1‐Allyl‐3‐methylimidazolium halometallate ionic liquids as efficient catalysts for the glycolysis of poly(ethylene terephthalate)

Series of 1‐allyl‐3‐methylimidazolium halometallate ionic liquids (ILs) were synthesized and used to degrade poly(ethylene terephthalate) (PET) as catalysts in the solvent of ethylene glycol. One important feature of these new IL catalysts is that most of them, especially [amim][CoCl₃] and [amim][ZnCl₃], exhibit higher catalytic activity under mild reaction condition, compared to the traditional catalysts [e.g., Zn(Ac)₂], the conventional IL catalysts (e.g., [bmim]Cl), Fe‐containing magnetic IL catalysts (e.g., [bmim][FeCl₄]), and metallic acetate IL catalysts (e.g., [Deim][Zn(OAc)₃]). For example, using [amim][ZnCl₃] as catalyst, the conversion of PET and the selectivity of bis(hydroxyethyl) terephthalate (BHET) reach up to 100% and 80.1%, respectively, under atmospheric pressure at 175°C for only 1.25 h. Another important feature is that BHET can be easily separated from the catalyst and has a high purity. Finally, based on the experimental phenomena, in ‐situ infrared spectra, and experimental results, the possible mechanism of degradation with synthesized IL is proposed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Organic acids catalyzed polymerization of ε‐caprolactone: Synthesis and characterization

Environmentally friendly organocatalytic synthesis of aliphatic polyesters was studied. The catalysis investigated is novel, and lends itself well to the potential production of valuable biodegradable products. The reactions were based on an organic acids‐catalyzed ring‐opening polymerization of ε‐caprolactone with fatty acid derivatives as the initiator and were performed in the absence of solvents. The chemical structures of the functionalized polymers were confirmed by ¹H and ¹³C‐NMR spectra. Polymers with different molecular weights, in the range 10,900–15,200 were obtained in the presence of fumaric acid as catalyst. The thermal properties of the functionalized PCLs were determined by modulated differential scanning calorimetry and thermogravimetric analysis. The MDSC results verified that the crystallinity and the melting point of the lipid‐functionalized polymers were lower than that of the unfunctionalized poly(ε‐caprolactone). The hydrolytic degradation of the functionalized polymer was also investigated. The result shows the degradation rate was affected by the presence of oleic acid derivatives in the polymer molecule. The lipid‐functionalized polymers synthesized by the metal‐free polymerization systems seem to be suitable biodegradable polyesters for use in biomedical and pharmacological applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Microwave assisted glycolysis of poly(ethylene terephthalate) catalyzed by 1‐butyl‐3‐methylimidazolium bromide ionic liquid

The combination of ionic liquid (IL) associated with microwave energy may have some potential application in the chemical recycling of poly (ethylene terephthalate). In this processes, glycolysis of waste poly (ethylene terephthalate) recovered from bottled water containers were thermally depolymerized with solvent ethylene glycol (EG) in the presence of 1‐butyl‐3‐methyl imidazolium bromide ([bmim]Br) as catalyst (IL) under microwave condition. It was found that the glycolysis products consist of bis (2‐hydroxyethyl) terephthalate (BHET) monomer that separated from the catalyst IL in pure crystalline form. The conversion of PET reach up to 100% and the yield of BHET reached 64% (wt %). The optimum performance was achieved by the use of 1‐butyl‐3‐methyl imidazolium bromide as a catalyst, microwave irradiations temperature (170–175°C) and reaction time 1.75–2 h. The main glycolysis products were analyzed by ¹H NMR, ¹³C NMR, LC‐MS, FTIR, DSC, and TGA. When compared to conventional heating methods, microwave irradiation during glycolysis of PET resulted in short reaction time and more control over the temperature. This has allowed substantial saving in energy and processing cost. In addition, a more efficient, environmental‐friendly, and economically feasible chemical recycling of waste PET was achieved in a significantly reduced reaction time. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41666.     

