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Swelling properties and molecular simulation of PNIPA porous hydrogels

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Abstract

A series of porous intelligent hydrogels, which exhibited appropriate lower critical solution temperature (LCST) and fast response behavior, were synthesized by radiation method. The structure and surface morphology of hydrogels were examined by the infrared radiation and the scanning electron microscopy, respectively. The influences of the content of crosslinking agent and relative molecular mass of polyethylene glycol (PEG) on the swelling properties of hydrogels were discussed. The molecular mechanics simulations were performed to investigate the phase transformation mechanism of poly(N-isopropyl acrylamide) (PNIPA) hydrogel. The results show that macropores are observed in hydrogels, whereas hydrogels prepared without using PEG have a dense surface. LCST of hydrogels increases with the increase of relative molecular mass of PEG. The swelling mechanism of PNIPA porous hydrogels follows non-Fickian diffusion model. The theoretical maximum water absorption S∞ is approximately consistent with experimental value according to the second-order kinetics model established by Schott. The molecule chains of PNIPA hydrogel begin folding and curling, resulting in volume shrinkage at 305 K. There are much intramolecular nonbonding interactions in molecule chains of hydrogels. The porous hydrogels are expected to be applied in the field of artificial intelligence material.

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References

  1. LONG Qing-de, PAN Chun-yue, MENG Yan-hua, ZHANG Bao-**, XU Cheng-xi. Synthesis and property of temperature and pH sensitive xanthan-MA/PNIPAAm hydrogels [J]. Journal of Central South University of Technology, 2009, 16(1): 66–72.

    Article  Google Scholar 

  2. KEIR N, WOODS C A, DUMBLETON K. Clinical performance of different care systems with silicone hydrogel contact lenses [J]. Contact Lens & Anterior Eye, 2010, 33(4): 189–195.

    Article  Google Scholar 

  3. DAHLMANN J, KRAUSE A, MÖLLER L, KENSAH G, MÖWES M, DIEKMANN A, MARTIN U, KIRSCHNING A, GRUH I, DRÄGER G. Fully defined in situ cross-linkable alginate and hyaluronic acid hydrogels for myocardial tissue engineering [J]. Biomaterials, 2013, 34(4): 940–951.

    Article  Google Scholar 

  4. GAO **ao-ye, HE Chao-liang, XIAO Chun-sheng, ZHUANG **u-li, CHEN Xue-si. Synthesis and characterization of biodegradable pH-sensitive poly(acrylic acid) hydrogels crosslinked by 2-hydroxyethyl methacrylate modified poly(L-glutamic acid) [J]. Materials Letters, 2012, 77: 74–77.

    Article  Google Scholar 

  5. PAWAR H V, TETTEH J, BOATENG J S. Preparation, optimisation and characterisation of novel wound healing film dressings loaded with streptomycin and diclofenac [J]. Colloids and Surfaces B: Biointerfaces, 2013, 102: 102–110.

    Article  Google Scholar 

  6. MURPHY D J, SANKALIA M G, LOUGHLIN R G, DONNELLY R F, JENKINS M G. Physical characterisation and component release of poly(vinyl alcohol)-tetrahydroxyborate hydrogels and their applicability as potential topical drug delivery systems [J]. International Journal of Pharmaceutics, 2012, 423(2): 326–334.

    Article  Google Scholar 

  7. TANAKA T, HIROKAWA Y. Volume-phase transitions of ionized N-isopropylacrylamide gels [J]. Chemical Physics, 1987, 81(2): 1392–1395.

    Google Scholar 

  8. DONG Jun, WENG Jian, DAI Li-zong. The effect of graphene on the lower critical solution temperature of poly(N-isopropylacrylamide) [J]. Carbon, 2013, 52: 326–336.

    Article  Google Scholar 

  9. SUN De-lin, ZHOU Jian. Effect of water content on microstructures and oxygen permeation in PSiMA-IPN-PMPC hydrogel: A molecular simulation study [J]. Chemical Engineering Science, 2012, 78: 236–245.

    Article  Google Scholar 

  10. LIU Yuan-dong, DING Jian-nan, QIU Guan-zhou, WANG Hai-dong. Homology modeling and docking studies of IscS from extremophile Acidithiobacillus ferrooxidans [J]. Journal of Central South University of Technology, 2007, 14(6): 742–748.

