Swelling, Interfacial Behavior, and Rheology of Soft Core-Shell Microgels Introducing Acid Isomer for pH-Temperature Dual-responsiveness

Li Zhang; Xin-Rui Li; Xia-Hui Xiao; Li-Dan Zhou; Yu-Wei Zhu; Jia-Yu Chen; Hang Jiang; Jie Han; Wei Liu; To Ngai

doi:10.1007/s10118-025-3310-1

Your Location：

Home >

Browse articles >

Swelling, Interfacial Behavior, and Rheology of Soft Core-Shell Microgels Introducing Acid Isomer for pH-Temperature Dual-responsiveness

RESEARCH ARTICLE | Updated：2025-07-14

- Swelling, Interfacial Behavior, and Rheology of Soft Core-Shell Microgels Introducing Acid Isomer for pH-Temperature Dual-responsiveness
- Chinese Journal of Polymer Science Vol. 43, Issue 5, Pages: 745-755(2025)
- Affiliations：
  
  a.The Key Laboratory of Synthetic and Biological Colloids, Ministry of Education & School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China
  b.Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong 999077, China
  c.School of Science and Technology, Hong Kong Metropolitan University, Homantin, Kowloon, Hong Kong 999077, China
- Author bio：
  
  weiliu@jiangnan.edu.cn (W.L.)
  tongai@cuhk.edu.hk (T.N.)
- Funds：
- DOI：10.1007/s10118-025-3310-1
  CLC：
- Received：16 December 2024，
  
  Revised：2025-01-21，
  
  Accepted：23 January 2025，
  
  Online First：07 April 2025，
  
  Published：30 April 2025
- Accepted：
Scan QR Code
Zhang, L.; Li, X. R.; Xiao, X. H.; Zhou, L. D.; Zhu, Y. W.; Chen, J. Y.; Jiang, H.; Han, J.; Liu, W.; Ngai, T. Swelling, interfacial behavior, and rheology of soft core-shell microgels introducing acid isomer for pH-temperature dual-responsiveness. Chinese J. Polym. Sci. 2025, 43, 745–755

Li Zhang, Xin-Rui Li, Xia-Hui Xiao, et al. Swelling, Interfacial Behavior, and Rheology of Soft Core-Shell Microgels Introducing Acid Isomer for pH-Temperature Dual-responsiveness[J]. Chinese Journal of Polymer Science, 2025, 43(5): 745-755.
Zhang, L.; Li, X. R.; Xiao, X. H.; Zhou, L. D.; Zhu, Y. W.; Chen, J. Y.; Jiang, H.; Han, J.; Liu, W.; Ngai, T. Swelling, interfacial behavior, and rheology of soft core-shell microgels introducing acid isomer for pH-temperature dual-responsiveness. Chinese J. Polym. Sci. 2025, 43, 745–755 DOI： 10.1007/s10118-025-3310-1.

Li Zhang, Xin-Rui Li, Xia-Hui Xiao, et al. Swelling, Interfacial Behavior, and Rheology of Soft Core-Shell Microgels Introducing Acid Isomer for pH-Temperature Dual-responsiveness[J]. Chinese Journal of Polymer Science, 2025, 43(5): 745-755. DOI： 10.1007/s10118-025-3310-1.

摘要

By incorporating cis-trans isomers of dicarboxylic acids—citraconic acid and mesaconic acid—into the polymer network of poly(

-isopropylacrylamide)

pH-temperature dual-responsive core-shell microgels were successfully synthesized. Molecular structure and crosslinking position of the dicarboxylic acids significantly affected the interfacial behavior and bulk viscoelasticity of the core-shell microgels.

Abstract

In this study

a pair of dicarboxylic acids as

cis

trans

isomerism—citraconic acid (CA) and mesaconic acid (MA)

was incorporated into polymeric networks of poly(

-isopropylacrylamide) (PNIPAM)-based core-shell microgels

via

semi-batch precipitation polymerization. We demonstrated that the pH-temperature dual responsiveness of the core-shell microgels is highly correlated with the structure and position of the acid isomers. Both the

cis

trans

molecular structure and the crosslinking position of the dicarboxylic acids significantly influenced the hydration capacity and surface charge density of the core-shell microgels. These diverse properties first influenced the swelling behavior

further affecting the interfacial behavior of the microgels

including the oil-water dynamic interfacial tension and air-water compression isotherms. Furthermore

the rheological behavior of the microgel suspensions also displayed distinct dependences on the frequency and temperature

illustrating that the

cis-trans

molecular structure and crosslinked position of the dicarboxylic acids also significantly influenced the interparticle clustering in the bulk solution. Our results suggest that the pH sensitivity of the

cis

trans

dicarboxylic acid isomer affects the ionization and surface charge distribution of the core or shell layers of individual microgels

which further determines the interparticle interaction and cooperative rearrangement at interfaces and in the bulk.

