FRET-Integrated Polymer Brushes for Spatially Resolved Sensing of Changes in Polymer Conformation

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2021 May 12

PMID 33979032

Citations 15

Authors

Quinn A Besford

Huaisong Yong

Holger Merlitz

Andrew J Christofferson

Jens-Uwe Sommer

Petra Uhlmann

Andreas Fery

Affiliations

Soon will be listed here.

Abstract

Polymer brush surfaces that alter their physical properties in response to chemical stimuli have the capacity to be used as new surface-based sensing materials. For such surfaces, detecting the polymer conformation is key to their sensing capabilities. Herein, we report on FRET-integrated ultrathin (<70 nm) polymer brush surfaces that exhibit stimuli-dependent FRET with changing brush conformation. Poly(N-isopropylacrylamide) polymers were chosen due their exceptional sensitivity to liquid mixture compositions and their ability to be assembled into well-defined polymer brushes. The brush transitions were used to optically sense changes in liquid mixture compositions with high spatial resolution (tens of micrometers), where the FRET coupling allowed for noninvasive observation of brush transitions around complex interfaces with real-time sensing of the liquid environment. Our methods have the potential to be leveraged towards greater surface-based sensing capabilities at intricate interfaces.

Citing Articles

Molecular Design Strategies to Enhance the Electroresponse of Polyelectrolyte Brushes: Effects of Charge Fraction and Chain Length Dispersity.

Smook L, de Beer S Macromolecules. 2025; 58(3):1185-1195.

PMID: 39958485 PMC: 11823628. DOI: 10.1021/acs.macromol.4c02579.

Capturing Conformational Transitions of Fluorescently-Coupled Polyelectrolyte Brushes with High Spatiotemporal Resolution.

Yadav J, Hermes I, Fery A, Besford Q Small. 2025; 21(8):e2409323.

PMID: 39838810 PMC: 11855223. DOI: 10.1002/smll.202409323.

On the Road to Circular Polymer Brushes: Challenges and Prospects.

Brio Perez M, Wurm F, de Beer S Langmuir. 2024; 40(14):7249-7256.

PMID: 38556745 PMC: 11008239. DOI: 10.1021/acs.langmuir.3c03683.

PNIPAM Brushes in Colloidal Photonic Crystals Enable Ex Situ Ethanol Vapor Sensing.

Diepenbroek E, Brio Perez M, de Beer S ACS Appl Polym Mater. 2024; 6(1):870-878.

PMID: 38230366 PMC: 10788857. DOI: 10.1021/acsapm.3c02397.

PolyNC: a natural and chemical language model for the prediction of unified polymer properties.

Qiu H, Liu L, Qiu X, Dai X, Ji X, Sun Z Chem Sci. 2024; 15(2):534-544.

PMID: 38179518 PMC: 10763023. DOI: 10.1039/d3sc05079c.

References

Khan A, Scruggs C, Hicks D, Liu G . Two-Dimensional Plasmonic Nanoparticle as a Nanoscale Sensor to Probe Polymer Brush Formation. Anal Chem. 2017; 89(14):7541-7548. DOI: 10.1021/acs.analchem.7b01361. View

Enami S, Colussi A . Reactions of Criegee Intermediates with Alcohols at Air-Aqueous Interfaces. J Phys Chem A. 2017; 121(27):5175-5182. DOI: 10.1021/acs.jpca.7b04272. View

Tokarev I, Tokareva I, Minko S . Optical nanosensor platform operating in near-physiological pH range via polymer-brush-mediated plasmon coupling. ACS Appl Mater Interfaces. 2011; 3(2):143-6. DOI: 10.1021/am101250x. View

Zhao Y, Liu L, Zhao H . Surface Reconstruction by a Coassembly Approach. Angew Chem Int Ed Engl. 2019; 58(31):10577-10581. DOI: 10.1002/anie.201903798. View

Bischofberger I, Calzolari D, Trappe V . Co-nonsolvency of PNiPAM at the transition between solvation mechanisms. Soft Matter. 2014; 10(41):8288-95. DOI: 10.1039/c4sm01345j. View

