Abstract
Diatom frustules, considered as novel bio-functional materials, display a diversity of patterns and unique micro- and nanostructures which may be useful in many areas of application. Existing devices directly use the original structure of the biosilica frustules, limiting their function and structural scale. Current research into the shapes, materials and structural properties of frustules are considered; a series of frustule processing methods including structure processing, material modification, bonding and assembly techniques are reviewed and discussed. The aim is to improve the function of diatom frustules allowing them to meet the design requirements of different types of micro devices. In addition, the importance of the comprehensive use of diatom processing methods in device research is discussed using biosensors and solar cells as examples, and the potential of bio-manufacturing technology based on diatom frustules is examined.
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Dai Z, Tong J, Ren L. Researches and developments of biomimetics in tribology. Chin Sci Bull, 2006, 51: 2681–2689
Zhang D, Cai J, Li X, et al. Bioforming methods of bionic manufacturing (in Chinese). J Mech Eng, 2010, 45: 88–92
Li X, Li Y, Cai J, et al. Metallization of bacteria cells. Sci China Ser E: Technol Sci, 2003, 46: 161–167
Zhang D, Li Y, Han X, et al. High-precision bio-replication of synthetic drag reduction shark skin. Chin Sci Bull, 2011, 56: 938–944
Han X, Zhang D. Study on the micro-replication of shark skin. Sci China Ser E: Technol Sci, 2008, 51: 890–896
Dickerson M B, Sandhage K H, Naik R R. Protein- and peptide- directed syntheses of inorganic materials. Chem Rev, 2008, 108: 4935–4978
Hamm C E, Merkel R, Springer O, et al. Architecture and material properties of diatom shells provide effective mechanical protection. Nature, 2003, 421: 841–843
Losic D, Short K, Mitchell J G, et al. AFM nanoindentations of diatom biosilica surfaces. Langmuir, 2007, 23: 5014–5021
Qi Y, Li J. Chinese Freshwater Algae Chapter 10: Bacillariophyta (in Chinese). Beijing: Science Press, 2004
Qian S, Liu D, Sun J. Phylology Chapter 9: Bacillariophyta (in Chinese). Qingdao: Qingdao Ocean University Press, 2005
Bozarth A, Maier U G, Zauner S. Diatoms in biotechnology: Modern tools and applications. Appl Microbiol Biotechnol, 2009, 82: 195–201
Losic D, Rosengarten G, Mitchell J G, et al. Pore architecture of diatom frustules: Potential nanostructured membranes for molecular and particle separations. J Nanosci Nanotechnol, 2006, 6: 982–989
De Stefano L, Rea I, Rendina I, et al. Lensless light focusing with the centric marine diatom Coscinodiscus walesii. Opt Express, 2007, 15: 18082–18088
De Stefano L, Rendina I, De Stefano M, et al. Marine diatoms as optical chemical sensors. Appl Phys Lett, 2005, 87: 233902. 1–3
Fuhrmann T, Landwehr S, El Rharbi-Kucki M, et al. Diatoms as living photonic crystals. Appl Phys B, 2004, 78: 257–260
Parkinson J, Gordon R. Beyond micromachining: The potential of diatoms. Trends Biotechnol, 1999, 17: 190–196
Gordon R, Losic D, Tiffany M A, et al. The glass menagerie: Diatoms for novel applications in nanotechnology. Trends Biotechnol, 2009, 27: 116–127
Yang W, Lopez P J, Rosengarten G. Diatoms: Self assembled silica nanostructures, and templates for bio/chemical sensors and biomimetic membranes. Analyst, 2011, 136: 42–53
Jeffryes C, Campbell J, Li H, et al. The potential of diatom nanobiotechnology for applications in solar cells, batteries, and electroluminescent devices. Energy Environ Sci, 2011, 4: 3930–3941
Gordon R, Sterrenburg F A S, Sandhage K H. Diatom Nanotechnology: Special issue. New York: American Scientific Publishers, 2005
