Formation of the Self-assembled Multilayers Containing the Temperature/ pH Dual-responsive Microgels

Author(s): Gang Liu, Chunlin Liu, Yuyuan Chen, Shuai Qin, Suyuan Yang, Dun Wu, Haitao Xi, Zheng Cao*.

Journal Name: Nanoscience & Nanotechnology-Asia

Volume 9 , Issue 2 , 2019

Become EABM
Become Reviewer

Graphical Abstract:


Abstract:

Background: Stimuli-responsive microgels have attracted extensive investigations due to their potential applications in drug delivery, catalysis, and sensor technology. The self-assembled mcirogel films can contain different functional groups (e.g., -COOH, -NH2, -C=ONH2) to interact with specific molecules and ions in water, and their study is becoming increasingly important for developing both absorbent materials and sensor coatings. This paper is aimed to obtain a better understanding of the LbL multilayer formation of microgels and the branched PEI using the mass sensitive QCM. Additionally the influence of the temperature and pH on the formation of the microgel films can be achieved.

Methods: The temperature and pH sensitive P(NIPAM-co-AA-co-TMSPMA) microgels were prepared by surfactant-free emulsion polymerization and confirmed by FT-IR, laser particle size analysis, and SEM. The obtained microgel and PEI were further used to prepare multilayer thin films by the LbL self-assembly technique monitored by QCM, and their morphology and hydrophilic properties were determined by AFM and water contact angle measurements.

Results: The thermosensitive and pH sensitive P(NIPAM-co-AA-co-TMSPMA) microgels were prepared by surfactant-free emulsion polymerization. The size and swelling properties of the microgels prepared are highly dependent on the preparation conditions such as the AA and crosslinker content, and microgels showed good temperature and pH responsive properties. SEM images showed that microgels dispersed evenly on the substrate and had a uniform particle size distribution, which was consistent with the light particle size analysis results. Furthermore, multilayer films composed of the negatively charged microgels and the positively charged PEI have been built up by a facile LbL assembly method and the influence of the deposition conditions on their formation was monitored in real time by QCM. Compared to the temperature of 25 °C, the high temperature of 35°C above the phase transition temperature leads to the more adsorbed mass of microgels on the gold surface of QCM sensors. The absorbed mass values at the deposition pH 7 and 10 are 9.82 and 7.28 µg cm-2, respectively, which are much higher than 1.51 µg cm-2 of the layers deposited at pH 4. The water contact angle and AFM both confirmed the wettability properties and morphology of multilayers on the gold surface of QCM sensors.

Conclusion: The formation of the multilayer films on the gold surface by the layer-by-layer deposition technique of the negatively charged microgels and the oppositely charged PEI can be achieved. The controllable multilayer formation can be attributed to the size difference, changes in the hydrophilic property and surface charge density of microgels responsive to the external temperature and pH.

Keywords: Microgel, stimuli-responsive, multilayer, preparation, property, microgels films.