    Article  Google Scholar 

  11. LEE S G, BRUNELLO G F, JANG S S, BUCKNALL D G. Molecular dynamics simulation study of P(VP-co-HEMA) hydrogels: Effect of water content on equilibrium structures and mechanical properties [J]. Biomaterials, 2009, 30: 6130–6141.

    Article  Google Scholar 

  12. WALTER J, ERMATCHKOV V, VRABEC J, HASSE H. Molecular dynamics and experimental study of conformation change of poly(N-isopropylacrylamide) hydrogels in water [J]. Fluid Phase Equilibria, 2010, 296: 164–172.

    Article  Google Scholar 

  13. CHEN Jun, LIU Ming-zhu, ZHANG Nai-yan. Influence of the grafted chain length on responsive behaviors of the grafted poly(DEA-co-DMAEMA) hydrogel [J]. Sensors and Actuators B: Chemical, 2010, 149(1): 34–43.

    Article  Google Scholar 

  14. KHAN F, KHANAM A, PARIHAR M S, BILGAINYA R, RAI K, KHAN F. Dissipative convective structures and nanoparticles encapsulation in Cu/alginate/dextran composite hydrogels and sponges [J]. Carbohydrate Polymers, 2011, 83(2): 586–590.

    Article  Google Scholar 

  15. FERRER G G, PRADAS M M, RIBELLES J L. Influence of the nature of the porous confining network on the sorption, diffusion and mechanical properties of hydrogel IPNs [J]. European Polymer Journal, 2010, 46(4): 774–782.

    Article  Google Scholar 

  16. TOPUZ F, OKAY O. Macroporous hydrogel beads of high toughness and superfast responsivity [J]. Reactive and Functional Polymers, 2009, 69(5): 273–280.

    Article  Google Scholar 

  17. LYNN A D, BLAKNEY A K, KYRIAKIDES T R, BRYANT S J. Temporal progression of the host response to implanted poly(ethylene glycol)-based hydrogels [J]. Journal of Biomedical Materials Research Part A, 2011, 96(4): 621–631.

    Article  Google Scholar 

  18. ZAMANI A, HENRIKSSON D, TAHERZADEH M J. A new foaming technique for production of superabsorbents from carboxymethyl chitosan [J]. Carbohydrate Polymers, 2010, 80(4): 1091–1101.

    Article  Google Scholar 

  19. CHEN Mei-ling, ZHU **-tang, QI Gui-**, HE Chang-cheng, WANG Hui-liang. Anisotropic hydrogels fabricated with directional freezing and radiation-induced polymerization and crosslinking method [J]. Materials Letters, 2012, 89: 104–107.

    Article  Google Scholar 

  20. QIU Y, PARK K. Environment-sensitive hydrogels for drug delivery [J]. Advanced Drug Delivery Reviews, 2012, 64: 49–60.

    Article  Google Scholar 

  21. MICIC M, STAMENIC D, SULJOVRUJIC E. Radiation-induced synthesis and swelling properties of p(2-hydroxyethyl methacrylate/ itaconic acid/oligo (ethylene glycol) acrylate) terpolymeric hydrogels [J]. Radiation Physics and Chemistry, 2012, 81(9): 1451–1455.

    Article  Google Scholar 

  22. WENCESLAU A C, SANTOS F G, RAMOS E R F, NAKAMURA C V, RUBIRA A F, MUNIZ E C. Thermo- and pH-sensitive IPN hydrogels based on PNIPAAm and PVA-Ma networks with LCST tailored close to human body temperature [J]. Materials Science and Engineering C, 2012, 32(5): 1259–1265.

    Article  Google Scholar 

  23. COUGHLAN D C, CORRIGAN O I. Release kinetics of benzoic acid and its sodium salt from a series of poly(N-isopropylacrylamide) matrices with various percentage crosslinking [J]. Journal of Pharmaceutical Sciences, 2008, 97(1): 318–330.

    Article  Google Scholar 

  24. IYER G, TILLEKERATNE L M V, COLEMAN M R, NADARAJAH A. Equilibrium swelling behavior of thermally responsive metal affinity hydrogels, Part I: Compositional effects [J]. Polymer, 2008, 49(17): 3737–3743.