Losic D, Mitchell J G, Voelcker N H. Diatomaceous lessons in nanotechnology and advanced materials. Adv Mater, 2009, 21: 2947–2958
Lettieri S, Setaro A, De Stefano L, et al. The gas-detection properties of light-emitting diatoms. Adv Funct Mater, 2008, 18: 1257–1264
Losic D, Yu Y, Aw M S, et al. Surface functionalisation of diatoms with dopamine modified iron-oxide nanoparticles: Toward magnetically guided drug microcarriers with biologically derived morphologies. Chem Commun, 2010, 46: 6323–6325
Townley H E, Parker A R, White-Cooper H. Exploitation of diatom frustules for nanotechnology: Tethering active biomolecules. Adv Funct Mater, 2008, 18: 369–374
Gale D K, Gutu T, Jiao J, et al. Photoluminescence detection of biomolecules by antibody-functionalized diatom biosilica. Adv Funct Mater, 2009, 19: 926–933
De Stefano L, Rotiroti L, De Stefano M, et al. Marine diatoms as optical biosensors. Biosens Bioelectron, 2009, 24: 1580–1584
Lin K-C, Kunduru V, Bothara M, et al. Biogenic nanoporous silica- based sensor for enhanced electrochemical detection of cardiovascular biomarkers proteins. Biosens Bioelectron, 2010, 25: 2336–2342
Kroth P. Molecular Biology and the Biotechnological Potential of Diatoms Transgenic Microalgae as Green Cell Factories. New York: Springer, 2007
Hildebrand M. Biological processing of nanostructured silica in diatoms. Prog Org Coat, 2003, 47: 256–266
Martin-Jézéquel V, Hildebrand M, Brzezinski M A. Silicon metabolism in diatoms: Implications for growth. J Phycol, 2000, 36: 821–840
Nassif N, Livage J. From diatoms to silica-based biohybrids. Chem Soc Rev, 2011, 40: 849–859
Ramachandra T V, Mahapatra D M, Karthick B, et al. Milking diatoms for sustainable energy: Biochemical engineering versus gasoline-secreting diatom solar panels. Ind Eng Chem Res, 2009, 48: 8769–8788
Brayner R, Couté A, Livage J, et al. Micro-algal biosensors. Anal Bioanal Chem, 2011, 401: 581–597
Neethirajan S, Gordon R, Wang L. Potential of silica bodies (phytoliths) for nanotechnology. Trends Biotechnol, 2009, 27: 461–467
Round F E, Crawford R M, Mann D G. The Diatoms: Biology and Morphology of the Genera. Cambridge: Cambridge University Press, 1990
Fan T X, Chow S K, Zhang D. Biomorphic mineralization: From biology to materials. Prog Mater Sci, 2009, 54: 542–659
Grachev M A, Annenkov V V, Likhoshway Y V. Silicon nanotechnologies of pigmented heterokonts. BioEssays, 2008, 30: 328–337
Umemura K, Noguchi Y, Ichinose T, et al. Diatom cells grown and baked on a functionalized mica surface. J Biol Phys, 2008, 34: 189–196
Zhang D Y, Wang Y, Zhang W Q, et al. Enlargement of diatom frustules pores by hydrofluoric acid etching at room temperature. J Mater Sci, 2011, 46: 5665–5671
Crawford S A, Chiovitti A, Pickett-Heaps J, et al. Micromorphogenesis during diatom wall formation produces siliceous nanostructures with different properties. J Phycol, 2009, 45: 1353–1362
Wang Y, Pan J, Cai J, et al. Assembling and patterning of diatom frustules onto PDMS substrates using photo-assisted chemical bonding. Chem Lett, 2011, 40: 1354–1356
Zhang D, Cai J, Pan J, et al. Bonding method of diatom shell or kieselguhr and glass. PRC Patent, CN 101786799-A, 2010-7-28
Matthias S, Muller F. Asymmetric pores in a silicon membrane acting as massively parallel brownian ratchets. Nature, 2003, 424: 53–57
Zhang D Y, Wang Y, Pan J F, et al. Separation of diatom valves and girdle bands from Coscinodiscus diatomite by settling method. J Mater Sci, 2010, 45: 5736–5741
Zhang D, Cai J, Wang Y, et al. Method for separating and extracting shell pieces and clitellum from kieselguhr or diatoms. PRC Patent, CN 101792145-A, 2010-8-4
Losic D, Triani G, Evans P J, et al. Controlled pore structure modification of diatoms by atomic layer deposition of TiO2. J Mater Chem, 2006, 16: 4029–4034
