APPLICATION OF NANOFIBRES Nanotechnology, which refers to creation of technology at a nano-scale by manipulating matter, is providing new solutions and opportunities

to ensure sustainable energy and environments for the future. This technology has tremendously impacted many different science and engineering disciplines, such as electronics, materials science, and polymer engineeringand both, research and applications are equally diverse, ranging from extensions of conventional methodology to completely new approaches based upon molecular self-assembly. Nanofibres, are now becoming attractive to solve numerous energy and environmental issues. Produced by electrospinning, which is a simple and low cost technique. In addition, electrospinning allows the production of nanobers from various materials e.g. organics and inorganics in different congurations and assemblies. What are Nanofibres? Nanofibers, while referring to both textile and fibre science applications, are highly engineered fibers with diameters between 100 nm and 500 nm (1 nm = 10-9 m). In comparison meltblown or spunbond micro fibers range in the area of 0.9 to several micrometers and e.g. merino wool fibers range around 12-24 micrometers. A human hair has a diameter around 80 micrometers and is about 200 times bigger in diameter than an average nanofiber. Nanofibers are an exciting new class of material used for several value added applications such as medical, filtration, barrier, wipes, personal care, composite, garments, insulation, and energy storage.

HOW ARE NANOFIBRES MADE? NANOFIBERS FROM SPLITTING BICOMPONENT FIBERS

Figure 2. Nanofibers from Bicomponent fibers [3].

!"#$%&'($&)%"*+,&(-#'(.'#/,)*"0("1"#-*2&'3(*3(3.*""*"0(2*4)#5.#"&"$(-*2&'36(
spinning bicomponent fibers that split or dissolve
Most often, bicomponent fibres used are Islands-In-The-Sea fibers and segmented pie structures.in 1-3 denier filaments with from 240 to possibly as much as 1120 filaments surrounded by dissolvable polymer. Bicomponent fibers are split with the

help of the high forces of air or water jets.

Unlike electrospinning and melt spinning, the nanofibers produced with this technique had a very narrow diameter range.

USING ELECTROSPINNING: 78&)$'#3.*""*"0(*3(1(,"*+,&(1..'#1)%(,3*"0(&8&)$'#3$1$*)(-#')&3($#(.'#/,)&(-*"&(-*2&'3(1"/(*3($%&'&-#'&( &5.8#9&/(-#'(3.*""*"0("1"#-*2'&36(This method has been known since 1934 when the first patent on electrospinning was filed. :%&(1/;1"$10&3(#-($%&(&8&)$'#3.*""*"0(.'#)&33(1'&(*$3($&)%"*)18(3*5.8*)*$9(1"/( *$3(&139(1/1.$12*8*$96(:%&(1..1'1$,3(,3&/(-#'(&8&)$'#3.*""*"0(*3(3*5.8&(*"()#"3$',)$*#"6 :%&(&8&)$'#3.*""*"0(.'#)&33(,3&3(1(%*0%(;#8$10& (>50kv) electric field to produce electrically charged jets from polymer solution or melts, which on drying by means of evaporation of the solvent produce nanofibers. The highly charged fibers are field directed towards the oppositively charged collector, which can be a flat surface or a rotating drum, to collect the fibers. In normal conventional spinning techniques, the fiber is subjected to a group of tensile, gravitational, aerodynamic, rheological, and inertial forces.3 In electrospinning, the spinning of fibers is achieved primarily by the tensile forces created in the axial direction of the flow of the polymer by the induced charges in the presence of an electric field.
The production of nanofibers by the electrospinning process is influenced both by the electrostatic forces and the viscoelastic behavior of the polymer. Process parameters, like solution feed rate, applied voltage, nozzle-collector distance, and spinning environment, and material properties, like solution concentration, viscosity, surface tension, conductivity, and solvent vapor pressure, influence the structure and properties of electrospun nanofibers. The production rate of this process is

measured in grams per hour. Therefore, unless the production rate of this technique can be increased by several orders of magnitude, the cost of nanofibers production will continue to relegate them to mostly a laboratory curiosity.

