Formation mechanism of zigzag patterned P(NIPAM-co-AA)/CuS composite microspheres by in situ biomimetic mineralization for morphology modulation

Poly(N-isopropylacrylamide-co-acrylic acid)/copper sulfide (P(NIPAM-co-AA)/CuS) composite microspheres with variable zigzag patterned surfaces have been synthesized by employing an in situ biomimetic mineralization reaction between H2S and Cu2+ immersed in P(NIPAM-co-AA) microspheres for morphology modulation. The morphology and composition of the P(NIPAM-co-AA)/CuS composite microspheres with zigzag patterned surfaces prepared in different conditions were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectrometry (FT-IR). The polymeric microgels swelled by Cu(Ac)2 solution after freeze-drying treatment were of porous structure, indicating that there were polymeric frameworks and rich-water domains in the microgels before the deposition. Furthermore, due to the limited uneven deposition of metal sulfide on the polymeric skeleton of the hydrogel surface, the surface polymeric skeleton will be anisotropically shrunk when the composite microspheres lose water and shrink, thus forming a wrinkle pattern on the surface of the composite microspheres. The factors affecting the deposition amount and distribution of metal sulfide will affect the zigzag patterned morphology. Based on the experimental results, a formation mechanism of the P(NIPAM-co-AA)/CuS composite microspheres with zigzag patterned surface, “the deformed shrinkage of the surface texture”, has been proposed. The formation mechanism of the surface morphology in the composite microspheres is helpful for understanding and controlling the process of mineralization, for preparing materials expected by controlling the experiment conditions, and for expanding the application of the composites.

[1]  M. Marcolongo,et al.  Biomimetic Mineralization of Hierarchical Nanofiber Shish-Kebabs in a Concentrated Apatite-Forming Solution , 2020, ACS Applied Bio Materials.

[2]  M. Epple,et al.  Hybrid chitosan/gelatin/nanohydroxyapatite scaffolds promote odontogenic differentiation of dental pulp stem cells and in vitro biomineralization. , 2020, Dental materials : official publication of the Academy of Dental Materials.

[3]  T. Troczynski,et al.  Biomimetically Mineralized Alginate Nanocomposite Fibers for Bone Tissue Engineering: Mechanical Properties and in Vitro Cellular Interactions. , 2020, ACS applied bio materials.

[4]  Chun‐Xia Zhao,et al.  Biomimetic core-shell silica nanoparticles using a dual-functional peptide. , 2020, Journal of colloid and interface science.

[5]  Keqing Huang,et al.  Egg-White-/Eggshell-Based Biomimetic Hybrid Hydrogels for Bone Regeneration. , 2019, ACS biomaterials science & engineering.

[6]  U. Şeker,et al.  Biomineralization of Calcium Phosphate Crystals Controlled by Protein-Protein Interactions. , 2019, ACS biomaterials science & engineering.

[7]  Jing Jin,et al.  Mechanical and slow-released property of poly(acrylamide) hydrogel reinforced by diatomite. , 2019, Materials science & engineering. C, Materials for biological applications.

[8]  Kuan-Ju Chen,et al.  Synthesis of silica/polypeptide hybrid nanomaterials and mesoporous silica by molecular replication of sheet-like polypeptide complexes through biomimetic mineralization. , 2019, Journal of colloid and interface science.

[9]  N. Wada,et al.  Crystallization of Calcium Phosphate in Agar Hydrogels in the Presence of Polyacrylic Acid under Double Diffusion Conditions , 2017 .

[10]  W. Nie,et al.  Role of surface functionality on the formation of raspberry-like polymer/silica composite particles: Weak acid-base interaction and steric effect , 2015 .

[11]  A. Hernández-Arana,et al.  Biomimetic sol-gel synthesis of TiO₂ and SiO₂ nanostructures. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[12]  J. M. Astilleros,et al.  Influence of Gelatin Hydrogel Porosity on the Crystallization of CaCO3 , 2014 .

[13]  Jianshu Li,et al.  Multifunctional hydrogels based on β-cyclodextrin with both biomineralization and anti-inflammatory properties. , 2014, Carbohydrate polymers.

[14]  J. Lu,et al.  Controllable stabilization of poly(N-isopropylacrylamide)-based microgel films through biomimetic mineralization of calcium carbonate. , 2012, Biomacromolecules.