Crawford S A, Higgins M J, Mulvaney P, et al. Nanostructure of the diatom frustule as revealed by atomic force and scanning electron microscopy. J Phycol, 2001, 37: 543–554
Hildebrand M, Volcani B E, Gassmann W, et al. A gene family of silicon transporters. Nature, 1997, 385: 688–689
Sumper M. A Phase Separation model for the nanopatterning of diatom biosilica. Science, 2002, 295: 2430–2433
Kröger N, Deutzmann R, Sumper M. Polycationic peptides from diatom biosilica that direct silica nanosphere formation. Science, 1999, 286: 1129–1132
Sumper M, Kroger N. Silica formation in diatoms: The function of long-chain polyamines and silaffins. J Mater Chem, 2004, 14: 2059–2065
Kröger N, Lorenz S, Brunner E, et al. Self-assembly of highly phosphorylated silaffins and their function in biosilica morphogenesis. Science, 2002, 298: 584–586
Telford R J, Vandvik V, Birks H J B. How many freshwater diatoms are pH specialists? A response to Pither & Aarssen (2005). Ecol Lett, 2006, 9: E1–E5
Vrieling E, Sun Q, Tian M, et al. Salinity-dependent diatom biosilicification implies an important role of external ionic strength. Proc Natl Acad Sci USA, 2007, 104: 10441–10446
Townley H E, Woon K L, Payne F P, et al. Modification of the physical and optical properties of the frustule of the diatom Coscinodiscus wailesii by nickel sulfate. Nanotechnology, 2007, 18: 295101.1–295101.5
Jeffryes C, Solanki R, Rangineni Y, et al. Electroluminescence and photoluminescence from nanostructured diatom frustules containing metabolically inserted germanium. Adv Mater, 2008, 20: 2633–2637
Jeffryes C, Gutu, T, Jiao J, et al. Two-stage photobioreactor process for the metabolic insertion of nanostructured germanium into the silica microstructure of the diatom Pinnularia sp. Mater Sci Eng C, 2008, 28: 107–118
Poulsen N, Chesley P M, Kroger N. Molecular genetic manipulation of the diatom Thalassiosira pseudonana (Bacillariophyceae). J Phycol, 2006, 42: 1059–1065
Cai Y, Allan S M, Sandhage K H. Three-dimensional magnesia-based nanocrystal assemblies via low-temperature magnesiothermic reaction of diatom microshells. J Am Ceram Soc, 2005, 88: 2005–2010
Lee S J, Huang C H, Shian S, et al. Rapid hydrolysis of organophosphorous esters induced by nanostructured, fluorine-doped titania replicas of diatom frustules. J Am Ceram Soc, 2007, 90: 1632–1636
Bao Z, Weatherspoon M R, Shian S, et al. Chemical reduction of three-dimensional silica micro-assemblies into microporous silicon replicas. Nature, 2007, 446: 172–175
Sandhage K H, Dickerson M B, Huseman P M, et al. Novel, bioclastic route to self-assembled, 3D, chemically tailored meso/nanostructures: Shape-preserving reactive conversion of biosilica (diatom) microshells. Adv Mater, 2002, 14: 429–433
Shian S, Cai Y, Weatherspoon M R, et al. Three-dimensional assemblies of zirconia nanocrystals via shape-preserving reactive conversion of diatom microshells. J Am Ceram Soc, 2006, 89: 694–698
Weatherspoon M R, Haluska M S, Cai Y, et al. Phosphor microparticles of controlled three-dimensional shape from phytoplankton. J Electrochem Soc, 2006, 153: H34–H37
Dudley S, Kalem T, Akinc M. Conversion of SiO2 diatom frustules to BaTiO3 and SrTiO3. J Am Ceram Soc, 2006, 89: 2434–2439
Bao Z, Song M-K, Davis S C, et al. High surface area, micro/mesoporous carbon particles with selectable 3-D biogenic morphologies for tailored catalysis, filtration, or adsorption. Energy Environ Sci, 2011, 4: 3980–3984
Anderson M W, Holmes S M, Hanif N, et al. Hierarchical pore structures through diatom zeolitization. Angew Chem Int Ed, 2000, 39: 2707–2710
Anderson M W, Holmes S M, Mann R, et al. Zeolitisation of diatoms. J Nanosci Nanotechnol, 2005, 5: 92–95