[1]
Ali, M.M.; Su, S.; Filipe, C.D.; Pelton, R.; Li, Y. Enzymatic manipulations of DNA oligonucleotides on microgel: Towards development of DNA-microgel bioassays. Chem. Commun., 2007, 43, 4459-4461.
[2]
Das, M.; Mardyani, S.; Chan, W.C.W.; Kumacheva, E. Biofunctionalized pH responsive microgels for cancer cell targeting: Rational design. Adv. Mater., 2006, 18, 80-83.
[3]
Heller, D.A.; Levi, Y.; Pelet, J.M.; Doloff, J.C.; Wallas, J.; Pratt, G.W.; Jiang, S.; Sahay, G.; Schroeder, A.; Schroeder, J.E. Modular ‘click-in-emulsion’ bone-targeted nanogels. Adv. Mater., 2013, 25, 1449-1454.
[4]
Nayak, S.; Lee, H.; Chmielewski, J.; Andrew, L.L. Folate-mediated cell targeting and cytotoxicity using thermoresponsive microgels. J. Am. Chem. Soc., 2004, 126, 10258-10259.
[5]
Wu, W.; Shen, J.; Banerjee, P.; Zhou, S. Water-dispersible multifunctional hybrid nanogels for combined curcumin and photothermal therapy. Biomaterials, 2011, 32, 598-609.
[6]
Wu, W.; Shen, J.; Gai, Z.; Hong, K.; Banerjee, P.; Zhou, S. Multi-functional core-shell hybrid nanogels for pH-dependent magnetic manipulation, fluorescent pH-sensing, and drug delivery. Biomaterials, 2011, 32, 9876-9887.
[7]
Wu, W.; Mitra, N.; Yan, E.C.; Zhou, S. Multifunctional hybrid nanogel for integration of optical glucose sensing and self-regulated insulin release at physiological pH. ACS Nano, 2010, 4, 4831-4839.
[8]
Ulbricht, M. Membrane separations using molecularly imprinted polymers. J. Chromatogr. B Analyt. Technol. Biomed. Life Sci., 2004, 804, 113-125.
[9]
Zhang, M.; Zhang, W. Pd nanoparticles immobilized on pH-responsive and chelating nanospheres as an efficient and recyclable catalyst for suzuki reaction in water. J. Phys. Chem. C, 2008, 112, 6245-6252.
[10]
Li, D.; Dunlap, J.R.; Zhao, B. Thermosensitive Water-dispersible hairy particle-supported pd nanoparticles for catalysis of hydrogenation in an aqueous/organic biphasic system. Langmuir, 2008, 24, 5911-5918.
[11]
Contrerascaceres, R.; Dawson, C.; Formanek, P.; Fischer, D.; Simon, F.; Janke, A.; Uhlmann, P. Stamm, Polymers as templates for au and au@ag bimetallic nanorods: Uv–vis and surface enhanced raman spectroscopy. Chem. Mater., 2017, 25, 158-169.
[12]
Wang, Y.Q.; Zhang, Y.Y.; Wu, X.G.; He, X.W.; Li, W.Y. Rapid facile in situ synthesis of the Au/Poly(N-isopropylacrylamide) thermosensitive gels as temperature sensors. Mater. Lett., 2015, 143, 326-329.
[13]
Zhang, Y.; Liu, K.; Guan, Y.; Zhang, Y. Assembling of gold nanorods on P(NIPAM-AAPBA) microgels: A large shift in the plasmon band and colorimetric glucose sensing. RSC Adv, 2012, 2, 4768-4776.
[14]
Cao, Z.; Chen, Y.; Zhang, Q.; Xia, Y.; Liu, G.; Wu, D.; Ma, W.; Cheng, J.; Liu, C. Preparation and ion sensing property of the self-assembled microgels by QCM. Nanofabrication, 2017, 3, 16-25.
[15]
Gu, Z.; Dang, T.T.; Ma, M.; Tang, B.C.; Cheng, H.; Jiang, S.; Dong, Y.; Zhang, Y.; Anderson, D.G. Glucose-responsive microgels integrated with enzyme nanocapsules for closed-loop insulin delivery. ACS Nano, 2013, 7, 6758-6766.
[16]
Liu, J.; Bu, W.; Pan, L.; Shi, J. NIR-triggered anticancer drug delivery by upconverting nanoparticles with integrated azobenzene-modified mesoporous silica. Angew. Chem. Int. Ed., 2013, 52, 4375-4379.
[17]
Yang, J.; Wang, D.; Liu, W.; Zhang, X.; Bian, F.; Yu, W. Palladium supported on a magnetic microgel: An efficient and recyclable catalyst for Suzuki and Heck reactions in water. Green Chem., 2013, 15, 3429-3437.
[18]
Parasuraman, D.; Serpe, M.J. Poly (N-Isopropylacrylamide) microgel-based assemblies for organic dye removal from water. ACS Appl. Mater. Interfaces, 2011, 3, 4714-4721.
[19]