[15]  Shaofei Song,et al.  Microhydrogel surface-supported quaternary ammonium peroxotungstophosphate as reusable catalytic materials for oxidation of DBT , 2011 .

[16]  J. Bai,et al.  Simple approach to fabricate AgBr nanoparticles/polyvinylpyrrolidone microspheres , 2010 .

[17]  Qingsheng Wu,et al.  A simple route to synthesize CuS framework with porosity , 2010 .

[18]  T. Zhou,et al.  Composite microspheres with PAM microgel core and polymerisable surfactant/polyoxometalate complexes shell , 2009 .

[19]  Fiona C. Meldrum,et al.  Controlling Mineral Morphologies and Structures in Biological and Synthetic Systems , 2009 .

[20]  F. Meldrum,et al.  Controlling mineral morphologies and structures in biological and synthetic systems. , 2008, Chemical reviews.

[21]  Ying Zhang,et al.  Controllable synthesis of CuS-P(AM-co-MAA) composite microspheres with patterned surface structures. , 2008, Journal of colloid and interface science.

[22]  Daodao Hu,et al.  Synthesis of PAM/TiO2 Composite Microspheres with Hierarchical Surface Morphologies , 2007 .

[23]  Yu Fang,et al.  Novel Method for Preparation of Structural Microspheres Poly(N-isopropylacrylamide-co-acrylic acid)/SiO2 , 2006 .

[24]  Ying Zhang,et al.  Studies on the Template Composition Dependence of the Surface Morphologies of the Metal Sulfides-P(NIPAM-co-MAA) Composite Microspheres , 2006 .

[25]  M. Akashi,et al.  [Spectra studies on the interaction of Mn2+ and poly N-isopropylacrylamide]. , 2005, Guang pu xue yu guang pu fen xi = Guang pu.

[26]  Ying Zhang,et al.  CuS-poly (N-isopropylacrylamide-co-acrylic acid) composite microspheres with patterned surface structures: Preparation and characterization , 2004 .

[27]  Ying Zhang,et al.  Preparation of metal sulfide-polymer composite microspheres with patterned surface structures. , 2004, Chemical communications.

[28]  Yi Xie,et al.  Fabrication of novel urchin-like architecture and snowflake-like pattern CuS , 2004 .

[29]  Ying Zhang,et al.  Synthesis of novel metal sulfide-polymer composite microspheres exhibiting patterned surface structures. , 2004, Langmuir.

[30]  Dong Yang,et al.  Well-defined star-shaped calcite crystals formed in agarose gels. , 2003, Chemical communications.

[31]  Jiandong Ding,et al.  The Wetting Process of a Dry Polymeric Hydrogel , 2002 .

[32]  O. Steinbock,et al.  Frontal polymerization synthesis of temperature-sensitive hydrogels. , 2001, Journal of the American Chemical Society.

[33]  G. Falini.  Crystallization of calcium carbonates in biologically inspired collagenous matrices , 2000 .

[34]  Atsushi Suzuki,et al.  Shrinking pattern and phase transition velocity of poly(N-isopropylacrylamide) gel , 1999 .

[35]  B. Vincent,et al.  Microgel particles as model colloids : theory, properties and applications , 1999 .

[36]  Toyoichi Tanaka,et al.  Patterns in shrinking gels , 1992, Nature.

[37]  Herbert H. Hooper,et al.  Swelling equilibria for positively ionized polyacrylamide hydrogels , 1990 .

[38]  Toyoichi Tanaka,et al.  Mechanical instability of gels at the phase transition , 1987, Nature.

[39]  Toyoichi Tanaka.  Kinetics of phase transition in polymer gels , 1986 .

[40]  M. Ilavský,et al.  Phase transition in swollen gels , 1984 .

[41]  Toyoichi Tanaka,et al.  Salt effects on the phase transition of ionic gels , 1982 .

[42]  Michal Ilavsky,et al.  Phase transition in swollen gels. 2. Effect of charge concentration on the collapse and mechanical behavior of polyacrylamide networks , 1982 .

[43]  Shao-Tang Sun,et al.  Phase transitions in ionic gels , 1980 .

[44]  B D Ratner,et al.  Plasma polymerized N-isopropylacrylamide: synthesis and characterization of a smart thermally responsive coating. , 2001, Biomacromolecules.