Hernandez-Ramirez O, Hill P I, Doocey D J, et al. Removal and immobilisation of cobalt ions by a novel, hierarchically structured, diatomite/zeolite Y composite. J Mater Chem, 2007, 17: 1804–1808
Sanhueza V, Kelm U, Cid R, et al. Synthesis of ZSM-5 from diatomite: A case of zeolite synthesis from a natural material. J Chem Technol Biotechnol, 2004, 79: 686–690
Jeffryes C, Gutu T, Jiao J, et al. Metabolic insertion of nanostructured TiO2 into the patterned biosilica of the diatom Pinnularia sp by a two-stage bioreactor cultivation process. ACS Nano, 2008, 2: 2103–2112
Payne E K, Rosi N L, Xue C, et al. Sacrificial biological templates for the formation of nanostructured metallic microshells. Angew Chem Int Ed, 2005, 44: 5064–5067
Yu Y, Addai-Mensah J, Losic D. Synthesis of self-supporting gold microstructures with three-dimensional morphologies by direct replication of diatom templates. Langmuir, 2010, 26: 14068–14072
Gaddis C S, Sandhage K H. Freestanding microscale 3D polymeric structures with biologically-derived shapes and nanoscale features. J Mater Res, 2004, 19: 2541–2545
Holmes S M, Graniel-Garcia B E, Foran P, et al. A novel porous carbon based on diatomaceous earth. Chem Commun, 2006, 2662–2663
Cai X, Zhu G, Zhang W, et al. Diatom-templated synthesis of ordered meso/macroporous hierarchical materials. Eur J Inorg Chem, 2006: 3641–3645
Kusari U, Bao Z, Cai Y, et al. Formation of nanostructured, nanocrystalline boron nitride microparticles with diatom-derived 3-D shapes. Chem Commun, 2007, 1177–1179
Zhao J, Gaddis C S, Cai Y, et al. Free-standing microscale structures of nanocrystalline zirconia with biologically replicable three-dimensional shapes. J Mater Res, 2005, 20: 282–287
Liu Z, Fan T, Zhou H, et al. Synthesis of ZnFe2O4/SiO2 composites derived from a diatomite template. Bioinspi Biomim, 2007, 2: 30
Lee D H, Gutu T, Jeffryes C, et al. Nanofabrication of green luminescent Zn2SiO4:Mn using biogenic silica. Electrochem Solid-State Lett, 2007, 10: K13–K16
Weatherspoon M R, Allan S M, Hunt E, et al. Sol-gel synthesis on self-replicating single-cell scaffolds: Applying complex chemistries to nature’s 3-D nanostructured templates. Chem Commun, 2005, 651–653
Ernst E M, Church B C, Gaddis C S, et al. Enhanced hydrothermal conversion of surfactant-modified diatom microshells into barium titanate replicas. J Mater Res, 2007, 22: 1121–1127
Bao Z H, Ernst E M, Yoo S, et al. Syntheses of porous self-supporting metal-nanoparticle assemblies with 3D morphologies inherited from biosilica templates (diatom Frustules). Adv Mater, 2009, 21: 474–478
Li X W, Bian C Q, Chen W, et al. Polyaniline on surface modification of diatomite: A novel way to obtain conducting diatomite fillers. Appl Surf Sci, 2003, 207: 378–383
Zhang D, Zhang W, Cai J. Magnetization of microorganism cells by thermal decomposition method. Sci China Technol Sci, 2011, 54: 1275–1280
Zhang W, Zhang D, Cai J. Fabrication of flake-shaped core-shell micro particles by way of thermal decomposition of pentacarbonyl iron on diatomite surface. Adv Eng Mater, 2011: 730–733
Lan M, Zhang D, Cai J, et al. Electroless plating of silver on microorganism cells. Adv Mater Res, 2011: 531–535
Cai J, Zhang D Y, Lan M M, et al. Research on magnetic metallization of microorganism cells using electroplating technique. Sci China Technol Sci, 2011, 54: 1525–1531
Zhang D, Zhang W, Cai J. Fabrication and electromagnetic properties of flake ferrite particles based on diatomite. J Magn Magn Mater, 2011, 323: 2305–2309
Losic D, Mitchell J G, Lal R, et al. Rapid fabrication of micro- and nanoscale patterns by replica molding from diatom biosilica. Adv Funct Mater, 2007, 17: 2439–2446
Wang W, Gutu T, Gale D K, et al. Self-assembly of nanostructured diatom microshells into patterned arrays assisted by polyelectrolyte multilayer deposition and inkjet printing. J Am Chem Soc, 2009, 131: 4178–4179