Thermal and mechanical properties of poly(ε‐caprolactone) crosslinked with γ radiation in the presence of triallyl isocyanurate

Poly(?‐caprolactone) was crosslinked by γ radiation in the presence of triallyl isocyanurate. The influence of γ‐radiation crosslinking on the thermal and mechanical properties of poly(?‐caprolactone)/triallyl isocyanurate was investigated. Differential scanning calorimetry analyses showed differences between the first and second scans. Dynamic mechanical analysis showed an increase in the glass‐transition temperature as a result of the radiation crosslinking of poly(?‐caprolactone). Thermogravimetric analysis showed that γ‐radiation crosslinking slightly improved the thermal stability of poly(?‐caprolactone). The γ radiation also strongly influenced the mechanical properties. At room temperature, crosslinking by radiation did not have a significant influence on the Young's modulus and yield stress of poly(?‐caprolactone). However, the tensile strength at break and the elongation at break generally decreased with an increase in the crosslinking level. When the temperature was increased above the melting point, the tensile strength at break, elongation at break, and Young's modulus of poly(?‐caprolactone) were also reduced with an increase in the crosslinking level. The yield stress disappeared as a result of the disappearance of the crystallites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2676–2681, 2007     

Antimicrobial properties and thermal stability of polycarbonate modified with 1‐alkyl‐3‐methylimidazolium tetrafluoroborate ionic liquids

Four water immiscible ionic liquids (ILs): 1‐hexyl‐3‐methylimidazolium tetrafluoroborate, 1‐heptyl‐3‐methylimidazolium tetrafluoroborate, 1‐octyl‐3‐methylimidazolium tetrafluoroborate and 1‐dodecyl‐3‐methylimidazolium tetrafluoroborate have been synthesized. Polycarbonate (PC) films containing ILs were prepared by solvent casting from methylene chloride solutions. Scanning electron microscopy measurements showed the high homogeneity of PC/IL films with the IL content up to 4 wt %. The tendency to IL aggregation was observed for polymeric films with higher IL content (5%). PC/IL composites were found to have the reduced thermal decomposition temperature under both an air and a nitrogen atmosphere in comparison with the neat PC. The effect of IL content on the antimicrobial activity of PC films against Escherichia coli bacteria was studied. Pronounced antimicrobial efficacy was revealed for PC/IL films for all studied ILs starting from 3 wt % of IL. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40050.     

Self‐assembled micelles prepared from poly(ɛ‐caprolactone)–poly(ethylene glycol) and poly(ɛ‐caprolactone/glycolide)–poly(ethylene glycol) block copolymers for sustained drug delivery

A series of poly(?‐caprolactone)–poly(ethylene glycol) (PCL‐PEG) and poly(?‐caprolactone/glycolide)–poly(ethylene glycol) [P(CL/GA)‐PEG] diblock copolymers were prepared by ring‐opening polymerization of ?‐caprolactone or a mixture of ?‐caprolactone and glycolide using monomethoxy PEG (mPEG) as macroinitiator and Sn(Oct)₂ as catalyst. The resulting copolymers were characterized using ¹H‐NMR, gel permeation chromatography, differential scanning calorimetry, and wide‐angle X‐ray diffraction. Copolymer micelles were prepared using the nanoprecipitation method. The morphology of the micelles was spherical or worm‐like as revealed by transmission electron microscopy, depending on the copolymer composition and the length of the hydrophobic block. Introduction of the glycolide component, even in small amounts (CL/GA = 10), disrupted the chain structure and led to the formation of spherical micelles. Interestingly, the micelle size decreased with the encapsulation of paclitaxel. Micelles prepared from mPEG5000‐derived copolymers exhibited better drug loading properties and slower drug release than those from mPEG2000‐derived copolymers. Drug release was faster for copolymers with shorter PCL blocks than for those with longer PCL chains. The introduction of glycolide moieties enhanced drug release, but the overall release rate did not exceed 10% in 30 days. In contrast, drug release was enhanced in acidic media. Therefore, these bioresorbable micelles and especially P(CL/GA)‐PEG micelles with excellent stability, high drug loading content, and prolonged drug release could be promising for applications as drug carriers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45732.     