Dalmont, H.; Pinprayoon, O.; Saunders, B.R. Study of pH-responsive microgels containing methacrylic acid: Effects of particle composition and added calcium. Langmuir, 2008, 24, 2834-2840.
[20]
Yang, J.; Liu, X.; Yan, J.; Lan, L.I.; Zha, L. pH/temperature dual stimuli responsive microgels based on interpenetration polymer network strucutre. Acta Polymer. Sin, 2009, 009, 638-644.
[21]
Kong, S.K.; Vincent, B. pH and temperature-sensitive behaviors of Poly(4-vinyl pyridine-co-N-isopropyl acrylamide) microgels. Polymer. J., 2005, 37, 565-570.
[22]
Laisheng, L.; Jing, T.; Juan, W.; Jinzhi, D.; Jun, W. Synthesis and characterization of polyethylenimine poly(ethylene glycol) diacrylate nanogel as a s1rna carrier; Acta Polymer. Sin, 2009, pp. 257-263.
[23]
Cao, Z.; Chen, T-Y.; Guo, X-l.; Zhou, X-J.; Nie, J-J.; Xu, J-T.; Fan, Z-Q.; Du, B-Y. Synthesis and properties of organic-inorganic hybrid P(NIPAM-co-AM-co-TMSPMA) microgels. Chinese J. Polymer. Sci., 2011, 29, 439-449.
[24]
Bradley, M.; Vincent, B. Poly(vinylpyridine) Core/Poly(N-isopropylacrylamide) shell microgel particles: Their characterization and the uptake and release of an anionic surfactant. Langmuir, 2008, 24, 2421-2425.
[25]
Cao, Z.; Tsoufis, T.; Svaldo-Lanero, T.; Duwez, A-S.; Rudolf, P.; Loos, K. The dynamics of complex formation between amylose brushes on gold and fatty acids by QCM-D. Biomacromolecules, 2013, 14, 3713-3722.
[26]
Cao, Z.; Guo, J.; Fan, X.; Xu, J.; Fan, Z.; Du, B. Detection of heavy metal ions in aqueous solution by P(MBTVBC-co-VIM)-coated QCM sensor. Sensors. Actuat B Chem., 2011, 157, 34-41.
[27]
Wu, Z.; Liu, J.; Li, Y.; Cheng, Z.; Li, T.; Zhang, H.; Lu, Z.; Yang, B. Self-assembly of nanoclusters into mono-, few-, and multilayered sheets via dipole-induced asymmetric van der waals attraction. ACS Nano, 2015, 9, 6315-6323.
[28]
Cao, Z.; Gordiichuk, P.I.; Loos, K.; Sudholter, E.J.R.; de Smet, L.C.P.M. The effect of guanidinium functionalization on the structural properties and anion affinity of polyelectrolyte multilayers. Soft Matter, 2016, 12, 1496-1505.
[29]
Wang, L.; Wang, X.; Xu, M.; Chen, D.; Sun, J. Layer-by-layer assembled microgel films with high loading capacity: Reversible loading and release of dyes and nanoparticles. Langmuir, 2008, 24, 1902-1909.
[30]
Serpe, M.J.; Lyon, L.A. Optical and acoustic studies of pH-dependent swelling in microgel thin films. Chem. Mater., 2004, 16, 4373-4380.
[31]
Herman, E.S.; Lyon, L.A. Polyelectrolyte exchange and diffusion in microgel multilayer thin films. Colloid Polymer. Sci., 2015, 293, 1535-1544.
[32]
Wang, L.; Chen, D.; Sun, J. Layer-by-layer deposition of polymeric microgel films on surgical sutures for loading and release of ibuprofen. Langmuir, 2009, 25, 7990.
[33]
Nolan, C.M.; Michael, J.S.; Lyon, L.A. Thermally modulated insulin release from microgel thin films. Biomacromolecules, 2004, 5, 1940.
[34]
Serpe, M.J.; Yarmey, K.A.; Christine, M.N.; Lyon, L.A. Doxorubicin uptake and release from microgel thin films. Biomacromolecules, 2004, 6, 408.
[35]
Feil, H.; Bae, Y.H.; Feijen, J.; Kim, S.W. Effect of comonomer hydrophilicity and ionization on the lower critical solution temperature of N-isopropylacrylamide copolymers. Macromolecules, 1993, 26, 2496-2500.
[36]
Vo, C.D.; Kuckling, D.; Adler, H.J.P.; Schönhoff, M. Preparation of thermosensitive nanogels by photo-cross-linking. Colloid Polym. Sci., 2002, 280, 400-409.
[37]
Cao, Z.; Du, B.; Chen, T.; Nie, J.; Xu, J.; Fan, Z. Preparation and properties of thermo-sensitive organic/inorganic hybrid microgels. Langmuir, 2008, 24, 12771-12778.


Rights & PermissionsPrintExport Cite as

Article Details

VOLUME: 9
ISSUE: 2
Year: 2019
Page: [267 - 277]
Pages: 11
DOI: 10.2174/2210681208666180416154332
Price: $58

Article Metrics

PDF: 14
HTML: 1