4) Organic/Inorganic Hybrid Materials
Biominerals such as seashells, pearls, exoskeletons of crustaceans, and bones are good models for the development of new hybrid synthetic materials with significant properties and environmental benignity. For example, the nacre of the shell has layered structures of calcium carbonate and biopolymers, resulting in their high mechanical toughness and unique optical properties. The exoskeletons of crustaceans are also fascinating biominerals in the view of materials science because they are ductile, tough, and lightweight. The elaborate structures of these biominerals are controlled by the cooperative effects of the biopolymers.
We have focused on synthetic approaches to the preparation of organic/calcium carbonate hybrid materials by mimicking the formation process of the nacre of shells and other biominerals. Polymer/calcium carbonate layered thin films have been successfully obtained by using these self-organization processes. The interactions between the functional group of polymers and calcium ions play key roles in thin film crystallization of calcium carbonate. We have also succeeded in the formation of thin films with selected morphologies of calcite, aragonite, and vaterite by tuning assembled structures of synthetic polymer templates. In addition, patterned thin-film composites of calcium carbonate have been developed, whose structures have not yet been seen in nature. Furthermore, we have succeeded in preparing uniaxially oriented calcium carbonate thin-film crystals on a polymer matrix by using a natural peptide (CAP-1) isolated from the exoskeleton of a crayfish.
(The study using the natural peptide (CAP-1) is conducted by collaboration with Prof. H. Nagasawa at Graduate School of Agricultural and Life Sciences.)
Selected original papers on this subject:
Rapid and Topotactic Transformation from Octacalcium Phosphate to Hydroxyapatite (HAP): A New Approach to Self-Organization of Free-Standing Thin-Film HAP-Based Nanohybrids
Satoshi Kajiyama, Takeshi Sakamoto, Moe Inoue, Tatsuya Nishimura, Taishi Yokoi, Chikara Ohtsuki, and Takashi Kato
CrystEngComm, 18, 8388-8395 (2016) (Back Cover).
Biomineralization-Inspired Preparation of Zinc Hydroxide Carbonate/Polymer Hybrids and Their Conversion to Zinc Oxide Thin-Film Photocatalysts
Shunichi Matsumura, Yoshimasa Horiguchi, Tatsuya Nishimura, Hideki Sakai, and Takashi Kato
Chem. Eur. J., 22, 7094-7101 (2016) (Hot Paper) (Frontispiece).
Liquid-Crystalline Calcium Carbonate: Biomimetic Synthesis and Alignment of Nanorod Calcite
Masanari Nakayama, Satoshi Kajiyama, Tatsuya Nishimura, and Takashi Kato
Chem. Sci., 6, 6230-6234 (2015).
Formation of Helically Structured Chitin/CaCO3 Hybrids through an Approach Inspired by the Biomineralization Processes of Crustacean Cuticles
Shunichi Matsumura, Satoshi Kajiyama, Tatsuya Nishimura, and Takashi Kato
Small, 11, 5127-5133 (2015).
Liquid-Crystalline Biomacromolecular Templates for the Formation of Oriented Thin Film Hybrids Composed of Ordered Chitin and Alkaline-Earth Carbonate
Tatsuya Nishimura, Ken Toyoda, Takahiro Ito, Yuya Oaki, Yukiko Namatame, and Takashi Kato
Chem. Asian J., 10, 2356-2360 (2015).
Tuning of Morphology and Polymorphs of Carbonate/Polymer Hybrids Using Photoreactive Polymer Templates
Takeshi Sakamoto, Yosuke Nishimura, and Takashi Kato
CrystEngComm, 17, 6947-6954 (2015).
