Abstract
Combining various synthetic chemical processes and biological assemblies provides a promising strategy for the design and fabrication of functional materials with tailored structures and properties. The unique multilevel structures and morphologies of natural cellulose substances such as ordinary commercial laboratory filter paper make them ideal platforms for the self-assemblies of various functional guest molecules that are to be deposited on the surfaces of their fine structures, and the resulting composite matters show significant potentials for various applications. The surface sol-gel process was employed to deposit ultrathin metal-oxide (e.g., titania and zirconia) gel films to coat the cellulose nanofibers in bulk filter papers; thereafter, monolayers of specific guest substrates were immobilized onto the surfaces of the metal-oxide gel films. Highly selective, sensitive, and reversible chemosensors based on the surface modification of filter paper were obtained toward the fluorescence and colorimetric detection of various analytes such as heavy-metal ions, inorganic anions, amino acids, and gases. Cellulose-based composite materials with superhydrophobic, antibacterial, or luminescent properties were fabricated by self-assembly approaches toward practical applications.
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References
Brinchi L, Cotana F, Fortunati E, Kenny JM. Production of nanocrystalline cellulose from lignocellulosic biomass: technology and applications. Carbohydr Polym, 2013, 94: 154–169
Henriksson M, Berglund LA. Structure and properties of cellulose nanocomposite films containing melamine formaldehyde. J Appl Polym Sci, 2007, 106: 2817–2824
Iwamoto S, Nakagaito AN, Yano H. Nano-fibrillation of pulp fibers for the processing of transparent nanocomposites. Appl Phys A Mater, 2007, 89: 461–466
Klemm D, Heublein B, Fink HP, Bohn A. Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed, 2005, 44: 3358–3393
Siqueira G, Bras J, Dufresne A. Cellulose whiskers versus microfibrils: influence of the nature of the nanoparticle and its surface functionalization on the thermal and mechanical properties of nanocomposites. Biomacromolecules, 2009, 10: 425–432
Stenstad P, Andresen M, Tanem BS, Stenius P. Chemical surface modifications of microfibrillated cellulose. Cellulose, 2008, 15: 35–45
Kalia S, Boufi S, Celli A, Kango S. Nanofibrillated cellulose: surface modification and potential applications. Colloid Polym Sci, 2014, 292: 5–31
Gong R, Cai W, Li N, Chen J, Liang J, Cao J. Preparation and application of thiol wheat straw as sorbent for removing mercury ion from aqueous solution. Desalin Water Treat, 2010, 21: 274–279
Chen ML, Ma HJ, Zhang SQ, Wang JH. Mercury speciation with L-cysteine functionalized cellulose fibre as adsorbent by atomic fluorescence spectrometry. J Anal At Spectrom, 2011, 26: 613–617
Liu H, Wang D, Song Z, Shang S. Preparation of silver nanoparticles on cellulose nanocrystals and the application in electrochemical detection of DNA hybridization. Cellulose, 2011, 18: 67–74
Shateri-Khalilabad M, Yazdanshenas ME. Fabrication of superhydrophobic, antibacterial, and ultraviolet-blocking cotton fabric. J Text Inst, 2013, 104: 861–869
Zhang X, Huang J. Functional surface modification of natural cellulose substances for colorimetric detection and adsorption of Hg2+ in aqueous media. Chem Commun, 2010, 46: 6042–6044
Xiao W, Luo Y, Zhang X, Huang J. Highly sensitive colourimetric anion chemosensors fabricated by functional surface modification of natural cellulose substance. RSC Adv, 2013, 3: 5318–5323
Gu Y, Huang J. Colorimetric detection of gaseous ammonia by polyaniline nanocoating of natural cellulose substances. Colloid Surf A-Physicochem Eng Asp, 2013, 433: 166–172
Xiao W, Hu H, Huang J. Colorimetric detection of cysteine by surface functionalization of natural cellulose substance. Sens Actuator B-Chem, 2012, 171-172: 878–885