    Article  Google Scholar 

  25. ZHUO Ren-xi, LI Wei. Preparation and characterization of macroporous poly(N-isopropylacrylamide) hydrogels for thecontrolled release of proteins [J]. Journal of Polymer Science Part A: Polymer Chemistry, 2003, 41: 152–159.

    Article  Google Scholar 

  26. FEIL H, BAE Y H, FEIJEN J. Effect of comonomer hydrophilicity and ionization on the lower critical solution temperature of N-isopropylacrylamide copolymers [J]. Macromolecules, 1993, 26: 2496–2500.

    Article  Google Scholar 

  27. WU X S, HOFMAN A S, YAGER P. Synthesis and characterization of thermally reversible macroporous poly(N-isopropylacrylamide) hydrogels [J]. Journal of Polymer Science Part A: Polymer Chemistry, 1992, 30: 2121–2129.

    Article  Google Scholar 

  28. CHEN Jun, LIU Ming-zhu, LIU Hong-liang, MA Li-wei. Synthesis, swelling and drug release behavior of poly(N, N-diethylacrylamide-co-N-hydroxymethyl acrylamide) hydrogel [J]. Materials Science and Engineering C, 2009, 29: 2116–2123.

    Article  Google Scholar 

  29. LIU Hong-liang, LIU Ming-zhu, JIN Shu-**, CHEN Shi-lan. Synthesis and characterization of fast responsive thermo- and pH-sensitive poly[(N,N-diethylacrylamide)-co-(acrylic acid)]_hydrogels [J]. Polymer International, 2008, 57(10): 1165–1173.

    Article  Google Scholar 

  30. RITGER P L, PEPPAS N A. A simple equation for description of solute release II: Fickian and anomalous release from swellable devices [J]. Journal of Controlled Release, 1987, 5(1): 37–42.

    Article  Google Scholar 

  31. LUO Yan-ling, WEI Qing-bo, Xu Feng, CHEN Ya-shao, FAN Li-hua, ZHANG Chang-hu. Assembly, characterization and swelling kinetics of Ag nanoparticles in PDMAA-g-PVA hydrogel networks [J]. Materials Chemistry and Physics, 2009, 118(2/3): 329–336.

    Article  Google Scholar 

  32. KIM S J, YOON S G, KIM I Y, KIM S I. Swelling characterization of the semi-interpenetrating polymer network hydrogels composed of chitosan and poly(diallyldimethylammonium chloride) [J]. Journal of Applied Polymer Science, 2004, 91: 2876–2880.

    Article  Google Scholar 

Download references

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Authors and Affiliations

  1. School of Materials Science and Engineering, Zhengzhou University, Zhengzhou, 450052, China

    Zhi-hui Li  (**智慧), Wen-tao Liu  (刘文涛), **ang-yuan Duan  (段翔远), Xu-**g Gao  (高旭静), Su-qin He  (何素芹) & Cheng-shen Zhu  (朱诚身)

  2. Shenzhen Academy of Metrology & Quality Inspection, Shenzhen, 518131, China

    Zhong-yuan Li  (**中原)

  3. Key Laboratory for Special Functional Materials of Ministry of Education, Henan University, Kaifeng, 475001, China

    Yun-cai Li  (**蕴才)

  4. Isotope Institute of Henan Academy of Sciences, Zhengzhou, 450015, China

    Ming-cheng Yang  (杨明成)

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  1. Zhi-hui Li  (**智慧)
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  2. Wen-tao Liu  (刘文涛)
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  6. Yun-cai Li  (**蕴才)
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  7. Ming-cheng Yang  (杨明成)
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  8. Su-qin He  (何素芹)
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Correspondence to Wen-tao Liu  (刘文涛).

Additional information

Foundation item: Project(102101210100) supported by the Key Science and Technology Project of Henan Province, China; Projects(2011B430023, 12B430021) supported by the Natural Science Foundation of Henan Province, China

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Li, Zh., Liu, Wt., Li, Zy. et al. Swelling properties and molecular simulation of PNIPA porous hydrogels. J. Cent. South Univ. 20, 1161–1172 (2013). https://doi.org/10.1007/s11771-013-1599-3

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  • DOI: https://doi.org/10.1007/s11771-013-1599-3

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