Morphological,thermal, and mechanical properties of poly(ε‐caprolactone)/poly(ε‐caprolactone)‐grafted‐cellulose nanocrystals mats produced by electrospinning

Electrospun nanocomposites of poly(ε‐caprolactone) (PCL) incorporated with PCL‐grafted cellulose nanocrystals (PCL‐g‐CNC) were produced. PCL chains were grafted from cellulose nanocrystals (CNC) surface by ring‐opening polymerization. Grafting was confirmed by infrared spectroscopy (FTIR) and thermogravimetric analyses (TGA). The resulting PCL‐g‐CNC were then incorporated into a PCL matrix at various loadings. Homogeneous nanofibers with average diameter decreasing with the addition of PCL‐g‐CNC were observed by scanning electron microscopy (SEM). PCL‐g‐CNC domains incorporated into the PCL matrix were visualized by transmission electron microscopy (TEM). Thermal and mechanical properties of the mats were analyzed by differential scanning calorimetry (DSC), TGA and dynamic mechanical analysis (DMA). The addition of PCL‐g‐CNC into the PCL matrix caused changes in the thermal behavior and crystallinity of the electrospun fibers. Significant improvements in Young's modulus and in strain at break with increasing PCL‐g‐CNC loadings were found. These results highlighted the great potential of cellulose nanocrystals as a reinforcement phase in electrospun PCL mats, which can be used as biomedical materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43445.     

Thermal,mechanical, and rheological properties of poly(ε‐caprolactone)/halloysite nanotube nanocomposites

Naturally available halloysite nanotubes (HNTs) with hollow nanotubular structures were used as reinforcement in poly(ε‐caprolactone) (PCL). The PCL/HNT nanocomposites were prepared by melt mixing the polymer with as‐received HNTs up to 10 wt % in an internal batch mixer. Transmission electron microscopy analysis indicated that the HNTs were dispersed uniformly on the nanoscale throughout the PCL matrix. Differential scanning calorimeter studies revealed that the PCL crystallinity was decreased in the nanocomposites, and the HNTs dispersed in the PCL matrix led to an increase in the non‐isothermal crystallization temperature of the PCL. Tensile and dynamic mechanical tests showed great enhancement in strength and stiffness at low HNT content, while still maintaining the ductility of the PCL. The glass transition temperature (T_g) of the pristine PCL was substantially increased with increase in filler loading, which indicates good reinforcing effect imparted by the addition of HNT. Melt rheological studies revealed that the nanocomposites exhibited strong shear thinning behavior, and a percolated network of HNT particles was formed. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and in vitro drug‐release behavior of 5‐fluorouracil‐loaded poly(hydroxybutyrate‐co‐hydroxyhexanoate) nanoparticles and microparticles

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) (PHBHHx) copolymeric microparticles (MPs) and nanoparticles (NPs) were prepared by the double‐emulsion solvent‐evaporation technique. 5‐Fluorouracil (5‐Fu), an anticancer drug, was entrapped in PHBHHx NPs and MPs. A variety of parameters, including the species and concentration of different surfactants, power and time of ultrasonication for particle dispersion, and organic/aqueous solution ratio, that affected the production of the 5‐Fu‐loaded PHBHHx NP and MP particles and the release of 5‐Fu were studied. The results show that the prepared NPs and MPs were spherical in shape and about 160 nm and 3 μm in size, respectively, when cetyltrimethyl ammonium bromide was used as the emulsifier. The drug‐loading content (DLC) varied from 3.53 to 8.03% for 5‐Fu‐loaded NPs and from 4.83 to 18.87% for 5‐Fu‐loaded MPs and depended on the different initial feeding amounts of 5‐Fu. The encapsulation efficiency decreased with increasing DLC. The in vitro drug‐release characteristics appeared to have two phases with an initial burst effect occurring within the first 8 h; this was more obvious for the particles with low DLCs. The NPs with high DLC (8.03%) had the slowest release rate, 49.6% of 5‐Fu within 24 h. Therefore, PHBHHx copolymeric NPs and MPs can possibly be applied as drug‐delivery carrier materials in the future. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and dielectric properties of poly(ε‐caprolactone) compounded with “bucky gels”‐like mixture

