Abstract
The porous template synthesis method has attracted significant interest as a versatile approach to prepare tubular nanomaterials with tailored properties. The process involves deposition or synthesis of various materials such as polymers, nanoparticles, proteins, dyes, and organic or inorganic small molecules within the porous templates, which are subsequently removed to yield free-standing nanotubes. At the same time, this approach permits the formation of composite nanotubes with the engineering features including size, shape, composition, and function. In this chapter, we summarize the synthesis and properties of various composite nanotubes based on template method combining with layer-by-layer assembly, sol—gel chemistry and polymerization. These nanotubes possess potential applications in biomedical fields such as bioseparation, biocatalysis, biosensor, and drug delivery.
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References
Aegerter MA, Mehrota RC, Oehme I, Reisfeld R, Sakka S, Wolfbeis O, Jorgensen CK (1996) Optical and electronic phenomena in sol-gel glasses and modern applications. Berlin: Springer-Verlag: 85
Ai S, He Q, Tao C, Zheng S, Li J (2005) Conductive polypyrrole and poly(allylamine hydrochloride) nanotubes fabricated with layer-by-layer assembly. Macromol Rapid Comm 20:1965–1969
Ai S, Lu G, He Q, Li J (2003) Highly flexible polyelectrolyte nanotubes. J Am Chem Soc 125:11140–11141
An Z, Lu G, Möhwald H, Li J (2004) Self-assembly of human serum albumin (HSA) and L-α dimyristoylphosphatidic acid (DMPA) microcapsules for controlled drug release. Chem Eur J 10:5848–5852
An Z, Tao C, Lu G, Möhwald H, Zheng S, Cui Y, Li J (2005) Fabrication and characterization of human serum albumin and L-α-dimyristoylphosphatidic acid microcapsules based on template technique. Chem Mater 17:2514–2519
Ariga K, Nakanishi T, Hill JP (2007) Self-assembled microstructures of functional molecules. Curr Opin Colloid Interface 12:106–120
Baughman RH, Zakhidov AA, Heer WA (2002) Carbon nanotubes: the route toward applications. Science 297:787–792
Bertrand P, Jonas A, Laschewsky A, Legras R (2000) Ultrathin polymer coatings by complexation of polyelectrolytes at interfaces: suitable materials, structure and properties. Macromol Rapid Commun 21:319–348
Bischoff BL, Anderson MA (1995) Peptization process in the sol-gel preparation of porous anatase (TiO2). Chem Mater 7:1772–1778
Bruchez M, Moronne M, Gin P, Weiss S, Alivisatos AP (1998) Semiconductor nanocrystals as fluorescent biological labels. Science 281:2013
Brumlik CJ, Martin CR (1991) Template synthesis of metal microtubules. J Am Chem Soc 113:3174–3175
Brumlik CJ, Menon VP, Martin CR (1994) Template synthesis of metal microtubule ensembles utilizing chemical, electrochemical, and vacuum deposition techniques. J Mater Res 9:1174–1183
Cai Z, Lei J, Liang W, Martin CR (1991) Molecular and supermolecular origins of enhanced electronic conductivity in template-synthesized polyheterocyclic fibrils. 1. Supermolecular effects. Chem Mater 3:960–967
Cai Z, Martin CR (1989) Electronically conductive polymer fibers with mesoscopic diameters show enhanced electronic conductivities. J Am Chem Soc 111:4138–4139
Caruso F (2000) Hollow capsule processing through colloidal templating and self-assembly. Chem Eur J 6:413–419
Chen C, Liu Y, Wu C, Yeh C, Su M, Wu Y (2005) Preparation of fluorescent silica nanotubes and their application in gene delivery. Adv Mater 17:404–407
Chen J, Yoshida M, Maekawa Y, Tsubokawa N (2001) Temperature-switchable vapor sensor materials based on N-isopropylacrylamide and calcium chloride. Polymer 42:9361–9365
Cui Y, Tao C, Tian Y, He Q, Li J (2006) Synthesis of PNIPAM-co-MBAA copolymer nanotubes with composite control. Langmuir 22:8205–8208
