Abstract
The stabilizing role of carboxymethyl groups on the conformal deposition of Ag NPs over cellulosic fibers was elucidated while developing a method for the deposition of silver nanoparticles (NPs) on cellulose acetate (CA), cellulose and partially carboxymethylated cellulose (CMC) electrospun fibers. CMC fibers were prepared through judicious anionization of deacetylated cellulose acetate fibers. Ag NPs were chemically reduced from silver nitrate using sodium borohydride and further stabilized using citrate. Ag NPs were directly deposited onto CA, cellulose and CMC electrospun fibers at pH conditions ranging from 2.5 to 9.0. The resulting composites of Ag/fiber were characterized by field emission scanning electron microscopy (FESEM) and energy-dispersive X-ray spectroscopy (EDX). The results revealed that the amount of Ag agglomerates and NPs deposited on CMC fibers was higher than that deposited on cellulose fibers at similar pH conditions, and that barely any Ag agglomerates or NPs were deposited on the CA fibers. These results implied that functional groups on the cellulose backbone played two important roles in the deposition of NPs as follows: (1) Hydrogen bonding was the main driving force for agglomeration of NPs when the medium pH was below 4.4, which corresponds to the pKa of carboxylic acid groups; (2) Carboxymethyl groups could replace citrate groups as stabilizers allowing the fabrication of a uniform and evenly distributed Ag NPs layer over CMC fibers at higher pH values. This report also highlights the importance of the substrate’s surface charge and that of the pH of the medium used, on the deposition of NPs. The composite of Ag NPs on CMC electrospun fibers appears to be a promising candidate for wound dressing applications due to its superior antibacterial properties originated by the uniform and even distribution of Ag NPs on the surface of the fibers and the wound healing aptness of the CMC fibers.
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References
Borsa J, Racz I (1995) Carboxymethylcellulose of fibrous character. A survey. Cellul Chem Technol 29(6):657–663
Chen CY, Chiang CL (2008) Preparation of cotton fibers with antibacterial silver nanoparticles. Mater Lett 62(21–22):3607–3609
Chen J, Wang J, Zhang X, Jin YL (2008) Microwave-assisted green synthesis of silver nanoparticles by carboxymethyl cellulose sodium and silver nitrate. Mater Chem Phys 108(2–3):421–424
Craver CD, Carraher CE (2000) Applied polymer science: 21st century. Elsevier, New York
Daul GC, Reinhardt RM, Reid JD (1952) Studies on the partial carboxymethylation of cotton. Text Res J 22(12):787–792
Dong H, Hinestroza JP (2009) Metal nanoparticles on natural cellulose fibers: electrostatic assembly and in situ synthesis. ACS Appl Mat Interf 1(4):797–803
Dong H, Fey E, Gandelman A, Jones WE (2006) Synthesis and assembly of metal nanoparticles on electrospun poly(4-vinylpyridine) fibers and poly(4-vinylpyridine) composite fibers. Chem Mater 18(8):2008–2011
Dong H, Wang D, Sun G, Hinestroza JP (2008) Assembly of metal nanoparticles on electrospun nylon 6 nanofibers by control of interfacial hydrogen-bonding interactions. Chem Mater 20(21):6627–6632
Dubas ST, Kumlangdudsana P, Potiyaraj P (2006) Layer-by-layer deposition of antimicrobial silver nanoparticles on textile fibers. Colloids Surf A 289(1–3):105–109
Han SO, Youk JH, Min KD, Kang YO, Park WH (2008) Electrospinning of cellulose acetate nanofibers using a mixed solvent of acetic acid/water: Effects of solvent composition on the fiber diameter. Mater Lett 62(4–5):759–762
Hon DNS, Shiraishi N, NetLibrary I (2001) Wood and cellulosic chemistry. Marcel Dekker, New York
Hong KH, Park JL, Sul IH, Youk JH, Kang TJ (2006) Preparation of antimicrobial poly(vinyl alcohol) nanofibers containing silver nanoparticles. J Polym Sci B 44(17):2468–2474
Ifuku S, Tsuji M, Morimoto M, Saimoto H, Yano H (2009) Synthesis of silver nanoparticles templated by TEMPO-mediated oxidized bacterial cellulose nanofibers. Biomacromolecules 10(9):2714–2717
