Polycaprolactone and polycaprolactone/chitosan nanofibres functionalised with the pH-sensitive dye Nitrazine Yellow.

Nanofibres functionalised with pH-sensitive dyes could greatly contribute to the development of stimuli-responsive materials. However, the application of biocompatible polymers is vital to allow for their use in (bio)medical applications. Therefore, this paper focuses on the development and characterisation of pH-sensitive polycaprolactone (PCL) nanofibrous structures and PCL/chitosan nanofibrous blends with 20% chitosan. Electrospinning with added Nitrazine Yellow molecules proved to be an excellent method resulting in pH-responsive non-wovens. Unlike the slow and broad response of PCL nanofibres (time lag of more than 3h), the use of blends with chitosan led to an increased sensitivity and significantly reduced response time (time lag of 5 min). These important effects are attributed to the increased hydrophilic nature of the nanofibres containing chitosan. Computational calculations indicated stronger interactions, mainly based on electrostatic interactions, of the dye with chitosan (ΔG of -132.3 kJ/mol) compared to the long-range interactions with PCL (ΔG of -35.6 kJ/mol), thus underpinning our experimental observations. In conclusion, because of the unique characteristics of chitosan, the use of PCL/chitosan blends in pH-sensitive biocompatible nanofibrous sensors is crucial.

[1]  Tim L Dawson,et al.  Progress towards a greener textile industry , 2012 .

[2]  S. Hudson,et al.  Effect of the addition of a fugitive salt on electrospinnability of poly(ɛ-caprolactone) , 2009 .

[3]  M. El-Newehy,et al.  Preparation and characterizations of anisotropic chitosan nanofibers via electrospinning , 2011 .

[4]  K. D. Clerck,et al.  Polycaprolactone/chitosan blend nanofibres electrospun from an acetic acid/formic acid solvent system , 2012 .

[5]  C. Sangwichien,et al.  Density functional theory predictions of adsorption isotherms with hysteresis loops , 2002 .

[6]  R. Sanderson,et al.  Reversibly thermochromic micro-fibres by coaxial electrospinning , 2010 .

[7]  Miqin Zhang,et al.  Fabrication and cellular compatibility of aligned chitosan–PCL fibers for nerve tissue regeneration , 2011 .

[8]  R. Muzzarelli 10.06 – Nanochitins and Nanochitosans, Paving the Way to Eco-Friendly and Energy-Saving Exploitation of Marine Resources , 2012 .

[9]  Younan Xia,et al.  Electrospinning of Nanofibers: Reinventing the Wheel? , 2004 .

[10]  Robert Michael Christie,et al.  Textile applications of photochromic dyes. Part 1: establishment of a methodology for evaluation of photochromic textiles using traditional colour measurement instrumentation , 2010 .

[11]  Karen De Clerck,et al.  The development of polyamide 6.6 nanofibres with a pH-sensitive function by electrospinning , 2010 .

[12]  K. D. Clerck,et al.  An alternative solvent system for the steady state electrospinning of polycaprolactone , 2011 .

[13]  L. Xiaoqiang,et al.  Cellulose acetate nanofibers with photochromic property: Fabrication and characterization , 2010 .

[14]  Ivana Murković Steinberg,et al.  ORGANICALLY MODIFIED SILICATE THIN FILMS DOPED WITH COLOURIMETRIC PH INDICATORS METHYL RED AND BROMOCRESOL GREEN AS PH RESPONSIVE SOL–GEL HYBRID MATERIALS , 2010 .

[15]  V. V. Speybroeck,et al.  The influence of a polyamide matrix on the halochromic behaviour of the pH-sensitive azo dye Nitrazine Yellow , 2012 .

[16]  P. Westbroek,et al.  Electrospinning of chitosan nanofibrous structures: feasibility study , 2007 .

[17]  Jerzy Leszczynski,et al.  To stack or not to stack: Performance of a new density functional for the uracil and thymine dimers , 2008 .

[18]  R. Muzzarelli Biomedical Exploitation of Chitin and Chitosan via Mechano-Chemical Disassembly, Electrospinning, Dissolution in Imidazolium Ionic Liquids, and Supercritical Drying , 2011, Marine drugs.

[19]  K. D. Clerck,et al.  The Use of pH-indicator Dyes for pH-sensitive Textile Materials , 2010 .

[20]  Kadriye Ertekin,et al.  Photophysical and photochemical characteristics of an azlactone dye in sol-gel matrix; a new fluorescent pH indicator , 2003 .

[21]  D. Truhlar,et al.  The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals , 2008 .

[22]  Hongjun Wang,et al.  Acceleration of osteogenic differentiation of preosteoblastic cells by chitosan containing nanofibrous scaffolds. , 2009, Biomacromolecules.

[23]  H. Mattila Intelligent textiles and clothing , 2006 .

[24]  Andreas Greiner,et al.  Electrospinning: a fascinating method for the preparation of ultrathin fibers. , 2007, Angewandte Chemie.

[25]  L. Hermosilla,et al.  Competitive reactions of organophosphorus radicals on coke surfaces. , 2011, Chemistry.

[26]  N. de Kimpe,et al.  Intramolecular pi-pi stacking interactions in 2-substituted N,N-dibenzylaziridinium ions and their regioselectivity in nucleophilic ring-opening reactions. , 2010, The Journal of organic chemistry.

[27]  Richard G. Ellenbogen,et al.  Natural‐Synthetic Polyblend Nanofibers for Biomedical Applications , 2009 .

[28]  D. Gust,et al.  Preparation of photochromic poly(vinylidene fluoride-co-hexafluoropropylene) fibers by electrospinning , 2009 .

[29]  K. De Clerck,et al.  Investigating the halochromic properties of azo dyes in an aqueous environment by using a combined experimental and theoretical approach. , 2012, Chemistry.

[30]  R. A. Jishi,et al.  Density functional studies of Cu 2+ and Ni 2+ binding to chitosan , 2000 .

[31]  R. Muzzarelli Chitins and chitosans for the repair of wounded skin, nerve, cartilage and bone , 2009 .

[32]  M. C. Stuart,et al.  Emerging applications of stimuli-responsive polymer materials. , 2010, Nature materials.

[33]  John F. Kennedy,et al.  Carbohydrate polymers as wound management aids , 1997 .

[34]  K. D. Clerck,et al.  Coloration and application of pH‐sensitive dyes on textile materials , 2012 .

[35]  Seeram Ramakrishna,et al.  Electrospun biocomposite nanofibrous scaffolds for neural tissue engineering. , 2008, Tissue engineering. Part A.

[36]  S. Nair,et al.  Single step electrospinning of chitosan/poly(caprolactone) nanofibers using formic acid/acetone solvent mixture , 2010 .

[37]  Geunhyung Kim,et al.  Fabrication of electrospun polycaprolactone biocomposites reinforced with chitosan for the proliferation of mesenchymal stem cells , 2011 .

[38]  M. García-Heras,et al.  Optical behaviour of pH detectors based on sol–gel technology , 2005 .

[39]  O. Kwon,et al.  Electrospinning of chitosan dissolved in concentrated acetic acid solution. , 2005, Biomaterials.

[40]  L. Wadsö,et al.  On application of an isothermal sorption microcalorimeter , 2001 .

[41]  Yanlin Song,et al.  Thermochromic core–shell nanofibers fabricated by melt coaxial electrospinning , 2009 .