Poly(ε‐caprolactone) (PCL) was melt compounded with “Bucky gels”‐like mixture that prepared by grinding multiwalled carbon nanotubes (MWNTs) and ionic liquids (ILs). Raman spectrum showed the significant interaction between ILs and MWNTs. The dielectric behavior of PCL nanocomposites based on unmodified and IL‐modified MWNTs was studied from 40 Hz to 30 MHz. The addition of ILs significantly enhanced the dielectric property of PCL/IL/MWNT ternary nanocomposites, which was much higher than that of the sum of PCL/IL with PCL/MWNT binary nanocomposites. The dielectric properties of PCL/IL/MWNT nanocomposites were mainly influenced by ILs in low frequency and were dominated by MWNTs in high frequency. SEM results revealed that a more uniform and fine dispersion of MWNTs were achieved throughout the PCL matrix because of ILs. The addition of ILs in nanocomposites changed the crystallinity of PCL. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40231.     

Nanocomposites based on poly(ϵ‐caprolactone) and the montmorillonite treated with dibutylamine‐terminated ϵ‐caprolactone oligomer

Dibutylamine‐terminated ε‐caprolactone oligomers (CLOs: CLOL, CLOM, and CLOH) with number–averaged molecular weight (M_n), 500, 1300, and 2200, respectively, were synthesized by the ring‐opening polymerization of ε‐caprolactone initiated by 2‐(dibutylamino)ethanol in the presence of tin(II) 2‐ethylhexanoate. Nanocomposites based on poly(ε‐caploractone) (PCL) and the caprolactone oligomer‐treated montmorillonites (CLO‐Ms: CLOL‐M, CLOM‐M, and CLOH‐M) were prepared by melt intercalation method. The XRD and TEM analyses of the PCL composites revealed that the extent of exfoliation of the clay platelets increased with increasing molecular weight of the used CLOs. Tensile strength and modulus of the PCL/CLO‐M composites increased with increasing molecular weight of the CLO and increasing inorganic content. The tensile modulus of the PCL/CLOH‐M nanocomposite with inorganic content 5.0 wt % was three times higher than that of control PCL. Among the PCL/CLO‐M composites, the PCL/CLOM‐M composite had the highest crystallization temperature and melting temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Fabrication and drug release properties of poly(5‐benzyloxy‐trimethylene‐co‐glycolide) microspheres

Poly(5‐benzyloxy‐trimethylene carbonate‐co‐glycolide) random copolymers were synthesized through the ring‐opening polymerization of 5‐benzyloxy‐trimethylene carbonate and glycolide (GA). The copolymers with different compositions, PBG‐1 with 17% GA units and PBG‐2 with 45% GA units, were obtained. Using these copolymers, microsphere drug delivery systems with submicron sizes were fabricated using an “ultrasonic assisted precipitation method.” The in‐vitro drug release from these microspheres was investigated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and performance evaluation of tetracycline hydrochloride loaded wound dressing mats based on electrospun nanofibrous poly(lactic acid)/poly(ϵ‐caprolactone) blends

In this article, we present the drug‐release rate, water uptake, water permeability, morphology, and mechanical properties of a series of active wound dressing nanofibrous mats prepared via an electrospinning process of poly(lactic acid) (PLA), poly(?‐caprolactone) (PCL), and their (50/50) blends loaded with different doses of tetracycline hydrochloride antibiotic. The performance of these active wound dressings in terms of a sustained and suitable drug‐release rate, adequate water uptake and water permeability, and antibacterial activities were compared with those of a commercial wound dressing (Comfeel Plus). The results show that the dressings made from PCL and PLA/PCL blends showed better performance compared with the commercial wound dressing sample as far as these properties were concerned. The improved performance could be explained on the basis of the nanofibrous structure of the mats and the hydrophilicity of PCL and PLA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Evaluation of 1‐ethyl‐3‐methylimidazolium acetate based ionic liquid systems as a suitable solvent for collagen