关键词

Keywords

references

Pelton, R. H.; Chibante, P. Preparation of aqueous latices with N -isopropylacrylamide. Colloids Surfaces 1986 , 20 , 247−256..

Brézault, A.; Perrin, P.; Sanson, N. Multiresponsive supramolecular Poly( N -isopropylacrylamide) microgels. Macromolecules 2024 , 57 , 2651−2660..

Tavagnacco, L.; Zanatta, M.; B uratti, E.; Bertoldo, M.; Chiessi, E.; Appel, M.; Natali, F.; Orecchini, A.; Zaccarelli, E. Water slowing down drives the occurrence of the low temperature dynamical transition in microgels. Chem. Sci. 2024 , 15 , 9249−9257..

Vijayakumar, B.; Takatsuka, M.; Kita, R.; Shinyashiki, N.; Yagihara, S.; Rathinasabapathy, S. Dynamics of the Poly(N-Isopropylacrylamide) Microgel Aqueous Suspension Investigated by Dielectric Relaxation Spectroscopy. Macromolecules 2022 , 55 , 1218−1229..

Zanatta. M.; Tavagnacco, L.; Buratti, E.; Bertoldo, M.; Natali, F.; Chiessi, E.; Orecchini, A.; Zaccarelli, E. Evidence of a low-temperature dynamical transition in concentrated microgels. Sci. Adv. 2018 , 4 , 5895..

Liu, W.; Zhu, Y.; Zhang, T.; Zhu, H.; He, C.; Ngai, T. Microrheology of thermoresponsive poly( N -isopropylacrylamide) microgel dispersions near a substrate surface. J. Colloid Interface Sci. 2021 , 597 , 104−113..

Liu, W.; Zhu, Y.; Li, Y.; Han, J.; Ngai, T. Unveiling the structural relaxation of microgel suspensions at hydrophilic and hydrophobic interfaces. J. Colloid Interface Sci. 2023 , 633 , 948−958..

Vikulina, A. S.; Feoktistova, N. A.; Balabushevich, N. G. Klitzing, R.; Volodkin, D. Cooling-triggered release from mesoporous poly( N -isopropylacrylamide) microgels at physiological conditions. ACS Appl. Mater. Interfaces 2020 , 12 , 57401−57409..

Harrer, J.; Rey, M.; Ciarella, S.; Löwen, H.; Janssen, L. M. C. Vogel, N. Stimuli-responsive behavior of PNiPAm microgels under interfacial confinement. Langmuir 2019 , 35 , 10512−10521..

Kwok, M.; Li, Z.; Ngai, T. Controlling the synthesis and characterization of micrometer-sized PNIPAM microgels with tailored morphologies. Langmuir 2013 , 29 , 9581−9591..

Su, W.; Yang, M.; Zhao, K.; Ngai, T. Influence of charged groups on the structure of microgel and volume phase transition by dielectric analysis. Macromolecules 2016 , 49 , 7997−8008..

Karg, M.; Pastoriza-Santos, I.; Rodriguez-González, B.; Klitzing, R.; Wellert, S.; Hellweg, T. Temperature, pH, and ionic strength induced changes of the swelling behavior of PNIPAM-poly(allylacetic acid) copolymer microgels. Langmuir 2008 , 24 , 6300−6306..

Snowden, M. J.; Chowdhry, B. Z.; Vincent, B.; Morris, G. E. Colloidal copolymer microgels of N -isopropylacrylamide and acrylic acid: pH, ionic strength and temperature effects. J. Chem. Soc. Faraday Trans. 1996 , 92 , 5013−5016..

Hou, Y.; Yu, C.; Liu, G.; Ngai, T.; Zhang, G. Effects of anions on the aggregation of charged microgels. J. Phys. Chem. B 2010 , 114 , 3799−3803..

Zakrevskyy, Y.; Richter, M.; Zakrevska, S.; Lomadze, N.; Klitzing, R.; Santer, S. Light-controlled reversible manipulation of microgel particle size using azobenzene-containing surfactant. Adv. Funct. Mater. 2012 , 22 , 5000−5009..

Jelken, J.; Jung, S. H.; Lomadze, N.; Gordievskaya, Y. D.; Kramarenko, E. Y.; Pich, A.; Santer, S. Tuning the volume phase transition temperature of microgels by light. Adv. Funct. Mater. 2022 , 32 , 2107946..

