carbene-based SCNPs have been synthesized by Taton and colleagues and employed as advanced catalysts for the benzoin condensation reaction [38,39]. More recently, Yan and coworkers have reported CO2-folded SCNPs that can function as recyclable, intensified carboxylase mimics [40].…”

Section: Introductionmentioning

confidence: 99%

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“Clickase” Single-Chain Nanoparticles: Effect of Intra-Chain Distribution of Catalytic Sites on Catalytic Activity

Asenjo-Sanz¹,

Claros²,

González³

et al. 2021

Preprint

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“Clickase” single-chain nanoparticles (Ck-SCNPs) are folded, enzyme-mimetic unimolecular polymeric nano-objects containing copper (Cu) ions able to catalyze the azide-alkyne Huisgen cycloaddition reaction in water and/or selected organic solvents, often in the presence of a reductant. Herein, we investigate the effect of morphology on catalytic activity of Ck-SCNPs synthesized by means of two different routes. An amphiphilic random copolymer composed of oligo(ethylene glycol) methyl ether methyl methacrylate (OEGMA) and 2-acetoacetoxy ethyl methacrylate (AEMA) units was used as precursor of these Ck-SCNPs. Folding was promoted through metal complexation between Cu(II) ions and beta-ketoester-containing AEMA moieties. The first route resulted in Ck-SCNPs1 containing Cu ions homogeneously distributed within each nanoparticle, whereas the second one promoted intra-chain clustering of Cu ions inside Ck-SCNPs2. A model fluorogenic “click” reaction between 9-(azidomethyl)anthracene and phenylacetylene, which was catalyzed either by Ck-SCNPs1 or Ck-SCNPs2, was used to unravel the effect of morphology on catalytic activity. This work paves the way to improve the catalytic activity of metallo-folded SCNPs through control of the intra-chain distribution of catalytic sites.

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Section: Introductionmentioning

confidence: 99%

“…On one hand, a variety of sparse SCNPs endowed with catalytic properties have been reported [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43]. Hence, SCNPs showing reductase-and polymerase-like properties were developed by our team based on the entrapment of B(C6F5)3 into the SCNP nanodomains [29].…”

Section: Introductionmentioning

confidence: 99%

“Clickase” Single-Chain Nanoparticles: Effect of Intra-Chain Distribution of Catalytic Sites on Catalytic Activity

Asenjo-Sanz¹,

Claros²,

González³

et al. 2021

Preprint

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“…In the past two decades, intrachain collapsing of random polymeric coils into single-chain polymer nanoparticles (SCNPs) has attracted much attention, including in the biomedical field . A range of cross-linking chemistries have been employed to enable the intramolecular chain collapse such as the formation via covalent bonds, − dynamic covalent bonds, − or supramolecular interactions. − In each case, small nanoparticles (NPs) with diameters usually less than 10 nm were obtained. Recently, light-driven ligation chemistries have evolved as one of the preferred tools for the preparation of SCNPs. ,− Ligation chemistries that allow cross-linking under irradiation at different wavelengths of light include the [2 + 2] cycloaddition of stilbene, ,,, [4 + 4] cycloaddition of anthracene, ,, Diels–Alder, nitrile imine-mediated tetrazole-ene cycloaddition (NITEC), and nitrile imine-mediated carboxylic acid ligation (NICAL) reactions. , The advantages of these strategies over conventional chemical methods are that they are frequently high-yielding, relatively fast, and require no additional catalysts or postpurification.…”

Section: Introductionmentioning

confidence: 99%

Effects of Drug Conjugation on the Biological Activity of Single-Chain Nanoparticles

Vo,

Nothling,

Raveendran

et al. 2024

Biomacromolecules

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The field of single-chain nanoparticles (SCNPs) continues to mature, and an increasing range of reports have emerged that explore the application of these small nanoparticles. A key application for SCNPs is in the field of drug delivery, and recent work suggests that SCNPs can be readily internalized by cells. However, limited attention has been directed to the delivery of small-molecule drugs using SCNPs. Moreover, studies on the physicochemical effects of drug loading on SCNP performance is so far missing, despite the accepted view that such small nanoparticles should be significantly affected by the drug loading content. To address this gap, we prepared a library of SCNPs bearing different amounts of a covalently conjugated therapeutic drug−sulfasalazine (SSZ). We evaluated the impact of the conjugated drug loading on both the synthesis and biological activity of SCNPs on pancreatic cancer cells (AsPC-1). Our results reveal that covalent drug conjugation to the side chains of the SCNP polymer precursor interferes with chain collapse and cross-linking, which demands optimization of reaction conditions to reach high degrees of cross-linking efficiencies. Small-angle neutron scattering and diffusion-ordered spectroscopy nuclear magnetic resonance (DOSY NMR) analyses reveal that SCNPs with a higher drug loading display larger sizes and looser structures, as well as increased hydrophobicity associated with a higher SSZ content. Increased SSZ loading led to reduced cellular uptake when assessed in vitro, whereby SCNP aggregation on the surface of AsPC-1 cells led to reduced toxicity. This work highlights the effects of drug loading on the drug delivery efficiency and biological behavior of SCNPs.

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“…Synthetically, they can be either the polymerization products of IL monomers or accessed via chemical modification of pre-existent polymers through ion exchange, N -alkylation, ligation of reactive ILs onto a polymer backbone, and others. − PIL research in its essence is driven by the desire that such materials have joint properties and functions of ILs and classic polymers. Recent advances, however, have actually exceeded far more the expectation of the community, as unknown PIL chemistry and physics have been continuously discovered. − In the entire PIL family, the polyimidazolium group has been so far the most widely studied and reported for a long time, as they exhibit to a large extent the expected common properties of PILs . Nevertheless, there is a persistent effort in this field to seek for unexplored chemical structures, for example, exotic cations, anions, and backbones, to enrich the structure toolbox and to broaden the conventional property window of PILs. − …”

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confidence: 99%

Linear Main-Chain 1,2,4-Triazolium Poly(ionic liquid)s: Single-Step Synthesis and Stabilization of Cellulose Nanocrystals

et al. 2019

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Linear main-chain 1,2,4-triazolium-based poly(ionic liquid)s (PILs) were synthesized in this contribution. The polymerization process is experimentally very simple and involves only a single-step polycondensation of a commercially available monomer in DMSO as solvent at 120 °C. Their thermal stability and solubility were analyzed in terms of different counteranions. Due to the ease of this synthetic route, it was readily applied to graft onto sulfonated cellulose nanocrystals (CNCs) via a one-step in situ polymerization. The assynthesized PIL@CNC hybrid colloids exhibit adaptive dispensability in water and organic solvents.

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Self-catalysed folding of single chain nanoparticles (SCNPs) by NHC-mediated intramolecular benzoin condensation

Abstract: A self-catalysed folding strategy to form single chain nanoparticles (SCNPs) was developed via an intramolecular N-heterocyclic carbene (NHC)-mediated benzoin condensation.

Cited by 6 publications

References 46 publications

“Clickase” Single-Chain Nanoparticles: Effect of Intra-Chain Distribution of Catalytic Sites on Catalytic Activity

“Clickase” Single-Chain Nanoparticles: Effect of Intra-Chain Distribution of Catalytic Sites on Catalytic Activity

Effects of Drug Conjugation on the Biological Activity of Single-Chain Nanoparticles

Linear Main-Chain 1,2,4-Triazolium Poly(ionic liquid)s: Single-Step Synthesis and Stabilization of Cellulose Nanocrystals

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