Huang J, Ichinose I, Kunitake T. Biomolecular modification of hierarchical cellulose fibers through titania nanocoating. Angew Chem Int Ed, 2006, 45: 2883–2886
Xiao W, Huang J. Immobilization of oligonucleotides onto zirconia-modified filter paper and specific molecular recognition. Langmuir, 2011, 27: 12284–12288
Li S, Wei Y, Huang J. Facile fabrication of superhydrophobic cellulose materials by a nanocoating approach. Chem Lett, 2010, 39: 20–21
Jin C, Yan R, Huang J. Cellulose substance with reversible photo-responsive wettability by surface modification. J Mater Chem, 2011, 21: 17519–17525
Jin C, Jiang Y, Niu T, Huang J. Cellulose-based material with amphiphobicity to inhibit bacterial adhesion by surface modification. J Mater Chem, 2012, 22: 12562–12567
Xiao W, Xu J, Liu X, Hu Q, Huang J. Antibacterial hybrid materials fabricated by nanocoating of microfibril bundles of cellulose substance with titania/chitosan/silver-nanoparticle composite films. J Mater Chem B, 2013, 1: 3477–3485
Niu T, Gu Y, Huang J. Luminescent cellulose sheet fabricated by facile self-assembly of cadmium selenide nanoparticles on cellulose nanofibres. J Mater Chem, 2011, 21: 651–656
Huang J, Ichinose I, Kunitake T. Nanocoating of natural cellulose fibers with conjugated polymer: hierarchical polypyrrole composite materials. Chem Commun, 2005, 1717-1719
Díez-Gil C, Caballero A, Ratera I, Tárraga A, Molina P, Veciana J. Naked-eye and selective detection of mercury(II) ions in mixed aqueous media using a cellulose-based support. Sensors, 2007, 7: 3481–3488
You J, Hu H, Zhou J, Zhang L, Zhang Y, Kondo T. Novel cellulose polyampholyte-gold nanoparticle-based colorimetric competition assay for the detection of cysteine and mercury(II). Langmuir, 2013, 29: 5085–5092
Poplin JH, Swatlosk RP, Holbrey JD, Spera SK, Metlen A, Grätze M, Nazeeruddin MK, Rogers RD. Sensor technologies based on a cellulose supported platform. Chem Commun, 2007, 20: 2025–2027
Díez-Gil C, Martínez R, Ratera I, Tárraga A, Molina P, Veciana J. Nanocomposite membranes as highly selective and sensitive mercury( II) detectors. J Mater Chem, 2008, 18: 1997–2002
Kazemzadeh A, Daghighi S. Optical nitrite sensor based on chemical modification of a polymer film. Spectroc Acta Pt A-Molec Biomolec Spectr, 2005, 61: 1871–1875
Ensafi AA, Amini M. A highly selective optical sensor for catalytic determination of ultra-trace amounts of nitrite in water and foods based on brilliant cresyl blue as a sensing reagent. Sens Actuator B-Chem, 2010, 147: 61–66
Yasuda SK, Lambert JL. Cellulose supported thorium-alizarin red S reagent for fluoride ion determination. Anal Chem, 1958, 30: 1485–1489
Tang H, Thompson JE. Evaluation of microvolume regenerated cellulose (RC) microdialysis fibers for the sampling and detection of ammonia in air. Talanta, 2010, 81: 1350–1356
Peng L, Yang X, Yuan L, Wang L, Zhao E, Tian F, Liu Y. Gaseous ammoniafluorescence probe based on cellulose acetate modified microstructured optical fiber. Opt Commun, 2011, 284: 4810–4814
Waich K, Mayr T, Klimant I. Microsensors for detection of ammonia at ppb-concentration levels. Meas Sci Technol, 2007, 18: 3195–3201
Felix EP, Cardoso AA. A method for determination of ammonia in air using oxalic acid-impregnated cellulose filters and fluorimetric detection. J Braz Chem Soc, 2012, 23: 142–147
Aied A, Zheng Y, Pandit A, Wang W. DNA immobilization and detection on cellulose paper using a surface grown cationic polymer via ATRP. Appl Mater Interfaces, 2012, 4: 826–831
Liu H, Wang D, Song A, Shang S. Preparation of silver nanoparticles on cellulose nanocrystals and the application in electrochemical detection of DNA hybridization. Cellulose, 2011, 18: 67–74
Huang J, Kunitake T. Nano-precision replication of natural cellulosic substances by metal oxides. J Am Chem Soc, 2003, 125: 11834–11835