In the electrospinning process, fibers ranging from 50 nm to 1000 nm or greater (Reneker and Chun 1996; Shin et al 2001a; Fridrikh et al 2003) can be produced by applying an electric potential to a polymeric solution (Hohman et al 2001a, 2001b) (see Figure 1a). The solution is held at the tip of a capillary tube by virtue of its surface tension. The electrical potential applied provides a charge to the polymer solution. Mutual charge repulsion in the polymer solution induces a force that is directly opposite to the surface tension of the polymer solution. An increase in the electrical potential initially leads to the elongation of the hemispherical surface of the solution at the tip of the capillary tube to form a conical shape known as the Taylor cone (Doshi and Reneker 1995; Yarin et al 2001). A further increase causes the electric potential to

reach a critical value, at which it overcomes the surface tension forces to cause the formation of a jet that is ejected from the tip of the Taylor cone. The charged jet undergoes instabilities and gradually thins in air primarily due to elongation and solvent evaporation (Zeleny 1914; Reneker et al 2000; Shin et al 2001a, 2001b; Frenot et al 2003). The charged jet eventually forms randomly oriented nanofibers that can be collected on a stationary or rotating grounded metallic collector (Doshi and Reneker 1995; Kameoka and Craighead 2003) (see Figure 1b).

The most often used fibers in this technique are nylon, polystyrene, polyacrylonitrile, polycarbonate, PEO, PET and water-soluble polymers. The polymer ratio is generally 80% islands and 20% sea. The resulting nanofibers after dissolving the sea polymer component have a diameter of approximately 300 nm. Compared to electrospinning, nanofibers produced with this technique will have a very narrow diameter range but are coarser.

PROPERTIES OF NANOFIBERS Nanofibers exhibit special properties mainly due to extremely high surface to weight ratio compared to conventional nonwovens. Lower density, high pore volume and tight pore size are commonly seen 1.Physical Properties: 1. Low Density 2. High Pore Volume 3.Tight Pore Size MECHANICAL PROPERTIES High Surface Area As the fiber diameter shrinks into the nanoscale, the surface area to volume ratio increases up to 1,000 times higher than a microfiber. This property generally tends to bestow the mat of thousands of fibers with enhanced properties over one fiber in the form of:

Chemical Delivery Catalysis Electron & Photon Transfer

Slip Flow

Tensile Strength Tensile strength has been shown to increase by up to 40% over the same weight of material in a bulk or larger format.

Reduced Crack Propagation Achieving the same level of strength with less amount of material is enhanced by the fact that the probability of the failure of one fiber is much higher than the failure of thousands of fibers. Furthermore, upon the development of a structural flaw or crack, it is impossible to propagate to other discrete structural components. Thermal Properties Thermal conductivity testing has shown that decreasing fiber diameter into the nanoscale increases thermal resistance of popular insulative materials by almost 50%. Electrical Properties Many materials when processed into nanofiber dramatically improve electron transfer. Combined with the extremely thin nature of a nanofiber web, these properties have substantial benefits in energy storage, photocatalytics and sensors.

Applications of nanofibers Nanomaterials have been attracting the attention of global materials research these days primarily due to their enhanced properties required for various application in specific areas like catalysis, filtration, NEMS, nanocomposites, nanofibrous structures, tissue scaffolds, drug delivery systems, protective textiles, storage cells for hydrogen fuel cells amongst others. Carbon and graphitic nanofibers Carbon nanofibers are finding enormous applications in unconventional energy sources and storage cells due to their enhanced conductivity and high aspect ratio. Their mechanical properties enable them to be used as fillers in composites that find applications in synthetic and rubber industries.61 Carbon nanofiber reinforced composites offer increased stiffness, high strength and low electrical resistivity. Also, aligned nanofiber composites provide enhanced mechanical properties than the randomly aligned nanofiber composite structure.62 Ma et al. studied the morphology and mechanical properties of polyethylene terphthalate (PET) resins compounded with carbon nanofibers (CNF).63 The compressive and torsional properties of the composites increased up to 50% compared to the normal PET fiber, while its tensile modulus showed only moderate improvement.63 Tissue scaffolds and drug delivery Nanofibers with high surface area and porosity have enormous scope for applications in engineering mechanically stable and biologically functional tissue scaffolds. The tissue scaffolding material must be selected carefully to ensure its biocompatibility with the body cells. The biocompatibility depends on the surface chemistry of the scaffolds, which is influenced by the material properties. The high surface to volume ratio of the nanofiber provides more room for the cell attachment than the regular fibers Poly (D, L-

