Reversible temperature-responsive and lectin-recognizing glycosylated block copolymers synthesized by RAFT polymerization

Tanaka, Tomonari; Okamoto, Masaru

doi:10.1038/s41428-018-0038-6

Cited by 18 publications

(14 citation statements)

References 33 publications

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“…We have previously fully resolved the 1 H NMR spectra of homopolymers based on M 1 EMA and M 2 EMA 18 and the spectrum of poly(NIPAm) is well-known. 34 , 35 …”

Section: Resultsmentioning

confidence: 99%

“…We have previously fully resolved the 1 H NMR spectra of homopolymers based on M 1 EMA and M 2 EMA 18 and the spectrum of poly(NIPAm) is well-known. 34,35 The polymerizations were monitored by measuring monomer conversions over time using 1 H NMR data. For all the poly(NIPAm-co-M n EMA)s, the NMR data acquired during the reaction showed that the conversions given in Table 1 were reached after 2 h of reaction and there was no further increase after this time.…”

Section: Methodsmentioning

confidence: 99%

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Thermoresponsive Glycopolymers Based on Enzymatically Synthesized Oligo-β-Mannosyl Ethyl Methacrylates and N-Isopropylacrylamide

et al. 2021

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We present here a series of thermoresponsive glycopolymers in the form of poly( N -isopropylacrylamide) -co- (2-[β-manno[oligo]syloxy] ethyl methacrylate)s. These copolymers were prepared from oligo-β-mannosyl ethyl methacrylates that were synthesized through enzymatic catalysis, and were subsequently investigated with respect to their aggregation and phase behavior in aqueous solution using a combination of 1 H NMR spectroscopy, dynamic light scattering, cryogenic transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). The thermoresponsive glycopolymers were prepared by conventional free radical copolymerization of different mixtures of 2-(β-manno[oligo]syloxy)ethyl methacrylates (with either one or two saccharide units) and N -isopropylacrylamide (NIPAm). The results showed that below the lower critical solution temperature (LCST) of poly(NIPAm), the glycopolymers readily aggregate into nanoscale structures, partly due to the presence of the saccharide moieties. Above the LCST of poly(NIPAm), the glycopolymers rearrange into a heterogeneous mixture of fractal and disc/globular aggregates. Cryo-TEM and SAXS data demonstrated that the presence of the pendant β-mannosyl moieties in the glycopolymers induces a gradual conformational change over a wide temperature range. Even though the onset of this transition is not different from the LCST of poly(NIPAm), the gradual conformational change offers a variation of the temperature-dependent properties in comparison to poly(NIPAm), which displays a sharp coil-to-globule transition. Importantly, the compacted form of the glycopolymers shows a larger colloidal stability compared to the unmodified poly(NIPAm). In addition, the thermoresponsiveness can be conveniently tuned by varying the sugar unit-length and the oligo-β-mannosyl ethyl methacrylate content.

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“…We have previously fully resolved the 1 H NMR spectra of homopolymers based on M 1 EMA and M 2 EMA 18 and the spectrum of poly(NIPAm) is well-known. 34 , 35 …”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Thermoresponsive Glycopolymers Based on Enzymatically Synthesized Oligo-β-Mannosyl Ethyl Methacrylates and N-Isopropylacrylamide

et al. 2021

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“…However, no LCST was obtained for P1-P4 in the pH 7 and 8 buffer solutions, whereas the temperature was notably higher. It is known that the addition of a hydrophilic unit, such as a saccharide-containing unit, to the PNIPAM-based copolymer, increases the LCST of the copolymer [32,33]. For example, Ehe et al reported that the LCST values of PNIPAM bearing glucose (Glc) moieties increased significantly from 56 • C to 81 • C with an increase in the unit ratio of the Glc-bearing monomer from 9% to 15%.…”

Section: Aggregation Behavior Of Glycopolymers In Aqueous Mediamentioning

confidence: 99%

Synthesis and Aggregation Behavior of Temperature- and pH-Responsive Glycopolymers as Sugar-Displaying Conjugates

et al. 2020

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Stimuli-responsive polymers have attracted significant interest in the fields of advanced materials and biomaterials. Herein, temperature- and pH-responsive glycopolymers, which are composed of N-isopropylacrylamide, methacrylic acid, and an acrylamide derivative bearing a lactose moiety, were synthesized via radical copolymerization. The series of resulting glycopolymers had different degrees of substitution of the lactose moieties, were responsive to temperatures between 26.6 °C and 47.6 °C, and formed aggregates above the lower critical solution temperature limit in mild acidic aqueous media (pH 4–6). The temperature-responsive behavior was dependent on the prevailing pH conditions, as no aggregation was observed in neutral and basic aqueous media (pH > 7). The aggregates had saccharide moieties on the surface in aqueous media. The number of saccharide moieties on the surface depended on the saccharide-containing unit ratio in the glycopolymer. The ratio was determined via enzymatic hydrolysis of the lactose moieties using β-galactosidase and the subsequent detection of the released galactose.

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“…The incorporation of hydrophilic or hydrophobic co-monomers allows the cloud point of copolymers to be tuned. The attractive and tunable properties of PNIPAM has resulted in the synthesis of many copolymers and hydrogels using PNIPAM which are used in various applications such as drug delivery and recyclable absorbents [16,17,18,19,20,21,22,23].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Alkali Metal Ion-Binding Copolymers Bearing Dibenzo-24-crown-8 Ether Moieties

et al. 2018

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Dibenzo-24-crown-8 (DB24C8)-bearing copolymers were synthesized by radical copolymerization using a DB24C8-carrying acrylamide derivative and N-isopropylacrylamide monomers. The cloud point of the resulting copolymers changed in aqueous solution in the presence of cesium ions. In addition, the 1H NMR signals of DB24C8-bearing copolymers shifted in the presence of alkali metal. This shift was more pronounced following the addition of Cs+ compared to Rb+, K+, Na+, and Li+ ions due to recognition of the Cs+ ion by DB24C8.

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Reversible temperature-responsive and lectin-recognizing glycosylated block copolymers synthesized by RAFT polymerization

Cited by 18 publications

References 33 publications

Thermoresponsive Glycopolymers Based on Enzymatically Synthesized Oligo-β-Mannosyl Ethyl Methacrylates and N-Isopropylacrylamide

Thermoresponsive Glycopolymers Based on Enzymatically Synthesized Oligo-β-Mannosyl Ethyl Methacrylates and N-Isopropylacrylamide

Synthesis and Aggregation Behavior of Temperature- and pH-Responsive Glycopolymers as Sugar-Displaying Conjugates

Synthesis and Characterization of Alkali Metal Ion-Binding Copolymers Bearing Dibenzo-24-crown-8 Ether Moieties

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