Collagen, a prominent biopolymer, which is famous for its excellent biological activity, has been used extensively for tissue engineering applications. In this study, a novel solvent system for collagen was developed with an ionic liquid, 1‐ethyl‐3‐methylimidazolium acetate ([EMIM][Ac]), solvent system. A series of sodium salts were introduced into this solvent system to enhance collagen's dissolution procedure. The results show that the solubility of collagen was significantly influenced by the temperature and sodium salts. The solubility reached up to approximately 11% in the [EMIM][Ac]/Na₂HPO₄ system at 45°C. However, the structure of the regenerated collagen (Col‐regenerated) may have been damaged. Hence, we focused on the structural integrity of the collagen regenerated from the [EMIM][Ac] solvent system by the methods of sodium dodecyl sulfate–polyacrylamide gel electrophoresis, Fourier transform infrared spectroscopy, ultrasensitive differential scanning calorimetry, atomic force microscopy, X‐ray diffraction, and circular dichroism because its signature biological and physicochemical properties were based on its structural integrity. Meanwhile, a possible dissolution mechanism was proposed. The results show that the triple‐helical structure of collagen regenerated from the [EMIM][Ac] solvent system below 35°C was retained to a large extent. The biocompatibility of Col‐regenerated was first characterized with a fibroblast adhesion and proliferation model. It showed that the Col‐regenerated had almost the same good biological activity as nature collagen, and this indicated the potential application of [EMIM][Ac] in tissue engineering. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2245–2256, 2013     

Spray‐drying microencapsulation of β‐carotene by soy protein isolate and/or OSA‐modified starch

Microencapsulation is an effective strategy to improve the storage stability of β‐carotene. This article investigated the potential and effectiveness of soy protein isolate (SPI) and octenylsuccinic anhydride‐modified starch (MS), alone or in combination (1:1, w/w), to encapsulate β‐carotene by spray drying. The results indicated that the microcapsule with MS exhibited much lower encapsulation efficiency (NE) and poorer dissolution behavior, but much better redispersion behavior, than that with SPI or its blends with MS. The NE was basically unaffected by total solid content (TC) or core/wall ratio; increasing the TC impaired the dissolution and/or redispersion behavior. The dispersion behavior was closely associated with the morphology of the microcapsules. The encapsulated β‐carotene suffered a progressive loss upon storage under high humid or temperature environment, but it exhibited extraordinary stability at low temperatures (e.g., 4°C). The β‐carotene degradation was independent of sunlight. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40399.     

Efficient wound odor removal by β‐cyclodextrin functionalized poly (ε‐caprolactone) nanofibers

Polymer‐cyclodextrin (CD) composite nanofibers, by virtue of the hollow cavities and abundant hydroxyl groups present in CDs, have tremendous potential in a variety of biomedical applications. However, in most cases, especially in aliphatic polyesters, polymer chains thread readily into CD cavities, therefore its potential has not yet been fully realized. Herein, we report the formation of poly(ε‐caprolactone) (PCL)/β‐CD functional nanofibers by electrospinning their mixture from chloroform/N,N‐dimethylformamide (60 : 40). The fiber diameters of the neat PCL and β‐CD functionalized fibers were measured from the images obtained from a scanning electron microscope and were found to be about 500 nm. The efficiency of wound odor absorbance by these composite fibers was studied using a simulated wound odor solution, consisting of butyric and propionic acids in ethanol. Immersion tests indicated that even under less than ideal test conditions, the nanofibers containing β‐CDs were very efficient in masking the odor. The odor masking capability of the β‐CD functionalized PCL nanofibers were further confirmed by thermogravimetric analyses and GC observations, with the former method showing unique degradation patterns. The PCL/β‐CD nanocomposites, by virtue of having their β‐CD cavities free and unthreaded by PCL, could potentially be an ideal substrate for removing wound odors through formation of inclusion compounds with odorants, while providing an ideal environment for the wound to heal. These results suggest tailoring polymer‐CD nanostructures for specific applications in wound odor absorbance, surface grafting of chemical moieties, and vehicles for drug delivery, as examples. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42782.     