lactide-co-glycolide) (PLGA), the commonly used biodegradable polymer in tissue engineering while electrospinning, produced highly suitable tissue scaffolds that have high porosity, pore diameter, and pore volume. The high porosity of the electrospun nanofiber scaffolds provides enough space for the cell accommodation and an easy passage for the nutrient intake and metabolic waste exchange. Mechanical properties like the modulus of elasticity and strain at failure are important for the application of electrospun nanofibers as tissue scaffolds. The material properties can be suitably tailored by varying the fiber orientation and solution concentration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hitosan is another natural biomaterial that has been used to make nanofibers (Geng et al 2005). Nonwoven or aligned chitosan/PEO (90:10) nanofibers have been developed using the electrospinning technique. These nanofibers possessed structural integrity in water and their cell studies demonstrated enhanced attachment of human osteoblasts and chondrocytes onto the nanofibers. In addition, the cells maintained their characteristic morphology and viability on these nanofibers, thereby indicating good cytocompatibility (Bhattarai et al 2005). Hence, chitosan nanofibers could be a good candidate material for scaffolds in tissue engineering. Silk fibroin is another potential natural biomaterial for nanofibrous scaffolds (Jin et al 2002). Min et al (2004) have reported the in vitro cytocompatibility of silk nanofibers with keratinocytes and fibroblasts. The cytocompatibility, fiber diameter, and high porosity together make it a suitable candidate material for scaffolding technology.

DRUG DELIVERY Nanofiber mats due to their high functional characteristics find application as drug carriers for the drug delivery system. Controlled delivery of drugs at a defined rate over a definite period of treatment is possible with biocompatible delivery matrices of either biodegradable or nonbiodegradable polymers. Kenawy et al. investigated the drug delivery potential of electrospun polymers by spinning poly (ethylene-co-vinyl acetate) (PEVA) and poly lactic acid with ethanol and tetracycline hydrochloride as the model drug.51 The release of

