Natural Cellulosic Substance Derived Nano-structured Materials

  • Yuanqing Gu
  • Jianguo HuangEmail author
Part of the Advanced Topics in Science and Technology in China book series (ATSTC)


When versatile synthetic chemical processes meet natural biological assemblies, a promising shortcut for the design and fabrication of functional materials with tailored structures and properties are lit up. By precisely replicating natural substrates with guest matrices, artificial materials are endowed with the initial biological structures and morphologies. To achieve faithful inorganic/organic replicas of the natural species for the corresponding finest structural details and morphological hierarchies, one effective and practical strategy is to coat the morphologically sophisticated surfaces of the biological structures with ultrathin films accompanied by subsequent removal of the biotemplate. With this process, the morphological hierarchies of initial biological substances can be replicated faithfully from macroscopic down to nanometer scales. And it was successfully applied to natural cellulosic substances such as filter paper, cotton, and cloth to yield the related metal oxide replicas. The hierarchical structure and highly detailed morphologies of the cellulosic substances are precisely memorized in metal oxide films to give macroscopic fossils; and the organic substances are removed by subsequent calcination. The resultant fossils are hierarchical ceramic materials, in which the structures of the original template substance are faithfully inherited. The ceramics are composed of metal oxide nano-tubes, as precise hollow replicas of the template cellulose nanofibers. This approach has been employed to synthesize titania, zirconia, tin oxide, and ITO nanotubular materials. Hierarchical titania nanotube-gold nanoparticle hybrid and polypyrrole composite materials are also achieved with using filter paper as a scaffold. Also, the titania-coated cellulose fibers are employed as a substrate for protein immobilization, resulting in novel bioactive materials. Furthermore, by dissolving the cellulose template instead of calcination, this approach is extended to the design and preparation of bio-inspired polymeric nanotubular materials.


Atom Transfer Radical Polymerization Cellulose Fiber Atomic Layer Deposition Cellulose Derive Cellulosic Substance 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