Liu L, Xia N, Liu H, Kang X, Liu X, Xue C, He X. Highly sensitive and label-free electrochemical detection of microRNAs based on triple signal amplification of multifunctional gold nanoparticles, enzymes and redox-cycling reaction. Biosens Bioelectron, 2014, 53: 399–405
Li S, Zhang S, Wang X. Fabrication of superhydrophobic cellulose-based materials through a solution-immersion process. Langmuir, 2008, 24: 5585–5590
Vasiljević J, Gorjanc M, Tomšič B, Orel B, Jerman I, Mozetič M, Vesel A, Simončič B. The surface modification of cellulose fibres to create super-hydrophobic, oleophobic and self-cleaning properties. Cellulose, 2013, 20: 277–289
Mirvakili MN, Hatzikiriakos SG, Englezo P. Superhydrophobic lignocellulosic wood fiber/mineral networks. Appl Mater Interfaces, 2013, 5: 9057–9066
Balu B, Breedveld V, Hess D. Fabrication of “roll-off” and “sticky” superhydrophobic cellulose surfaces via plasma processing. Langmuir, 2008, 24: 4785–4790
Wang H, Ding J, Xue Y, Wang X, Lin T. Superhydrophobic fabrics from hybrid silica sol-gel coatings: structural effect of precursors on wettability and washing durability. J Mater Res, 2010, 25: 1336–1343
Zhao Y, Tang Y, Wang X, Lin T. Superhydrophobic cotton fabric fabricated by electrostatic assembly of silica nanoparticles and its remarkable buoyancy. Appl Surf Sci, 2010, 256: 6736–6742
Gonçalves G, Marques PA, Trindade T, Neto CP, Gandini A. Superhydrophobic cellulose nanocomposites. J Colloid Interface Sci, 2008, 324: 42–46
Xu B, Cai Z, Wang W, Ge F. Preparation of superhydrophobic cotton fabrics based on SiO2 nanoparticles and ZnO nanorod arrays with subsequent hydrophobic modification. Surf Coat Technol, 2010, 204: 1556–1561
Liu J, Huang W, Xing Y, Li R, Dai J. Preparation of durable superhydrophobic surface by sol-gel method with water glass and citric acid. J Sol-Gel Sci Technol, 2011, 58: 18–23
Hao L, An Q, Xu W. Facile fabrication of superhydrophobic cotton fabric from stearyl methacrylate modified polysiloxane/silica nanocomposite. Fiber Polym, 2012, 13: 1145–1153
Xu L, Zhuang W, Xu B, Cai Z. Fabrication of superhydrophobic cotton fabrics by silica hydrosol and hydrophobization. Appl Surf Sci, 2011, 257: 5491–5498
Xue CH, Jia ST, Chen HZ, Wang M. Superhydrophobic cotton fabrics prepared by sol-gel coating of TiO2 and surface hydrophobization. Sci Technol Adv Mater, 2008, 9: 035001
Huang L, Chen K, Lin C, Yang R, Gerhardt RA. Fabrication and characterization of superhydrophobic high opacity paper with titanium dioxide nanoparticles. J Mater Sci, 2011, 46: 2600–2605
Guo R, Li Y, Lan J, Jiang S, Liu T, Yan W. Microwave-assisted synthesis of silver nanoparticles on cotton fabric modified with 3-aminopropyltrimethoxysilane. J Appl Polym Sci, 2013, 130: 3862–3868
Khalil-Abad MS, Yazdanshenas ME. Superhydrophobic antibacterial cotton textiles. J Colloid Interface Sci, 2010, 351, 293-298
Shang Y, Si Y, Raza A, Yang L, Mao X, Ding B, Yu J. An in situ polymerization approach for the synthesis of superhydrophobic and superoleophilic nanofibrous membranes for oil-water separation. Nanoscale, 2012, 4: 7847–7854
Li L, Breedveld V, Hess DW. Design and fabrication of superamphiphobic paper surfaces. Appl Mater Interfaces, 2013, 5: 5381–5386
Kang ZZ, Zhang B, Jiao YC, Xu YH, He QZ, Liang J. High-efficacy antimicrobial cellulose grafted by a novel quaternarized N-halamine. Cellulose, 2013, 20: 885–893
Liu Y, Ma K, Li R, Ren X, Huang TS. Antibacterial cotton treated with N-halamine and quaternary ammonium salt. Cellulose, 2013, 20: 3123–3130
Li J, Li R, Du J, Ren X, Worley SD, Huang TS. Improved UV stability of antibacterial coatings with N-halamine/TiO2. Cellulose, 2013, 20: 2151–2161
Lin WC, Lien CC, Yeh HJ, Yu CM, Hsu SH. Bacterial cellulose and bacterial cellulose-chitosan membranes for wound dressing applications. Carbohydr Polym, 2013, 94: 603–611
Tang B, Kaur J, Sun L, Wang X. Multifunctionalization of cotton through in situ green synthesis of silver nanoparticles. Cellulose, 2013, 20: 3053–3065