Zhang D, Pan J, Cai J, et al. Hydrofluoric acid-assisted bonding of diatoms with SiO2-based substrates for microsystem application. J Micromech Microeng, 2012, 22: 35021–35029
Cai J, Wang Y, Zhang D, et al. A method of assembling and patterning diatom frustules onto PDMS substrates. PRC Patent, CN 201110326629. 1, 2011-10-25
Wang Y, Pan J, Cai J, et al. Floating assembly of diatom Coscinodiscus sp microshells. Biochem Biophys Res Commun, 2012, 420: 1–5
George M W, Grzybowski B. Self-assembly at all scales. Science, 2002, 295: 2418–2421
Whitesides G M, Boncheva M. Beyond molecules: Self-assembly of mesoscopic and macroscopic components. Proc Natl Acad Sci USA, 2002, 99: 4769–4774
Nagayama K. Science of Self-Aasembly. Tokyo: Maruzen Co., Ltd, 1997
Srinivasan U, Liepmann D, Howe R T. Microstructure to substrate self-assembly using capillary forces. J Microelectromech Syst, 2001, 10: 17–24
Kulkarni S A, Ogale S B, Vijayamohanan K P. Tuning the hydrophobic properties of silica particles by surface silanization using mixed self-assembled monolayers. J Colloid Interface Sci, 2008, 318: 372–379
Milligan A J, Morel F M M. A proton buffering role for silica in diatoms. Science, 2002, 297: 1848–1850
De Stefano M, De Stefano L, Congestri R. Functional morphology of micro- and nanostructures in two distinct diatom frustules. Superlattices Microstruct, 2009, 46: 64–68
Raven J A, Waite A M. The evolution of silicification in diatoms: Inescapable sinking and sinking as escape? New Phytol, 2004, 162: 45–61
Zhang F. Processing and Application of Diatomite (in Chinese). Beijing: Chemical Industry Press, 2006
Lin J. Study on preparation, characterization and dyes adsorption properties of diatomite-based adsorbent (in Chinese). Doctoral Dissertation. Hangzhou: Zhejiang University, 2007
Umemura K, Noguchi Y, Ichinose T, et al. Morphology and physical- chemical properties of baked nanoporous frustules. J Nanosci Nanotechnol, 2010, 10: 5220–5224
Wang Y, Zhang D, Pan J, et al. Key factors influencing the optical detection of biomolecules by their evaporative assembly on diatom frustules. J Mater Sci, 2012, doi: 10.1007/s10853-10012-16554-10854
Pan J, Cai J, Zhang D, et al. Micro-arraying of nanostructured diatom microshells on glass substrate using ethylene-vinyl acetate copolymer and photolithography technology for fluorescence spectroscopy application. Physica E, 2012, doi: 10.1016/j.physe.2012.1003.1032
Grätzel M. Dye-sensitized solar cells. J Photochem Photobiol C, 2003, 4: 145–153
Park K H, Gu H B, Jin E M, et al. Using hybrid silica-conjugated TiO2 nanostructures to enhance the efficiency of dye-sensitized solar cells. Electrochim Acta, 2010, 55: 5499–5505
Ito S, Murakami T N, Comte P, et al. Fabrication of thin film dye sensitized solar cells with solar to electric power conversion efficiency over 10%. Thin Solid Films, 2008, 516: 4613–4619
Jeffryes C, Gutu T, Jiao J, et al. Peptide-mediated deposition of nanostructured TiO2 into the periodic structure of diatom biosilica. J Mater Res, 2008, 23: 3255–3262
Wang Y, Zhang D, Cai J, et al. Biosilica structures obtained from Nitzschia, Ditylum, Skeletonema, and Coscinodiscus diatom by a filtration- aided acid cleaning method. Appl Microbiol Biotechnol, 2012, 95: 1165–1178
Gordon R. Preface to the Diatom Nanotechnology Special Issue. J Nanosci Nanotechnol, 2005, 5: 1–4
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Zhang, D., Wang, Y., Cai, J. et al. Bio-manufacturing technology based on diatom micro- and nanostructure. Chin. Sci. Bull. 57, 3836–3849 (2012). https://doi.org/10.1007/s11434-012-5410-x
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DOI: https://doi.org/10.1007/s11434-012-5410-x