Hou H, Yin J, Jiang X . Smart Patterned Surface with Dynamic Wrinkles. Acc Chem Res. 2019; 52(4):1025-1035. DOI: 10.1021/acs.accounts.8b00623. View

Kopec M, Tas S, Cirelli M, van der Pol R, de Vries I, Vancso G . Fluorescent Patterns by Selective Grafting of a Telechelic Polymer. ACS Appl Polym Mater. 2019; 1(2):136-140. PMC: 6433164. DOI: 10.1021/acsapm.8b00180. View

Wang T, Yu Y, Chen D, Wang S, Zhang X, Li Y . Naked eye plasmonic indicator with multi-responsive polymer brush as signal transducer and amplifier. Nanoscale. 2017; 9(5):1925-1933. DOI: 10.1039/c6nr09631j. View

Zhang D, Cheng Z, Kang H, Yu J, Liu Y, Jiang L . A Smart Superwetting Surface with Responsivity in Both Surface Chemistry and Microstructure. Angew Chem Int Ed Engl. 2018; 57(14):3701-3705. DOI: 10.1002/anie.201800416. View

10.

Sim X, Wang C, Liu X, Goto A . Multistimuli Responsive Reversible Cross-Linking-Decross-Linking of Concentrated Polymer Brushes. ACS Appl Mater Interfaces. 2020; 12(25):28711-28719. DOI: 10.1021/acsami.0c07508. View

11.

Ji Y, Lin X, Zhang H, Wu Y, Li J, He Q . Thermoresponsive Polymer Brush Modulation on the Direction of Motion of Phoretically Driven Janus Micromotors. Angew Chem Int Ed Engl. 2019; 58(13):4184-4188. DOI: 10.1002/anie.201812860. View

12.

Humphreys B, Wanless E, Webber G . Effect of ionic strength and salt identity on poly(N-isopropylacrylamide) brush modified colloidal silica particles. J Colloid Interface Sci. 2018; 516:153-161. DOI: 10.1016/j.jcis.2018.01.058. View

13.

de Beer S . Switchable friction using contacts of stimulus-responsive and nonresponding swollen polymer brushes. Langmuir. 2014; 30(27):8085-90. DOI: 10.1021/la5013473. View

14.

Yu Y, Lopez de la Cruz R, Kieviet B, Gojzewski H, Pons A, Vancso G . Pick up, move and release of nanoparticles utilizing co-non-solvency of PNIPAM brushes. Nanoscale. 2017; 9(4):1670-1675. DOI: 10.1039/c6nr09245d. View

15.

Yadav V, Jaimes-Lizcano Y, Dewangan N, Park N, Li T, Robertson M . Tuning Bacterial Attachment and Detachment via the Thickness and Dispersity of a pH-Responsive Polymer Brush. ACS Appl Mater Interfaces. 2017; 9(51):44900-44910. DOI: 10.1021/acsami.7b14416. View

16.

Besford Q, Yong H, Merlitz H, Christofferson A, Sommer J, Uhlmann P . FRET-Integrated Polymer Brushes for Spatially Resolved Sensing of Changes in Polymer Conformation. Angew Chem Int Ed Engl. 2021; 60(30):16600-16606. PMC: 8361709. DOI: 10.1002/anie.202104204. View

17.

Yong H, Rauch S, Eichhorn K, Uhlmann P, Fery A, Sommer J . Cononsolvency Transition of Polymer Brushes: A Combined Experimental and Theoretical Study. Materials (Basel). 2018; 11(6). PMC: 6024956. DOI: 10.3390/ma11060991. View

18.

Li Y, Mannel M, Hauck N, Patel H, Auernhammer G, Chae S . Embedment of Quantum Dots and Biomolecules in a Dipeptide Hydrogel Formed In Situ Using Microfluidics. Angew Chem Int Ed Engl. 2020; 60(12):6724-6732. PMC: 7986802. DOI: 10.1002/anie.202015340. View