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We report the straightforward, time-efficient synthesis of radical core-shell nanoparticles (NPs) by polymerization-induced self-assembly. A nitroxide-containing hydrophilic macromolecular precursor was prepared by ring-opening metathesis copolymerization of norbornenyl derivatives of TEMPO and oligoethylene glycol and was chain-extended in situ with norbornene in ethanolic solution, leading to simultaneous amphiphilic block copolymer formation and self-assembly. Without any intermediate purification from the monomers to the block copolymers, radical NPs with tunable diameters ranging from 10 to 110 nm are obtained within minutes at room temperature. The high activity of the radical NPs as chemoselective and homogeneous, yet readily recyclable catalysts is demonstrated through oxidation of a variety of alcohols and recovery by simple centrifugation. Furthermore, the NPs show biocompatibility and antioxidant activity in vitro.
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http://dx.doi.org/10.1002/anie.201813434 | DOI Listing |
J Polym Sci (2020)
June 2025
Gutekunst. School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia, 30332, United States.
Levoglucosenone () has emerged as a versatile synthon in target-oriented synthesis due to its availability from cellulose. While its functionality and chirality have found direct use as a small molecule building block, translation to polymerization has been more challenging. Monomers derived from have been difficult to polymerize through conventional chain-growth approaches due to lack of ring strain and steric hindrance.
View Article and Find Full Text PDFACS Cent Sci
August 2025
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
Ring-opening metathesis polymerization (ROMP) of norbornene derivatives enables access to polymeric materials for applications ranging from targeted drug delivery to high-performance thermosets; however, the carbon-carbon backbones of ROMP-derived poly-(norbornenes) resist deconstruction under mild, selective conditions. Cleavable comonomers (CCs) have been introduced to address this limitation, yet their implementation has been hindered by prohibitive costs and/or suboptimal reactivity. Moreover, the discovery of existing CCs has been largely empirical, lacking clear design principles.
View Article and Find Full Text PDFMacromol Rapid Commun
August 2025
Institute of Organic Chemistry and Macromolecular Chemistry, Heinrich Heine University Düsseldorf, Düsseldorf, Germany.
Three new norbornene monomers carrying naphthyl-based sidechains with varying levels of electron deficiency are synthesized, characterized by H NMR, 2D-NMR, UV-vis, and fluorescence spectroscopies, as well as mass spectrometry. The kinetics of their ring-opening polymerization using a third-generation Grubbs catalyst are established, and the resulting polymers are characterized by size-exclusion chromatography, along with UV-vis and fluorescence spectroscopies. These naphthalene-based polynorbornenes are shown to exhibit fluorescence, accompanied by a quenching behavior when exposed to an electron-rich aromatic compound.
View Article and Find Full Text PDFTalanta
August 2025
School of Biomedical Engineering, Shenzhen University Health Science Center, Shenzhen, Guangdong, 518060, PR China.
Accurate diagnosis of Gram-negative bacterial infections hinges critically on endotoxin detection, with ultrasensitive quantification playing a pivotal role in clinical diagnosis, precision therapy, food safety and environmental monitoring. Herein, we pioneer an electrochemical aptasensing platform based on metal-free photoinduced ring-opening metathesis polymerization (MF photo-ROMP) for endotoxin analysis. Specifically, the aptamer is employed for selective capture of endotoxin, whose glycan chain is then modified with 4-formylphenylboronic acid via boronate affinity.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Institute of Biotechnology, RWTH Aachen University, Worringerweg 3, 52074, Aachen, Germany.
Degradation of synthetic polymers inevitably leads to the formation of nanoplastics (NPs), and recent studies associate health risks with NPs. Therefore, catching and degrading NPs are important to manage environmental and human health risks. In this study, we developed a biohybrid catalyst system with two functionalities to capture (Hook) and degrade (Decay) NPs.
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