tetracycline from the electrospun mats was found much greater than from the cast films. They observed that the electrospun PEVA and 50/50 PLA/PEVA mats gave very smooth release of tetracycline over a period of five days.51 These observations stress the importance and application of electrospun fiber mats in controlled drug delivery systems and other biomedical applications. Controlled delivery systems are used to improve the therapeutic efficacy and safety of drugs by delivering them to the site of action at a rate dictated by the need of the physiological environment. A wide variety of polymeric materials have been used as delivery matrices, and the choice of the delivery vehicle polymer is determined by the requirements of the specific application (Heller and Hoffman 2004). Polymeric nanofibers have recently been explored for their ability to encapsulate and deliver bioactive molecules for therapeutic applications. Kenawy et al (2002) studied PEVA, PLA, and their 50:50 blend-based electrospun nanofibrous scaffolds for the delivery of tetracycline hydrochloride in periodontal applications. Their results demonstrated that the initial rate of release of tetracycline hydrochloride from the scaffold is high during the first 1012 hours, most likely due to release of drug sequestered on the nanofiber surface. Electrospun PEVA showed a higher release rate when compared with the electrospun nanofiber meshes of pure PLA or 50/50 PLA/PEVA. Electrospun PEVA released 65% of its drug content within 120 hours, whereas a 50/50 blend of PLA and PEVA gave about 50% release of tetracycline hydrochloride for the same duration. These results indicated that the rate of release of tetracycline hydrochloride can be controlled by modulating the ratio of PLA and PEVA in the polymeric blend. Therefore, the nanofibrous delivery system showed potential to be employed in the treatment of periodontal diseases. In another study, Verreck et al (2003b) have demonstrated the use of (nonbiodegradable polymer scaffolds) PU nanofibrous scaffolds produced by electro-spinning for the delivery of water-insoluble drugs such as intraconazole and ketanserin. In their study, the authors obtained an amorphous nanodispersion of the waterinsoluble drug on the nanofibrous scaffold. The large surface area of the nanofibrous scaffold allowed fast and efficient solvent evaporation that gave limited time for crystallization of incorporated drug, and favored the formation of an amorphous dispersion (Verreck et al 2003a). These studies demonstrated that the release of poorly water-soluble drugs from water-insoluble polymers is possible and that the rate of release can be tailored by altering the concentration of the polymer. Another study by Kim et al (2003, 2004) demonstrated the potential use of PLGA nanofibrous scaffolds for controlled release of hydrophilic antibiotics. The authors incorporated Mefoxin (cefotoxin sodium) into PLGA nanofibers during the process of electrospinning. Inhibited growth of Staphylococcus aureusindicated that the bioactivity and structure of the antibiotic drug is not affected by the process of electrospinning. The above studies elucidate that nanofibrous scaffolds are suitable carriers for both hydrophilic and hydrophobic drugs, and that the drug release rate can be tailored by modulation of the nanofibrous scaffolds morphology, porosity, and composition.

Synthetic polymeric materials for nanofibers Synthetic polymers represent the largest class of bio-materials (Peter et al 1998; Cooper et al 2004). A wide variety of synthetic polymers has been used to form nanofibers. These include PLA (Tu et al 2003;Yang et al 2004); poly(ethylene terephthalate) (PET) (Ma et al 2005b) for blood vessel tissue engineering; PCL (Li et al 2005c) in neural and cartilage tissue engineering; and several copolymeric compounds such as PLLA-CL as a biomimetic ECM for smooth muscle and endothelial cells (Mo et al 2004; Mo and Weber 2004); PLGA (Katti et al 2004; Uematsu et al 2005), one of the most commonly used polymers to fabricate nanofibers for bone and cartilage tissue engineering and controlled drug delivery; PEVA (Kenawy et al 2002) nanofibers for controlled drug delivery; and PLGA-poly(ethylene glycol) (PLGA-PEG) block copolymeric nanofibrous scaffolds produced via electro-spinning as a matrix for DNA delivery (Luu et al 2003). Recently, carbon and alumina nanofibers have been explored as biomaterials for applications in dental and orthopedic implants (Elias et al 2002; Price et al 2003a;Price et al 2003b; Webster et al 2005). Therefore, a large variety of synthetic polymers has been explored for nanofiber synthesis primarily because of the electrospinning technique that easily lends itself to synthetic polymer usage. Go to: Applications of nanofibers in tissue engineering A variety of methods has been reported previously for the fabrication of scaffolds to be used in tissue engineering (Atala and Lanza 2002). However, in the past decade, nanofibrous systems have been developed and explored as potential scaffolds for tissue engineering (Ma and Zhang 1999; Li et al 2002;Smith and Ma 2004; Ma et al 2005a). By virtue of their high surface area and porosity, they have the potential to provide enhanced cell adhesion and by virtue of the similarity of their 3D architecture to natural ECM, they provide an excellent micro/nano environment for cells to grow and perform their regular functions (Doshi and Reneker 1995; Stupp et al 1997; Zhang and Ma 2000). Therefore, nanofibrous systems have been strongly pursued as scaffolds for tissue engineering applications. Go to: Nanofibers for musculoskeletal tissue engineering Many materials (natural and synthetic) have been explored as nanofibrous scaffolding materials for bone, cartilage, ligament, and skeletal muscle tissue engineering, including HA (Ramay and Zhang 2003), chitosan (Bhattarai et al 2005), PLGA (Uematsu et al 2005), carbon (Price et al 2003b) and aluminum nanofibers (Webster et al 2005). Although nanofibers have been studied as scaffolds for multiple tissue types, musculoskeletal tissue is probably the most well studied. Nanofibers for bone tissue engineering The design of scaffolds for bone tissue engineering is based on the physical properties of bone tissue such as mechanical strength, pore size, porosity, hardness, and overall 3D architecture. For bone tissue engineering, scaffolds with a pore size in the range of 100350 !m and porosity greater than 90% are preferred for better cell/tissue in-growth and hence enhanced bone regeneration (Bruder and Caplan 2000; Hutmacher 2000). Yoshimoto et al (2003) developed nonwoven PCL scaffolds by electrospinning for the purpose of bone tissue engineering. To understand the influence of mesenchymal stem cells (MSCs) on nanofibers, MSCs