Synthesis,self‐assembly,and drug release behavior of star‐shaped poly(ε‐caprolactone)‐b‐poly(ethylene oxide) block copolymer with porphyrin core

A serial of star‐shaped poly(ε‐caprolactone)‐b‐poly(ethylene oxide) (SPPCL‐b‐PEO) block copolymers with porphyrin core were successfully synthesized from ring‐opening polymerization (ROP) of ε‐caprolactone (CL) initiated with porphyrin core, followed by coupling reaction with a hydrophilic polymer poly(ethylene oxide) (PEO) shell. The structure of this novel copolymer were synthesized and thoroughly characterized by Nuclear Magnetic Resonance (NMR), Gel Permeation Chromatography (GPC), Fourier Transform Infrared Spectroscopy (FTIR). Notably, the as‐prepared porphyrin‐cored star‐shaped copolymer could self‐assembly into different structures determined by transmission electron microscopy (TEM) and dynamic lighting scattering (DLS), which provides the great potential of using this well‐defined photodynamic therapy material for drug delivery system. Particularly, the doxorubicin‐loaded SPPCL‐b‐PEO nanosphere exhibits property of pH‐induced drug release. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40996.     

Fabrication of co‐continuous poly(ε‐caprolactone)/polyglycolide blend scaffolds for tissue engineering

The apparent inability of a single biomaterial to meet all the requirements for tissue engineering scaffolds has led to continual research in novel engineered biomaterials. One method to provide new materials and fine‐tune their properties is via mixing materials. In this study, a biodegradable powder blend of poly(ε‐caprolactone) (PCL), polyglycolide (PGA), and poly(ethylene oxide) (PEO) was prepared and three‐dimensional interconnected porous PCL/PGA scaffolds were fabricated by combining cryomilling and compression molding/polymer leaching techniques. The resultant porous scaffolds exhibited co‐continuous morphologies with ～50% porosity. Mean pore sizes of 24 and 56 μm were achieved by varying milling time. The scaffolds displayed high mechanical properties and water uptake, in addition to a remarkably fast degradation rate. The results demonstrate the potential of this fabrication approach to obtain PCL/PGA blend scaffolds with interconnected porosity. In general, these results provide significant insight into an approach that will lead to the development of new composites and blends in scaffold manufacturing. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42471.     

Application of the dry‐spinning method to produce poly(ε‐caprolactone) fibers containing bovine serum albumin laden gelatin nanoparticles

We designed and manufactured a polymeric system with combined hydrophilic–hydrophobic properties by loading gelatin nanoparticles (GNPs) containing bovine serum albumin (BSA) into poly(ε‐caprolactone) (PCL) fibers. Our ultimate goal was to create a device capable of carrying and releasing protein drugs. Such a system could find several biomedical applications, such as those in controlled release systems, surgical sutures, and bioactive scaffolds for tissue engineering. A two‐step desolvation method was used to produce GNPs, whereas PCL fibers were produced by a dry‐spinning method. The morphological, mechanical, and thermal properties of the produced system were investigated, and the distribution of nanoparticles both inside and on the surface of the fibers was examined. The effect of the particles on the biodegradability of the fibers was also evaluated. In vitro preliminary tests were performed to study the release of BSA from nanoparticle‐laden fibers and to compare this with its release from free nanoparticles. Our results indicate that the distribution of particles inside the fibers was quite homogeneous and only a few of them were present on the surface. The presence of the particles in the fibers did not affect the thermal properties of the PCL polymer matrix, although it created voids that affected the degradation characteristics so the PCL fibers favored faster erosion compared to the plain fibers. Preliminary results indicate that the release from GNP‐laden fibers occurred much more slowly compared to that in the free GNPs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44233.