Macromolecular Templates for the Development of Organic/Inorganic Hybrid Materials
Polym. J., 47, 235-243 (2015). (Focus Review, Open Access)
Hydroxyapatite Formation on Oxidized Cellulose Nanofibers in a Solution Mimicking Body Fluid
Seira Morimune-Moriya, Sakina Kondo, Ayae Sugawara-Narutaki, Tatsuya Nishimura, Takashi Kato and Chikara Ohtsuki
Polym. J., 47, 158-163 (2015). (Special Issue: Fusion Materials)
Organic/Inorganic Fusion Materials: Cyclodextrin-Based Polymer/CaCO3 Hybrids Incorporating Dye Molecules through Host-Guest Interactions
Fangjie Zhu, Tatsuya Nishimura, and Takashi Kato
Polym. J., 47, 122-127 (2015). (Special Issue: Fusion Materials)
Biomineralization-Inspired Approach to the Development of Hybrid Materials: Preparation of Patterned Polymer/Strontium Carbonate Thin Films Using Thermoresponsive Polymer Brush Matrices
Yulai Han, Tatsuya Nishimura, and Takashi Kato
Polym. J., 46, 499-504 (2014). (Special Issue: Biorelated Polymers and Materials)
Bioinspired Stiff and Flexible Composites of Nanocellulose-Reinforced Amorphous CaCO3
Tsuguyuki Saito, Yuya Oaki, Tatsuya Nishimura, Akira Isogai, and Takashi Kato
Materials Horizons, 1, 321-325 (2014).
Morphology Tuning in the Formation of Vaterite Crystal Thin Films with Thermoresponsive Poly(N-isopropylacrylamide) Brush Matrices
Yulai Han, Tatsuya Nishimura, and Takashi Kato
CrystEngComm, 16, 3540-3547 (2014).
Aragonite Nanorods in Calcium Carbonate/Polymer Hybrids Formed through Self-Organization Processes from Amorphous Calcium Carbonate Solution
Satoshi Kajiyama, Tatsuya Nishimura, Takeshi Sakamoto, and Takashi Kato
Small, 10, 1634-1641 (2014).
Supramolecular Effects on Formation of CaCO3 Thin Films on a Polymer Matrix
Fangjie Zhu, Tatsuya Nishimura, Hiroki Eimura, and Takashi Kato
CrystEngComm, 16, 1496-1501 (2014).
Tuning the Stability of CaCO3 Crystals with Magnesium Ions for Formation of Aragonite Thin Films on Organic Polymer Templates
Fangjie Zhu, Tatsuya Nishimura, Takeshi Sakamoto, Hidekazu Tomono, Hiroki Nada, Yasushi Okumura, Hirotsugu Kikuchi, and Takashi Kato
Chem. Asian J., 8, 3002-3009 (2013).
CaCO3/Chitin Hybrids: Effects of Recombinant Acidic Peptides Designed Based on a Peptide Extracted from an Exoskeleton of a
Crayfish on Morphologies of the Hybrids
Hiromu Kumagai, Ryou Matsunaga, Tatsuya Nishimura, Yuya Yamamoto, Satoshi Kajiyama, Yuya Oaki, Kei Akaiwa, Hirotaka Inoue, Hiromichi Nagasawa, Kohei Tsumoto, and Takashi Kato
Faraday Discuss., 159, 483-494 (2012).
Photoimaging of Self-Organized CaCO3/Polymer Hybrid Films by Formation of Regular Relief and Flat Surface Morphologies
Takeshi Sakamoto, Yosuke Nishimura, Tatsuya Nishimura, and Takashi Kato
Angew. Chem. Int. Ed., 50, 5856 (2011).
CaCO3/Chitin-Whisker Hybrids: Formation of CaCO3 Crystals in Chitin-Based Liquid-Crystalline Suspension
Yuya Yamamoto, Tatsuya Nishimura, Tsuguyuki Saito, and Takashi Kato
Polym. J., 42, 583 (2010).
Three-Dimensional Relief Structures of CaCO3 Crystal Assemblies Formed by Spontaneous Two-Step Crystal Growth on a Polymer Thin Film
Takeshi Sakamoto, Akira Oichi, Yuya Oaki, Tatsuya Nishimura, Ayae Sugawara, and Takashi Kato
Cryst. Growth Des., 9, 622 (2009).
Nanosegregated Amorphous Composites of Calcium Carbonate and an Organic Polymer
Yuya Oaki, Satoshi Kajiyama, Tatsuya Nishimura, Hiroaki Imai, and Takashi Kato
Adv. Mater., 20, 3633 (2008).