Khalil-Abad MS, Yazdanshenas ME, Nateghi MR (2009) Effect of cationization on adsorption of silver nanoparticles on cotton surfaces and its antibacterial activity. Cellulose 16(6):1147–1157
Kim CW, Frey MW, Marquez M, Joo YL (2005) Preparation of submicron-scale, electrospun cellulose fibers via direct dissolution. J Polym Sci B 43(13):1673–1683
Kim CW, Kim DS, Kang SY, Marquez M, Joo YL (2006) Structural studies of electrospun cellulose nanofibers. Polymer 47(14):5097–5107
Kinge S, Crego-Calama M, Reinhoudt DN (2008) Self-assembling nanoparticles at surfaces and interfaces. Chemphyschem 9(1):20–42
Lide DR (2000) CRC handbook of chemistry and physics, 2000–2001. CRC Press, Boca Raton
Liu HQ, Hsieh YL (2002) Ultrafine fibrous cellulose membranes from electrospinning of cellulose acetate. J Polym Sci B 40(18):2119–2129
Morones JR, Elechiguerra JL, Camacho A, Holt K, Kouri JB, Ramirez JT, Yacaman MJ (2005) The bactericidal effect of silver nanoparticles. Nanotechnology 16(10):2346–2353
Parikh DV, Sachinvala ND, Calamari TA, Negulescu I (2003) Carboxymethylated cotton for moist wound healing. AATCC Rev 3(6):15–19
Parikh DV, Fink T, Rajasekharan K, Sachinvala ND, Sawhney APS, Calamari TA, Parikh AD (2005) Antimicrobial silver/sodium carboxymethyl cotton dressings for burn wounds. Text Res J 75(2):134–138
Perelshtein I, Applerot G, Perkas N, Guibert G, Mikhailov S, Gedanken A (2008) Sonochemical coating of silver nanoparticles on textile fabrics (nylon, polyester and cotton) and their antibacterial activity. Nanotechnology 19(24):245705
Quan SL, Kang SG, Chin IJ (2010) Characterization of cellulose fibers electrospun using ionic liquid. Cellulose 17(2):223–230
Rai M, Yadav A, Gade A (2009) Silver nanoparticles as a new generation of antimicrobials. Biotechnol Adv 27(1):76–83
Sharma VK, Yngard RA, Lin Y (2009) Silver nanoparticles: green synthesis and their antimicrobial activities. Adv Colloid Interface Sci 145(1–2):83–96
Son WK, Youk JH, Lee TS, Park WH (2004a) Electrospinning of ultrafine cellulose acetate fibers: studies of a new solvent system and deacetylation of ultrafine cellulose acetate fibers. J Polym Sci B 42(1):5–11
Son WK, Youk JH, Lee TS, Park WH (2004b) Preparation of antimicrobial ultrafine cellulose acetate fibers with silver nanoparticles. Macromol Rapid Commun 25(18):1632–1637
Turkevich J, Stevenson PC, Hillier J (1951) A study of the nucleation and growth processes in the synthesis of colloidal gold. Discuss Faraday Soc 11:55–75
Vargantwar PH, Smith B, Hauser P (2007) Preparation of zwitterionic cotton fabrics and their wrinkle-resistant performance. AATCC Rev 7(12):42–46
Viswanathan G, Murugesan S, Pushparaj V, Nalamasu O, Ajayan PM, Linhardt RJ (2006) Preparation of biopolymer fibers by electrospinning from room temperature ionic liquids. Biomacromolecules 7(2):415–418
Xu XY, Yang QB, Wang YZ, Yu HJ, Chen XS, Jing XB (2006) Biodegradable electrospun poly(L-lactide) fibers containing antibacterial silver nanoparticles. Eur Polym J 42(9):2081–2087
Acknowledgments
This work was done in Cornell University and we acknowledge the US Department of Agriculture for partially funding this work under projects NRI-NCZ09462 and CRIS-Hatch NYC-329433. We would like to thank Mr. John Hunt, Malcolm Thomas and Yuanming Zhang (CCMR, Cornell University) for their assistance with FESEM, TEM imaging and EDX analysis. This work made use of the electron microscopy facility of the Cornell Center for Materials Research (CCMR) with support from the National Science Foundation Materials Research Science and Engineering Centers (MRSEC) program (DMR 0520404). Junlong Song is also grateful for the support of Talents Foundation of Nanjing Forestry University (163105003), Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20103204120005), and the Priority Academic Program Development of Jiangsu Higher Education Institutions.
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Song, J., Birbach, N.L. & Hinestroza, J.P. Deposition of silver nanoparticles on cellulosic fibers via stabilization of carboxymethyl groups. Cellulose 19, 411–424 (2012). https://doi.org/10.1007/s10570-011-9647-3
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DOI: https://doi.org/10.1007/s10570-011-9647-3