Yang J, Liu X, Huang L, Sun D. Antibacterial properties of novel bacterial cellulose nanofiber containing silver nanoparticles. Chin J Chem Eng, 2013, 21: 1419–1424
Wang J, Liu W, Li H, Wang H, Wang Z, Zhou W, Liu H. Preparation of cellulose fiber-TiO2 nanobelt-silver nanoparticle hierarchically structured hybrid paper and its photocatalytic and antibacterial properties. Chem Eng J, 2013, 228: 271–280
Azizi S, Ahmad MB, Hussein MZ, Ibrahim NA. Synthesis, antibacterial and thermal studies of cellulose nanocrystal stabilized ZnO-Ag heterostructure nanoparticles. Molecules, 2013, 18: 6269–6280
Fortunati E, Luzi F, Puglia D, Terenzi A, Vercellino M, Visai L, Santulli C, Torre L, Kenny JM. Ternary PVA nanocomposites containing cellulose nanocrystals from different sources and silver particles: part II. Carbohydr Polym, 2013, 97: 837–848
Xu X, Yang YQ, Xing YY, Yang JF, Wang SF. Properties of novel polyvinyl alcohol/cellulose nanocrystals/silver nanoparticles blend membranes. Carbohydr Polym, 2013, 98: 1573–1577
Fortunati E, Armentano I, Zhou Q, Iannoni A, Saino E, Visai L, Berglund LA, Kenny JM. Multifunctional bionanocomposite films of poly (lactic acid), cellulose nanocrystals and silver nanoparticles. Carbohydr Polym, 2012, 87: 1596–1605
Fortunati E, Rinaldi S, Peltzer M, Bloise N, Visai L, Armentano I, Jiménez A, Latterini L, Kenny JM. Nano-biocomposite films with modified cellulose nanocrystals and synthesized silver nanoparticles. Carbohydr Polym, 2014, 101: 1122–1133
Guibal E, Cambe S, Bayle S, Taulemesse JM, Vincent T. Silver/chitosan/cellulose fibers foam composites: from synthesis to antibacterial properties. J Colloid Interface Sci, 2013, 393: 411–420
Hanley CA, McCarthy JE, Purcell-Milton F, Gerard V, McCloskey D, Donegan J, Rakovich YP, Gun’ko YK. Preperation and investigation of quantum-dot-loaded hollow polymer microspheres. J Phys Chem C, 2013, 117: 24527–24536
Tian J, Gao R, Zhang Q, Zhang S, Li Y, Lan J, Qu X, Cao G. Enhanced performance of CdS/CdSe quantum dot cosensitized solar cells via homogeneous distribution of quantum dots in TiO2 film. J Phys Chem C, 2012, 116: 18655–18662
Zhu YF, Fan DH, Zhou GH, Lin YB, Liu L. A suitable chemical conversion route to synthesize ZnO/CdS core/shell heterostructures for photovoltaic applications. Ceram Int, 2014, 40: 3353–3359
Chen C, Li F, Li G, Tan F, Li S, Ling L. Double-sided transparent electrodes of TiO2 nanotube arrays for highly efficient CdS quantum dot-sensitized photoelectrodes. J Mater Sci, 2014, 49: 1868–1874
Li S, Xiao M, Zheng A, Xiao H. Cellulose microfibrils grafted with PBA via surface-initiated atom transfer radical polymerization for biocomposite reinforcement. Biomacromolecules, 2011, 12: 3305–3312
Xiao M, Li S, Chanklin W, Zheng A, Xiao H. Surface-initiated atom transfer radical polymerization of butyl acrylate on cellulose microfibrils. Carbohydr Polym, 2011, 83: 512–519
Toledano-Thompson T, Loría-Bastarrachea MI, Aguilar-Vega MJ. Characterization of henequen cellulose microfibers treated with an epoxide and grafted with poly (acrylic acid). Carbohydr Polym, 2005, 62: 67–73
Li J, Möhwald H, An Z, Lua G. Molecular assembly of biomimetic microcapsules. Soft Matter, 2005, 1: 259–264
He Q, Cui Y, Li J. Molecular assembly and application of biomimetic microcapsules. Chem Soc Rev, 2009, 38: 2292–2303
An Z, Möhwald H, Li J. pH controlled permeability of lipid/protein biomimetic microcapsules. Biomacromolecule, 2006, 7: 580–585
He Q, Möhwald H, Li J. Layer-by-layer assembled nanotubes as biomimetic nanoreactors for calcium carbonate deposition. Macromol Rapid Commun, 2009, 30: 1538–1542
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Luo, Y., Huang, J. Surface modification of natural cellulose substances: toward functional materials and applications. Sci. China Chem. 57, 1672–1682 (2014). https://doi.org/10.1007/s11426-014-5226-4
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DOI: https://doi.org/10.1007/s11426-014-5226-4