Macroscopically Ordered Polymer/CaCO3 Hybrids Prepared by Using a Liquid-Crystalline Template
Tatsuya Nishimura, Takahiro Ito, Yuya Yamamoto, Masafumi Yoshio, and Takashi Kato
Angew. Chem. Int. Ed., 47, 2800 (2008).
Effects of Peptides on CaCO3 Crystallization: Mineralization Properties of an Acidic Peptide Isolated from Exoskeleton of a Crayfish and Its Derivatives
Yuya Yamamoto, Tatsuya Nishimura, Ayae Sugawara, Hirotaka Inoue, Hiromichi Nagasawa, and Takashi Kato
Cryst. Growth Des., 8, 4062 (2008).
Self-Organization of Oriented Calcium Carbonate/Polymer Composites: Effects of a Matrix Peptide Isolated from the Exoskeleton of a Crayfish
Ayae Sugawara, Tatsuya Nishimura, Yuya Yamamoto, Hirotaka Inoue, Hiromichi Nagasawa, and Takashi Kato
Angew. Chem. Int. Ed., 45, 2876 (2006).
Assembled Structures of Nanocrystals in Polymer/Calcium Carbonate Thin-Film Composites Formed by Cooperation of Chitosan and Poly(Aspartate)
Ayae Sugawara, Akira Oichi, Hiroko Suzuki, Yuzo Shigesato, Toshihiro Kogure, and Takashi Kato
J. Polym. Sci. Part A: Polym. Chem., 44, 5153 (2006).
Self-Organization of Patterned Caco3/Polymer Composite Films: Tuning of Their Morphologies by the Change of Molecular Weights of Acidic Polymers
Takeshi Sakamoto, Akira Oichi, Ayae Sugawara, and Takashi Kato
Chem. Lett., 35, 310 (2006).
Calcium Carbonate/Polymer Composites: Polymorph Control for Aragonite
Ayae Sugawara and Takashi Kato
Compos. Interfaces, 11, 287 (2004).
Self-Organized Calcium Carbonate with Regular Surface-Relief Structures
Ayae Sugawara, Takeshi Ishii, and Takashi Kato
Angew. Chem. Int. Ed., 42, 5299 (2003).
Template Effect of Crystalline Poly(Vinyl Alcohol) for Selective Formation of Aragonite and Vaterite Caco3 Thin Films
Naoya Hosoda, Ayae Sugawara, and Takashi Kato
Macromolecules, 36, 6449 (2003).
Thin-Film Formation of Calcium Carbonate Crystals: Effects of Functional Groups of Matrix Polymers
Naoya Hosoda and Takashi Kato
Chem. Mater., 13, 688 (2001).
Aragonite CaCO3 Thin-Film Formation by Cooperation of Mg2+ and Organic Polymer Matrices
Ayae Sugawara and Takashi Kato
Chem. Commun., 2000, 487.
Layered Thin-Film Composite Consisting of Polymers and Calcium Carbonate: A Novel Organic/Inorganic Material with an Organized Structure
Takashi Kato, Takuo Suzuki, and Taku Irie
Chem. Lett., 2000, 186.
A New Approach to Organic/Inorganic Composites. Thin Film Coating of CaCO3 on a Chitin Fiber in the Presence of Acid-Rich Macromolecules
T. Kato and T. Amamiya
Chem. Lett., 1999, 199.
Effects of Macromolecules on the Crystallization of CaCO3 the Formation of Organic/Inorganic Composites
Takashi Kato, Takuo Suzuki, Takahiro Amamiya, Taku Irie, Makoto Komiyama, and Hiroshi Yui
Supramol. Sci., 5, 411 (1998).
Selected review papers on this subject:
Macromolecular Templating for the Formation of Inorganic-Organic Hybrid Structures
Takashi Kato, Takeshi Sakamoto, and Tatsuya Nishimura
MRS Bulletin, 35, 127 (2010).
Calcium Carbonate-Organic Hybrid Materials
Takashi Kato, Ayae Sugawara, and Naoya Hosoda
Adv. Mater., 14, 869 (2002).
Polymer/Calcium Carbonate Layered Thin-Film Composites
Adv. Mater., 12, 1543 (2000).