Cui Y, Tao C, Zheng S, He Q, Ai S, Li J (2005) Synthesis of thermosensitive PNIPAM-co-MBAA nanotubes by atom transfer radical polymerization within a porous membrane. Macromol Rapid Commun 26:1552–1556
Cunliffe D, Smart CA, Tsibouklis J, Young S, Alexander C, Vulfson EN (2000) Bacterial adsorption to thermoresponsive polymer surfaces. Biotechnol Lett 22:141–145
Decher G (1997) Fuzzy nanoassemblies: oward layered polymeric multicomposites. Science 277:1232–1237
Djuristic AB, Fritz T, Leo K (2000) Modeling the optical constants of organic thin films: application to 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA). Opt Commun 183:123–132
Donath E, Sukhorukov GB, Caruso F, Davis SA, Möhwald H (1998) Novel hollow polymer shells by colloid-templated assembly of polyelectrolytes. Angew Chem Int Ed 37:2202–2205
Duan L, He Q, Wang K, Yan X, Cui Y, Möhwald H, Li J (2007a) Adenosine triphosphate biosynthesis catalyzed by FoF1 atp synthase assembled in polymer microcapsules. Angew Chem Int Ed 46:6996–7000
Duan L, He Q, Yan X, Cui Y, Wang K, Li J (2007b) Hemoglobin protein hollow shells fabricated through covalent layer-by-layer technique. Biochem Biophys Res Commun 354:357–362
Feng C, Zhong X, Steinhart M, Caminade AM, Majoral J, Knoll W (2007) Graded-bandgap quantum-dot-modified nanotubes: a sensitive biosensor for enhanced detection of DNA hybridization. Adv Mater 19:1933–1936
Feng C, Zhong X, Steinhart M, Caminade AM, Majoral J, Knoll W (2008) Functional quantum-dot/dendrimer nanotubes for sensitive detection of DNA hybridization. Small 4:566–571
Ford WE, Kamat PV (1987) Photochemistry of 3,4,9,10-perylenetetracarboxylic dianhydride dyes.3. Singlet and triplet excited-state properties of the bis(2,5-di-tert-butylphenyl)imide derivative. J Phys Chem 91:6373–6380
Fu Q, Rao GVR, Basame SB, Keller DJ, Artyushkova K, Fulghum JE, Lopez GP (2004) Reversible control of free energy and topography of nanostructured surfaces. J Am Chem Soc 126:8904–8905
Gao Y, Banin U (1999) Synthesis and characterization of InAs/InP and InAs/CdSe core/shell nanocrystals. Angew Chem Int Ed 38:3692–3694
Gilcreest VP, Carroll WM, Rochev YA, Blute I, Dawson KA, Gorelov AV (2004) Thermoresponsive poly(N-isopropylacrylamide) copolymers: contact angles and surface energies of polymer films. Langmuir 20:10138–10145
Gooding JJ, Wibowo R, Liu J, Yang W, Losic D, Orbons S, Mearns F, Shapter JG, Hibbert DB (2003) Protein electrochemistry using aligned carbon nanotube arrays. J Am Chem Soc 125:9006–9007
Grawford GP, Steele LM, Ondris-Crawford R, Iannacchione GS, Yeager CJ, Doane JW, Finotello D (1992) Characterization of the cylindrical cavities of anopore and nuclepore membranes. J Chem Phys 96:7788–7796
Hammond PT (2004) Form and function in multilayer assembly: new applications at the nanoscale. Adv Mater 16:1271–1293
Harmon ME, Kuckling D, Frank CW (2003) Photo-cross-linkable PNIPAAm copolymers. 4. Effects of copolymerization and cross-linking on the volume-phase transition in constrained hydrogel layers. Langmuir 19:10947–10956
He Q, Cui Y, Ai S, Tian Y, Li J (2009) Self-assembly composite nanotubes and their applications. Curr Opin Colliod In 14:115–125
He Q, Song W, Möhwald H, Li J (2008a) Hydrothermal-induced structure transformation of polyelectrolyte multilayers: from nanotubes to capsules. Langmuir 24: 5508–5513
He Q, Tian Y, Cui Y, Möhwald H, Li J (2008b) Layer-by-layer assembly of magnetic polypeptide nanotubes as a DNA carrier. J Mater Chem 18:748–754
He Q, Zhang Y, Lu G, Miller R, Möhwald H, Li J (2008c) Dynamic adsorption and characterization of phospholipid and mixed phospholipid/protein layers at liquid/liquid interfaces. Adv Colloid Interface Sci 140:67–76
Hench LL, West JK (1990) The sol-gel process. Chem Rev 90:33–72
Hillebrenner H, Buyukserin F, Stewart JD, Martin CR (2006) Template synthesized nanotubes for biomedical delivery applications. Nanomedicine 1:39–50