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  1. Al-Muhtaseb SA, Ritter JA (2003) Preparation and properties of resorcinol-formaldehyde organic and carbon gels. Adv Mater 15:101–114CrossRefGoogle Scholar
  2. Anderson MW, Holmes SM, Hanif N, Cundy CS (2000) Hierarchical pore structures through diatom zeolitization. Angew Chem Int Ed 39:2707–2710CrossRefGoogle Scholar
  3. Aoki Y, Huang J, Kunitake T (2006) Electro-conductive nanotubular sheet of indium tin oxide as fabricated from the cellulose template. J Mater Chem 16:292–297CrossRefGoogle Scholar
  4. Baik NS, Sakai G, Miura N, Yamazoe N (2000) Hydrothermally treated sol solution of tin oxide for thin-film gas sensor. Sens Actuat B 63:74–79CrossRefGoogle Scholar
  5. Bao Z, Weatherspoon MR, Shian S, Cai Y, Graham PD, Allan SM, Ahmad G, Dickerson MB, Church BC, Kang Z, Abernathy HW III, Summers CJ, Liu M, Sandhage KH (2007) Chemical reduction of three-dimensional silica micro-assemblies into microporous silicon replicas. Nature 446:172–175CrossRefGoogle Scholar
  6. Cai J, Zhang L (2005) Rapid dissolution of cellulose in LiOH/urea and NaOH/urea aqueous solutions. Macromol Biosci 5:539–548CrossRefGoogle Scholar
  7. Cai J, Zhang L, Zhou J, Qi H, Chen H, Kondo T, Chen X, Chu B (2007) Multifilament fibers based on dissolution of cellulose in NaOH/urea aqueous solution: structure and properties. Adv Mater 19:821–825CrossRefGoogle Scholar
  8. Carlmark A, Malmström E (2002) Atom transfer radical polymerization from cellulose fibers at ambient temperature. J Am Chem Soc 124:900–901CrossRefGoogle Scholar
  9. Carswell ADW, O'Rear EA, Grady BP (2003) Adsorbed surfactants as templates for the synthesis of morphologically controlled polyaniline and polypyrrole nanostructures on flat surfaces: from spheres to wires to flat films. J Am Chem Soc 125: 14793–14800CrossRefGoogle Scholar
  10. Caruso RA (2004) Micrometer-to-nanometer replication of hierarchical structures by using a surface sol-gel process. Angew Chem Int Ed 43:2746–2748CrossRefGoogle Scholar
  11. Caruso RA, Antonietti M (2001) Sol—gel nanocoating: an approach to the preparation of structured materials. Chem Mater 13:3272–3282CrossRefGoogle Scholar
  12. Caruso RA, Schattka JH, Greiner A (2001) Titanium dioxide tubes from sol—gel coating of electrospun polymer fibers. Adv Mater 13:1577–1579CrossRefGoogle Scholar
  13. Chen Q, Zhou W, Du G, Peng L (2002) Trititanate nanotubes made via a single alkali treatment. Adv Mater 14:1208–1211CrossRefGoogle Scholar
  14. Chen RJ, Bangsaruntip S, Drouvalakis KA, Kam NWS, Shim M, Li Y, Kim W, Utz PJ, Dai H (2003) Noncovalent functionalization of carbon nanotubes for highly specific electronic biosensors. Proc Natl Acad Sci USA 100:4984–4989CrossRefGoogle Scholar
  15. Chia S, Urano J, Tamanoi F, Dunn B, Zink JI (2000) Patterned hexagonal arrays of living vells in sol-gel silica films. J Am Chem Soc 122:6488–6489CrossRefGoogle Scholar
  16. Cook G, Timms PL, Göltner-Spickermann C (2003) Exact replication of biological structures by chemical vapor deposition of silica. Angew Chem Int Ed 42:557–559CrossRefGoogle Scholar
  17. Cui Y, Wei Q, Park H, Lieber CM (2001) Nanowire nanosensors for highly sensitive and selective detection of biological and chemical species. Science 293:1289–1292CrossRefGoogle Scholar
  18. Davis SA, Burkett SL, Mendelson NH, Mann S (1997) Bacterial templating of ordered macrostructures in silica and silica-surfactant mesophases. Nature 385:420–423CrossRefGoogle Scholar
  19. Dong A, Wang Y, Tang Y, Ren N, Zhang Y, Yue Y, Gao Z (2002) Zeolitic tissue through wood cell templating. Adv Mater 14:926–929CrossRefGoogle Scholar
  20. Ekanayake EMIM, Preethichandra DMG, Kaneto K (2007) Polypyrrole nanotube array sensor for enhanced adsorption of glucose oxidase in glucose biosensors. Biosens Bioelectron 23:107–113CrossRefGoogle Scholar
  21. El-Zahab B, Jia H, Wang P (2004) Enabling multienzyme biocatalysis using nanoporous materials. Biotechnol Bioeng 87:178–183CrossRefGoogle Scholar
  22. Ercolessi F, Andreoni W, Tosatti E (1991) Melting of small gold particles: mechanism and size effects. Phys Rev Lett 66:911–914CrossRefGoogle Scholar
  23. Fullam S, Cottell D, Rensmo H, Fitzmaurice D (2000) Carbon nanotube templated self-assembly and thermal processing of gold nanowires. Adv Mater 12:1430–1432CrossRefGoogle Scholar
  24. Gu Y, Huang J (2009) Fabrication of natural cellulose substance derived hierarchical polymeric materials. J Mater Chem 19:3764–3770CrossRefGoogle Scholar
