Dual-Stimuli-Sensitive Microgels as a Tool for Stimulated Spongelike Adsorption of Biomaterials for Biosensor Applications

Sigolaeva, Larisa V.; Gladyr, Snezhana Yu.; Gelissen, Arjan P. H.; Mergel, Olga; Pergushov, Dmitry V.; Kurochkin, Ilya N.; Plamper, Felix A.; Richtering, Walter

doi:10.1021/bm5010349

Cited by 113 publications

(145 citation statements)

References 60 publications

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“…Copolymers allow intermeshed structures, core–shell structures, hollow multishell structures, or Janus particles . Such copolymer microgels can exhibit more than one VPTT and can be functionalized for two‐step responses . Recent applications of such functionalized microgels include actuating applications such as fiber contraction, membrane modification, surface coating, delivery systems, imaging, as well as targeted protein therapy …”

Section: Introductionmentioning

confidence: 99%

Monitoring Microgel Synthesis by Copolymerization of N‐isopropylacrylamide and N‐vinylcaprolactam via In‐Line Raman Spectroscopy and Indirect Hard Modeling

Meyer-Kirschner

Kather

Ksiazkiewicz

et al. 2018

Macro Reaction Engineering

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Functionalized microgels are typically based on structured copolymers, whose synthesis necessitates knowledge of interactions between different monomer units. This contribution presents in‐line Raman and turbidity monitoring of copolymer microgels based on monomers N‐vinylcaprolactam (VCL) and N‐isopropylacrylamide (NIPAM). During reaction, in‐line Raman spectra are evaluated via multivariate indirect hard modeling (IHM) regression, utilizing pure component models based on parameterized peak functions. To account for variation in Raman baseline intensity, the linear IHM baseline is replaced by a curved baseline, resulting in calibration R² above 0.98 and root‐mean‐squared errors of cross‐validation below 0.12 wt%. Spectra taken in‐line during microgel syntheses reveal NIPAM to react slower than VCL in homopolymerization, but faster than VCL in copolymerization. This effect can be used for synthesis of functional microgels, that is, with tunable volume phase transition temperature. This effect is not visible from turbidity measurements, demonstrating the advantage of in‐line Raman monitoring of chemical components in polymerization processes.

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Section: Introductionmentioning

confidence: 99%

Monitoring Microgel Synthesis by Copolymerization of N‐isopropylacrylamide and N‐vinylcaprolactam via In‐Line Raman Spectroscopy and Indirect Hard Modeling

Meyer-Kirschner

Kather

Ksiazkiewicz

et al. 2018

Macro Reaction Engineering

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show abstract

“…1, 2 Such triggered volume transitions are of interest in various applications, such as drug delivery, functional biomaterials, and biosensors. [3][4][5] In the context of drug delivery, microgels are of particular interest as carriers for biomacromolecular drugs, such as peptides and proteins, since they offer a water-rich environment for incorporated macromolecular drugs, thus reducing detrimental conformational changes and aggregation within the delivery system. 3 Furthermore, microgels offer various additional benefits as delivery systems for such drugs, including protection against enzymatic degradation and controlled or triggered release.…”

Section: Introductionmentioning

confidence: 99%

Factors Affecting Peptide Interactions with Surface-Bound Microgels

et al. 2016

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Effects of electrostatics and peptide size on peptide interactions with surfacebound microgels were investigated with ellipsometry, confocal microscopy, and atomic force microscopy (AFM). Results show that binding of cationic poly-L-lysine (pLys) to anionic, covalently immobilized, poly(ethyl acrylate-co-methacrylic acid) microgels increased with increasing peptide net charge and microgel charge density. Furthermore, peptide release was facilitated by decreasing either microgel or peptide charge density. Analogously, increasing ionic strength facilitated peptide release for short peptides. As a result of peptide binding, the surface-bound microgels displayed pronounced deswelling and increased mechanical rigidity, the latter quantified by quantitative nanomechanical mapping. While short pLys was found to penetrate the entire microgel network and to result in almost complete charge neutralization, larger peptides were partially excluded from the microgel network, forming an outer peptide layer on the microgels. As a result of this difference, microgel flattening was more influenced by the lower Mw peptide than the higher. Peptide-induced deswelling was found to be lower for higher Mw pLys, the latter effect not observed for the corresponding microgels in the dispersed state. While the effects of electrostatics on peptide loading and release were similar to those observed for dispersed microgels, there were thus considerable effects of the underlying surface on peptide-induced microgel deswelling, which need to be considered in the design of surface-bound microgels as carriers of peptide loads, e.g., in drug delivery or in functionalized biomaterials.

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“…[4] Weitverbreitete Beispiele fürk olloidale Tr äger in der heterogenen Katalyse sind Metalloxide, [5] Zeolithe [6] und Polymere. [14] Dank ihrer hohen Biokompatibilitätu nd chemischen Vielfältigkeit zeigen Mikrogele Potenzial in biologischen Anwendungen als Verabreichungssysteme fürW irkstoffe, [15] als Tr ägermaterialien fürd ie Zellkultur, [16] Biosensoren [17] und Biokatalysatoren. [8] Ferner kçnnen Mikrogele mit Hinblick auf stimuliresponsive Eigenschaften maßgeschneidert werden und so auf externe Reize wie Te mperatur, [9] Ionenstärke, [10] pH-Wert, [11] Druck, [12] elektrisches Potential [13] und Licht reagieren.…”

Section: Katalytische Systeme Spielen In Den Unterschiedlichstenunclassified

Selenmodifizierte Mikrogele als bioinspirierte Oxidationskatalysatoren

Tan

Stefka

et al. 2019

Angewandte Chemie

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Anhand des Vorbilds von Glutathionperoxidase (GPx) wurden Mikrogele mit Selenfunktionalitäten versehen und somit katalytisch aktive,k olloidale Mikrogele gewonnen. Diselenid-basierte Vernetzer (Se X-Linker) wurden synthetisiert und gemeinsam mit dem konventionellen Vernetzer N,N'-Methylenbis(acrylamid) (BIS) mittels Fällungspolymerisation in Mikrogele eingebracht. Die in den Mikrogelen verteilten Diselenidbrücken konnten selektiv mittels Oxidation durch H 2 O 2 gespalten und zu Selensäure umgesetzt werden, ohne dass die Mikrogele an struktureller Integritäte inbüßten. Auf diese Weise wurden katalytischaktive Mikrogele mit variablem Selensäuregehalt synthetisiert. Beachtenswert ist, dass die so erhaltenen Mikrogele in einer Modellreaktion, der Oxidation von Acrolein zu Acrylsäure (AA) und Methacrylsäure (MA), im Vergleichzum reinen Se X-Linker eine erhçhte katalytische Aktivitätaufweisen.

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Dual-Stimuli-Sensitive Microgels as a Tool for Stimulated Spongelike Adsorption of Biomaterials for Biosensor Applications

Cited by 113 publications

References 60 publications

Monitoring Microgel Synthesis by Copolymerization of N‐isopropylacrylamide and N‐vinylcaprolactam via In‐Line Raman Spectroscopy and Indirect Hard Modeling

Monitoring Microgel Synthesis by Copolymerization of N‐isopropylacrylamide and N‐vinylcaprolactam via In‐Line Raman Spectroscopy and Indirect Hard Modeling

Factors Affecting Peptide Interactions with Surface-Bound Microgels

Selenmodifizierte Mikrogele als bioinspirierte Oxidationskatalysatoren

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