Hou S, Wang J, Martin CR (2005a) Template-synthesized DNA nanotubes. J Am Chem Soc 127:8586–8587
Hou S, Wang J, Martin CR (2005b) Template-synthesized protein nanotubes. Nano Lett 5:231–234
Hulteen JC, Martin CR (1997) A general template-based method for the preparation of nanomaterials. J Mater Chem 7:1075–1087
Ichinose I, Senzu H, Kunitake T (1997) A surface sol—gel process of TiO2 and other metal oxide films with molecular precision. Chem Mater 9:1296–1298
Iijima S (1991) Helical microtubules of graphitic carbon. Nature 354:56–58
Jiang Y, Yan D, Gao X, Han C, Jin X, Li L (2003) Lamellar branching of poly(bisphenol A-co-decane) spherulites at different temperatures studied by high-temperature AFM. Macromolecules 36:3652–3655
Jirage KB, Hulteen JC, Martin CR (1997) Nanotubule-based molecular-filtration membranes. Science 278:655–658
Johnston APR, Mitomo H, Read ES, Caruso F (2006) Compositional and structural engineering of DNA multilayer films. Langmuir 22:3251–3258
Johnston APR, Read ES, Caruso F (2005) DNA multilayer films on planar and colloidal supports: sequential assembly of like-charged polyelectrolytes. Nano Lett 5:953–956
Kim DH, Karan P, Göring P, Leclaire J, Caminade AM, Majoral JP, Gösele U, Steinhart M, Knoll W (2005) Formation of dendrimer nanotubes by layer-by-layer deposition. Small 1:99–102
Kohli P, Blanchard GJ (2000) Applying polymer chemistry to interfaces: layer-by-layer and spontaneous growth of covalently bound multilayers. Langmuir 16:4655–4661
Kong H, Li W, Gao C, Yan D, Jin Y, Walton DRM, Kroto HW (2004) Poly(N-isopropylacrylamide)-coated carbon nanotubes: temperature-sensitive molecular nano-hybrids in water. Macromolecules 37:6683–6686
Kost J, Langer R (2001) Responsive polymeric delivery systems. Adv Drug Delivery Res 46:125–148
Kovtyukhova NI, Buzaneva EV, Waraksa CC, Martin B, Mallouk TE (2000) Surface sol—gel synthesis of ultrathin semiconductor films. Chem Mater 12:383–389
Kovtyukhova NI, Mallouk TE, Mayer TS (2003) Template surface sol—gel synthesis of SiO2 nanotubes and SiO2-insulated metal nanowires. Adv Mater 15:780–785
Kuckling D, Adler HJP, Arndt KF, Ling L, Habicher WD (2000) Temperature and pH dependent solubility of novel poly(N-isopropylacrylamide) copolymers. Marcomol Chem Phys 201:273–280
Lakshmi BB, Dorhout PK, Martin CR (1997a) Sol-gel template synthesis of semiconductor nanostructures. Chem Mater 9:857–862
Lakshmi BB, Patrissi CJ, Martin CR (1997b) Sol—gel template synthesis of semiconductor oxide micro-and nanostructures. Chem Mater 9:2544–2550
Lee AB, Koepsel RR, Morley SW, Matyjaszewski K, Sun Y, Russell AJ (2004) Permanent, nonleaching antibacterial surfaces. 1. Synthesis by atom transfer radical polymerization. Biomacromolecules 5:877–882
Lee DY, Nolte AJ, Kunz AL, Rubner MF, Cohen RE (2006) pH-Induced hysteretic gating of track-etched polycarbonate membranes: swelling/deswelling behavior of polyelectrolyte multilayers in confined geometry. J Am Chem Soc 128:8521–8529
Lee SB, Martin CR (2001) Controlling the transport properties of gold nanotubule membranes using chemisorbed thiols. Chem Mater 13:3236–3244
Lee SB, Mitchell DT, Trofin L, Nevanen TK, Soederlund H, Martin CR (2002) Antibody-based bio-nanotube membranes for enantiomeric drug separations. Science 296:2198–2200
Lei J, Menon VP, Martin CR (1992) Chemical preparation of conductive polypyrrole-polytetrafluoroethene composites. Polym Adv Technol 4:124–132
Li J, Möhwald H An Z, Lu G (2005) Molecular assembly of biomimetic microcapsules. Soft Matter 1:259–264
Li J, Zhang Y, Yan L (2001) Multilayer formation on a curved drop surface. Angew Chem Int Ed 40:891–894
Liang W, Martin CR (1990) Template-synthesized polyacetylene fibrils show enhanced supermolecular order. J Am Chem Soc 112:9666–9668