  25. Hall SR, Bolger H, Mann S (2003) Morphosynthesis of complex inorganic forms using pollen grain templates. Chem Commun: 2784–2785Google Scholar
  26. Han R, Xing X, Wang Y, Long Y, Sun Y, Zhao Z, Mi H (2008) Separation/enrichment of active natural low content protein using protein imprinted polymer. J Chromatogr B 873:113–118CrossRefGoogle Scholar
  27. Hassani A, Dupuis A, Skorobogatiy M (2008) Porous polymer fibers for low-loss Terahertz guiding. Opt Express 16:6340–6351CrossRefGoogle Scholar
  28. Huang J, Ichinose I, Kunitake T (2002a) Replication of dendrimer monolayer as nanopores in titania ultrathin film. Chem Commun:2070–2071Google Scholar
  29. Huang J, Ichinose I, Kunitake T (2005a) Nanocoating of natural cellulose fibers with conjugated polymer: hierarchical polypyrrole composite materials. Chem Commun: 1717–1719Google Scholar
  30. Huang J, Ichinose I, Kunitake T (2006a) Biomolecular modification of hierarchical cellulose fibers through titania nanocoating. Angew Chem Int Ed 45:2883–2886CrossRefGoogle Scholar
  31. Huang J, Ichinose I, Kunitake T, Nakao A (2002b) Preparation of nanoporous titania films by surface sol-gel process accompanied by low-temperature oxygen plasma treatment. Langmuir 18:9048–9053CrossRefGoogle Scholar
  32. Huang J, Ichinose I, Kunitake T, Nakao A (2002c) Zirconia-titania nanofilm with composition gradient. Nano Lett 2:669–672CrossRefGoogle Scholar
  33. Huang J, Kaner RB (2004) A general chemical route to polyaniline nanofibers. J Am ChemSoc 126:851–855CrossRefGoogle Scholar
  34. Huang J, Kunitake T (2003) Nano-precision replication of natural cellulosic substances by metal oxides. J Am Chem Soc 125:11834–11835CrossRefGoogle Scholar
  35. Huang J, Kunitake T, Onoue S (2004) A facile route to a highly stabilized hierarchical hybrid of titania nanotube and gold nanoparticle. Chem Commun, p 1008–1009Google Scholar
  36. Huang J, Matsunaga N, Shimanoe K, Yamazoe N, Kunitake T (2005b) Nanotubular SnO2 templated by cellulose fibers: synthesis and gas sensing. Chem Mater 17: 3513–3518CrossRefGoogle Scholar
  37. Huang J, Wang X, Wang Z (2006b) Controlled replication of butterfly wings for achieving tunable photonic properties. Nano Lett 6:2325–2331CrossRefGoogle Scholar
  38. Imai H, Iwaya Y, Shimizu K, Hirashima H (2000) Preparation of hollow fibers of tin oxide with and without antimony doping. Chem Lett 29:906–907CrossRefGoogle Scholar
  39. Kam NWS, Dai H (2005) Carbon nanotubes as intracellular protein transporters: generality and biological functionality. J Am Chem Soc 127:6021–6026CrossRefGoogle Scholar
  40. Kasuga T, Hiramatsu M, Hoson A, Sekino T, Niihara K (1998) Formation of titanium oxide nanotube. Langmuir 14:3160–3163CrossRefGoogle Scholar
  41. Kemell M, Pore V, Ritala M, Leskelä M, Lindén M (2005) Atomic layer deposition in nanometer-level replication of cellulosic substances and preparation of photocata-lytic TiO2/cellulose composites. J Am Chem Soc 127:14178–14179CrossRefGoogle Scholar
  42. Kim Y (2003) Small structures fabricated using ash-forming biological materials as templates. Biomacromolecules 4:908–913CrossRefGoogle Scholar
  43. Klemm D, Heublein B, Fink HP, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed 44:3358–3393CrossRefGoogle Scholar
  44. Kunitake T, Fujikawa S (2003) Nanocopying as a means of 3D nanofabrication: scope and prospects. Aust J Chem 56:1001–1003CrossRefGoogle Scholar
  45. Lakshmi BB, Dorhout PK, Martin CR (1997) Sol—gel template synthesis of semiconductor nanostructures. Chem Mater 9:857–862CrossRefGoogle Scholar
  46. Li Y, Cunin F, Link JR, Gao T, Betts RE, Reiver SH, Chin V, Bhatia SN, Sailor MJ (2003) Polymer replicas of photonic porous silicon for sensing and drug delivery applications. Science 299:2045–2047CrossRefGoogle Scholar
  47. Lin X, Blake AJ, Wilson C, Sun X, Champness NR, George MW, Hubberstey P, Mokaya R, Schröder M (2006) A porous framework polymer based on a Zinc (II) 4,4′-Bipyridine-2,6,2′,6′-tetracarboxylate: synthesis, structure, and “Zeolite-like” behaviors. J Am Chem Soc 128:10745–10753CrossRefGoogle Scholar
  48. Liu S, Gan L, Liu L, Zhang W, Zeng H (2002) Synthesis of single-crystalline TiO2 nanotubes. Chem Mater 14:1391–1397CrossRefGoogle Scholar
  49. Lundqvist M, Sethson I, Jonsson BH (2004) Protein adsorption onto silica nanoparticles: conformational changes depend on the particles' curvature and the protein stability. Langmuir 20:10639–10647CrossRefGoogle Scholar