Brugger, B.; Richtering, W. Magnetic, thermosensitive microgels as stimuli-responsive emulsifiers allowing for remote control of separability and stability of oil in wa ter-emulsions. Adv. Mater. 2007 , 19 , 2973−2978..

Nam, S.; Kim, H.; Lee, S. M.; Durukan, M. B.; Unalan, H. E.; Lee, H. J. A glucose-responsive microgel-based soft etalon as an epidermal glucose colorimetric sensor. Sensor. Actuat. B-Chem. 2023 , 396 , 134554..

Hoare, T.; Pelton, R. Engineering glucose swelling responses in poly( N -isopropylacrylamide)-based microgels. Macromolecules 2007 , 40 , 670−678..

Nigro, V.; Angelini, R.; Rosi, B.; Bertoldo, M.; Buratti, E.; Casciardi, S.; Sennato, S.; Ruzicka, B. Study of network composition in interpenetrating polymer networks of poly( N- isopropylacrylamide) microgels: the role of poly(acrylic acid). J. Colloid Interface Sci. 2019 , 545 , 210−219..

Kwok, M.; Ngai T. Emulsions stabilized by pH-responsive PNIPAM-based microgels: Effect of spatial distribution of functional carboxylic groups on the emulsion stability. J. Taiwan Inst. Chem. Eng. 2018 , 92 , 97−105..

Schmidt, S.; Liu, T.; Rütten, S.; Phan, K. ; Möller, M.; Richtering, W. Influence of microgel architecture and oil polarity on stabilization of emulsions by stimuli-sensitive core-shell poly( N -isopropylacrylamide- co -methacrylic acid) microgels: mickering versus pickering behavior. Langmuir 2011 , 27 , 9801−9806..

Dhanya, S.; Bahadur, D.; Kundu, G. C.; Srivastava, R. Maleic acid incorporated poly( N -isopropylacrylamide) polymer nanogels for dual-responsive delivery of doxorubicin hydrochloride. Eur. Polym. J. 2013 , 49 , 22−32..

Cui, X.; Tang, J.; Hartanto, Y.; Zhang, J.; Bi, J.; Dai, S.; Qiao, S. Z.; Cheng, K.; Zhang, H. NIPAM-based microgel microenvironment regulates the therapeutic function of cardiac stromal cells. ACS Appl. Mater. Interfaces 2018 , 10 , 37783−37796..

Minamia, S.; Yamamotoa, A.; Ourab, S.; Watanabe, T.; Suzuki, D.; Urayama, K. Criteria for colloidal gelation of thermo-sensitive poly( N -isopropylacrylamide) based microgels. J. Colloid Interface Sci. 2020 , 568 , 165−175..

Wilson, K. M.; Danielson, N. D. Micellar and sub-micellar chromatography with a cocamidopropyl betaine surfactant. J. Chromatogr. A 2022 , 1681 , 463442..

Brugger, B.; Richtering, W. Emulsions stabilized by stimuli-sensitive poly( N -isopropylacrylamide)- co -methacrylic acid polymers: microgels versus low molecular weight polymers. Langmuir 2008 , 24 , 7769−7777..

Rey, M.; Hou, X.; Tang, J. S. J.; Vogel, N. Interfacial arrangement and phase transitions of PNiPAm microgels with different crosslinking densities. Soft Matter 2017 , 13 , 8717−8727..

Views

150

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Microgels Deswell against Concentration and Solvent Molecular Mass

Droplet Bridging Effect in Polymer/Polymer/Filler Ternary Composites

Preparation and Rheological Characterization of Long Chain Branching Polyglycolide

Experimental Investigation of Graphene and TiO2 Reinforced Poly(vinyl alcohol)-based Fiber Metal Laminates

Alternating Poly(ether-alt-ester)s with High Glass Transition Temperature Enabled by Rotationally Constrained Biaryl Units

Related Author

Yi-Hui Zhu

Qing-Zhi Zou

Zhan-Hui Gan

Yi-Fu Ruan

Kai Qi

Peng-Fei Zhang

Geng-Xin Liu

Feng-Yi Hou

Related Institution

South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter & Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices, South China University of Technology

Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences

Lab, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai

State Key Laboratory of Advanced Fiber Materials, Center for Advanced Low-Dimension Materials, College of Materials Science and Engineering, Donghua University

Advanced Rheology Institute, Department of Polymer Science and Engineering, Shanghai Jiao Tong University

⁰