Liang ZJ, Susha AS, Yu AM, Caruso F (2003) Nanotubes prepared by layer-by-layer coating of porous membrane template. Adv Mater 15:1849–1853
Livage J, Henry M, Sanchez C (1988) Sol—gel chemistry of transition metal oxides. Prog Solid State Chem 18:259–341
Lu G, Ai S, Li J (2005) Layer-by-layer assembly of human serum albumin and phospholipid nanotubes based on a template. Langmuir 21:1679–1682
Lu G, Komatsu T, Tsuchida E (2007) Artificial hemoprotein nanotubes. Chem Commun 28:2980–2982
Lynn DM (2007) Peeling back the layers: controlled erosion and triggered disassembly of multilayered polyelectrolyte thin films. Adv Mater 19:4118–4130
Martin CR (1991) Template synthesis of polymeric and metal microtubules. Adv Mater 3:457–459
Martin CR (1994) Nanomaterials: a membrane-based synthetic approach. Science 266: 1961–1966
Martin CR, Parthasarathy R, Menon V (1993) Template synthesis of electronically conductive polymers: a new route for achieving higher electronic conductivities. Synth Met 55:1165–1170
Mitchell DT, Lee SB, Trofin L, Li N, Nevanen TK, Söderlund H, Martin CR (2002) Smart nanotubes for bioseparations and biocatalysis. J Am Chem Soc 124:11864–11865
Nishizawa M, Menon VP, Martin CR (1995) Metal nanotubule membranes with electrochemically switchable ion-transport selectivity. Science 268:700–702
Parthasarathy R, Martin CR (1994a) Synthesis of polymeric microcapsule arrays and their use for enzyme immobilization. Nature 369:298–301
Parthasarathy R, Martin CR (1994b) Template-synthesized polyaniline microtubules. Chem Mater 6:1627–1632
Patten TE, Maytjaszewski K (1998) Atom transfer radical polymerization and the synthesis of polymeric materials. Adv Mater 12:901–915
Peyratout CS, Daehne L (2004) Tailor-made polyelectrolyte microcapsules: from multilayers to smart containers. Angew Chem Int Ed 43:3762–3783
Quinn JF, Caruso F (2004) Facile tailoring of film morphology and release properties using layer-by-layer assembly of thermoresponsive materials. Langmuir 20:20–22
Quinn JF, Johnston APR, Such GK, Zelikin AN, Caruso F (2007) Next generation, sequentially assembled ultrathin films: beyond electrostatics. Chem Soc Rev 36:707–718
Reber N, Kuchel A, Spohr R, Wolf A, Yoshida M (2001) Transport properties of thermoresponsive ion track membranes. J Membr Sci 193:49–58
Serizawa T, Nanameki K, Yamamoto K, Akashi M (2002) Thermoresponsive ultrathin hydrogels prepared by sequential chemical reactions. Macromolecules 35:2184–2189
Shi D, Lian J, Wang W, Liu G, He P, Dong Z, Wang L, Ewing RC (2006) Luminescent carbon nanotubes by surface functionalization. Adv Mater 18:189–193
Steinhart M (2008) Supramolecular organization of polymeric materials in nanoporous hard templates. Adv Polym Sci 220:123–187
Steinhart M, Wehrspohn RB, Gösele U, Wendorff JH (2004) Nanotubes by template wetting: a modular assembly system. Angew Chem Int Ed 43: 1334–1344
Steinhart M, Wendorff JH, Greiner A, Wehrspohn RB, Nielsch K, Schilling J, Choi J, Gösele U (2002) Polymer nanotubes by wetting of ordered porous templates. Science 296:1997
Stockto WB, Rubner MF (1997) Molecular-level processing of conjugated polymers. 4. Layer-by-layer manipulation of polyaniline via hydrogen-bonding interactions. Macromolecules 30: 2717–2725
Such GK, Quinn JF, Quinn A, Tjipto E, Caruso F (2006) Assembly of ultrathin polymer multilayer films by click chemistry. J Am Chem Soc 128:9318–9319
Sukhishvili SA, Granick S (2000) Layered, erasable, ultrathin polymer films. J Am Chem Soc 122:9550–9551
Sukhishvili SA, Granick S (2002) Layered, erasable polymer multilayers formed by hydrogen-bonded sequential self-assembly. Macromolecules 35:301–310
Sun T, Wang G, Feng L, Liu B, Ma Y, Liang L, Zhu D (2004) Reversible switching between superhydrophilicity and superhydrophobicity. Angew Chem Int Ed 43:357–360