  50. Mariano MB, Gustavo CN, Maria CM, Cesar AB (2005) Porous carbon-carbon composite replicated from a natural fibre. Chem Commun: 5896–5898Google Scholar
  51. Martin CR (1994) Nanomaterials: a membrane-based synthetic approach. Science 266: 1961–1966CrossRefGoogle Scholar
  52. Meldrum FC, Seshadri R (2000) Porous gold structures through templating by echinoid skeletal plates. Chem Commun:29–30Google Scholar
  53. Morris RE, Wheatley PS (2008) Gas storage in nanoporous materials. Angew Chem Int Ed 47:4966–4981CrossRefGoogle Scholar
  54. Patzke GR, Krumeich F, Nesper R (2002) Oxidic nanotubes and nanorods: anisotropic modules for a future nanotechnology. Angew Chem Int Ed 41:2446–2461CrossRefGoogle Scholar
  55. Perez GP, Crooks RM (2004) Pore-bridging poly(dimethylsiloxane) membranes as selective interfaces for vapor-phase chemical sensing. Anal Chem 76:4137–4142CrossRefGoogle Scholar
  56. Pouget E, Dujardin E, Cavalier A, Moreac A, Valéry C, March-Artzner V, Weiss T, Renault A, Paternostre M, Artzner F (2007) Hierarchical architectures by synergy between dynamical template self-assembly and biomineralization. Nature Mater 6: 434–439CrossRefGoogle Scholar
  57. Sanchezl C, Arribart H, Guille MMG (2005) Biomimetism and bioinspiration as tools for the design of innovative materials and systems. Nature Mater 4:277–288CrossRefGoogle Scholar
  58. Schattka JH, Wong EHM, Antonietti M, Caruso RA (2006) Sol-gel templating of membranes to form thick, porous titania, titania/zirconia and titania/silica films. J Mater Chem 16:1414–1420CrossRefGoogle Scholar
  59. Shan D, He Y, Wang S, Xue H, Zheng H (2006) A porous poly(acrylonitrile-co-acrylic acid) film-based glucose biosensor constructed by electrochemical entrapment. Anal Biochem 356:215–221CrossRefGoogle Scholar
  60. Shigapov AN, Graham GW, McCabe RW, Plummer HK Jr (2001) The preparation of high-surface area, thermally-stable, metal-oxide catalysts and supports by a cellulose templating approach. Appl Catal A 210:287–300CrossRefGoogle Scholar
  61. Shin Y, Li X, Wang C, Coleman JR, Exarhos GJ (2004) Synthesis of hierarchical titanium carbide from titania-coated cellulose paper. Adv Mater 16:1212–1215CrossRefGoogle Scholar
  62. Shin Y, Liu J, Chang JH, Nie Z, Exarhos GJ (2001) Hierarchically ordered ceramics through surfactant-templated sol-gel mineralization of biological cellular structures. Adv Mater 13:728–732CrossRefGoogle Scholar
  63. Tanaka D, Higuchi M, Horike S, Matsuda R, Kinoshita Y, Yanai N, Kitagawa S (2008) Storage and sorption properties of acetylene in jungle-gym-like open frameworks. Chem Asian J 3:1343–1349CrossRefGoogle Scholar
  64. Vertegel AA, Siegel RW, Dordick JS (2004) Silica nanoparticle size influences the structure and enzymatic activity of adsorbed lysozyme. Langmuir 20:6800–6807CrossRefGoogle Scholar
  65. Welbes LL, Borovik AS (2005) Confinement of metal complexes within porous hosts: development of functional materials for gas binding and catalysis. Acc Chem Res 38:765–774CrossRefGoogle Scholar
  66. Xia Y, Yang P, Sun Y, Wu Y, Mayers B, Gates B, Yin Y, Kim F, Yan H (2003) One-dimensional nanostructures: synthesis, characterization, and applications. Adv Mater 15:353–389CrossRefGoogle Scholar
  67. Xiao R, Cho SI, Liu R, Lee SB (2007) Controlled electrochemical synthesis of conductive polymer nanotube structures. J Am Chem Soc 129:4483–4489CrossRefGoogle Scholar
  68. Xu C, Tamaki J, Miura N, Yamazoe N (1991) Grain size effects on gas sensitivity of porous SnO2-based elements. Sens Actuat B 3:147–155CrossRefGoogle Scholar
  69. Yang D, Qi L, Ma J (2002) Eggshell membrane templating of hierarchically ordered macroporous networks composed of TiO2 tubes. Adv Mater 14:1543–1546CrossRefGoogle Scholar
  70. Zabetakis D, Dinderman M, Schoen P (2005) Metal-coated cellulose fibers for use in composites applicable to microwave technology. Adv Mater 17:734–738CrossRefGoogle Scholar
  71. Zhang X, Goux WJ, Manohar SK (2004) Synthesis of polyaniline nanofibers by “nanofiber seeding”. J Am Chem Soc 126:4502–4503CrossRefGoogle Scholar
  72. Zhou J, Chang C, Zhang R, Zhang L (2007) Hydrogels prepared from unsubstituted cellulose in NaOH/urea aqueous solution. Macromol Biosci 7:804–809CrossRefGoogle Scholar

Copyright information

© Zhejiang University Press, Hangzhou and Springer-Verlag Berlin Heidelberg 2010

Authors and Affiliations

  1. 1.Department of ChemistryZhejiang UniversityHangzhou, ZhejiangChina

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