Tian Y, He Q, Cui Y, Li J (2006a) Fabrication of protein nanotubes based on layer-by-layer assembly. Biomacromolecules 7:2539–2542
Tian Y, He Q, Cui Y, Tao C, Li J (2006b) Assembly of nanotubes of poly(4-vinylpyridine) and poly(acrylic acid) through hydrogen bonding. Chem Eur J 12:4808–4812
Tian Y, He Q, Li J (2006c) Fabrication of fluorescent nanotubes based on layer-by-layer assembly via covalent bond. Langmuir 22:360–362
Tian Y, He Q, Tao C, Cui Y, Ai S, Li J (2006d) Fabrication of polyethyleneimine and poly(styrene-alt-maleic anhydride) nanotubes through covalent bond. J Nanosci Nanotechnol 6:2072–2076
Van Dyke LS, Martin CR (1990) Electrochemical investigations of electronically conductive polymers. 4. Controlling the supermolecular structure allows charge transport rates to be enhanced. Langmuir 6:1118–1123
Wang H, Zhou W, Yin X, Zhuang Z, Yang H, Wang X (2006) Template synthesized molecularly imprinted polymer nanotube membranes for chemical separations. J Am Chem Soc 128: 15954–15955
Wang K, He Q, Cui Y, Yan X, Qi W, Li J (2007) Encapsulated photosensitive drugs by biodegradable microcapsules to incapacitate cancer cells. J Mater Chem 17:4018–4021
Wang L, Wang Z, Zhang X, Shen J, Chi L, Fuchs H (1997) A new approach for the fabrication of an alternating multilayer film of poly(4-vinylpyridine) and poly(acry1ic acid) based on hydrogen bonding. Macromol Rapid Commun 18:509–514
Wang Y, Angelatos AS, Caruso F (2008) Template synthesis of nanostructured materials via layer-by-layer assembly. Chem Mater 20:848–858
Wang Z, Chumanov G (2003) WO3 sol—gel modified Ag nanoparticles arrays for electrochemical modulation of surface plasmon resonance. Adv Mater 15:1285–1289
Williams KA, Veenhuizen PT, Torre BG, Eritja R, Dekker C (2002) Nanotechnology: carbon nanotubes with DNA recognition. Nature 420:761
Willner I, Katz E (2000) Integration of layered redox proteins and conductive supports for bioelectronic applications. Angew Chem Int Ed 39:1180–1218
Willner I, Patolsky F, Wasserman J (2001) Photoelectrochemistry with controlled DNA-cross-linked CdS nanoparticle arrays. Angew Chem Int Ed 40:1861–1864
Wong EW, Sheehan PE, Lieber CM (1997) Nanobeam mechanics: elasticity, strength, and toughness of nanorods and nanotubes. Science 277:1971–1975
Yang S, Rubner MF (2002) Micropatterning of polymer thin films with pH-sensitive and cross-linkable hydrogen-bonded polyelectrolyte multilayers. J Am Chem Soc 124: 2100–2101
Yang Y, He Q, Duan L, Cui Y, Li J (2007) Assembled alginate/chitosan nanotubes for biological application. Biomaterials 28: 3083–3090
Yu A, Liang Z, Caruso F (2005) Enzyme multilayer-modified porous membranes as biocatalysts. Chem Mater 17:171–175
Zelenski CM, Dorhout PK (1998) Template synthesis of near-monodisperse microscale nanofibers and nanotubules of MoS2. J Am Chem Soc 120:734–742
Zelikin AN, Li Q, Caruso F (2006) Degradable polyelectrolyte capsules filled with oligonucleotide sequences. Angew Chem Int Ed 45:7743–7745
Zheng S, Tao C, He Q, Zhu H, Li J (2004) Self-assembly and characterization of polypyrrole and polyallylamine multilayer films and hollow shells. Chem Mater 16: 3677–3681
Zhi L, Wu J, Li J, Stepputat M, Kolb U, Muellen K (2005) Diels-alder reactions of tetraphenylcyclopentadienones in nanochannels: fabrication of nanotubes from hyperbranched polyphenylenes. Adv Mater 17:1492–1496
Zhou Y, Shimizu T (2008) Lipid nanotubes: a unique template to create diverse one-dimensional nanostructures. Chem Mater 20:625–633
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Cui, Y., He, Q., Li, J. (2010). Nanoporous Template Synthesized Nanotubes for Bio-related Applications. In: Li, J. (eds) Nanostructured Biomaterials. Advanced Topics in Science and Technology in China. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-05012-1_5
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