derived from bone marrow of neonatal rats were seeded on the nanofibrous scaffold. The results indicated that the MSCs migrated inside the scaffold and produced abundant extracellular matrix in the scaffold. In continuation to this study, Shin et al tested the PCL nanofibers along with MSCs in vivo in a rat model. Their results demonstrated ECM formation throughout the scaffold along with mineralization and type I collagen synthesis (Shin et al 2004). These studies demonstrated that PCL-based nanofibrous scaffolds are potential candidates for bone tissue engineering. In another study, Ramay et al used HA with "-tricalcium phosphate ("-TCP) to develop biodegradable nanocomposite porous scaffolds (Ramay and Zhang 2004). "-TCP/HA scaffolds built from HA nanofibers with "-TCP as a matrix were used to fabricate porous scaffolds by a technique that integrated the gel casting technique with the polymer sponge method (Ramay and Zhang 2003). Their in vitro results demonstrated that incorporation of HA nanofibers as a second component in "-TCP significantly increased the mechanical strength of the porous composite scaffolds. This study introduced nano-composites with HA nanofibers as a promising scaffolding system for load bearing applications such as bone tissue engineering. Nanofibers for cartilage tissue engineering Articular cartilage tissue has a limited capacity for repair due to the reduced availability of chondrocytes and complete absence of progenitor cells in the vicinity of the wound to mediate the repair process. The chondrocytes available for repair are embedded in the dense extracellular matrix of the articular surface which restricts their mobility and hence limits their contribution to the wound healing process (McPherson and Tubo 2000). In addition, articular cartilage is an avascular tissue which further limits its capacity to selfregenerate. To provide a solution to this problem, multiple surgical techniques have been developed, but with limited success (Colwell et al 2001). Therefore, tissue engineering as a potential approach to regenerate cartilage tissue holds good promise. One of the methods of engineering cartilage tissue is through the use of 3D scaffolds combined with chondrocytes or progenitor cells (Tuli et al 2003;Li et al 2005c). Li et al developed PCL-based nanofibrous scaffolds by electrospinning (Li et al 2003, 2005c). These scaffolds were then seeded with fetal bovine chondrocytes (FBC) and studied for their ability to maintain chondrocytes in a mature functional state. Their results demonstrated that FBCs seeded on the PCL nanofibers were able to maintain their chondrocytic phenotype by expressing cartilage-specific extracellular matrix genes like aggrecan, collagen type II and IX, and cartilage oligomeric matrix protein (Li et al 2003). Further, FBCs exhibited a spindle or round shape on the nanofibrous scaffold in contrast to a flat, wellspread morphology as seen when cultured on tissue culture polystyrene. Another interesting finding from this study was that serum-free medium produced more sulfated proteo-glycan-rich cartilaginous matrix when compared with the same cultured in monolayer on tissue culture polystyrene. These results demonstrated that the bioactivity of FBCs depends on the architecture of the scaffold and the composition of the culture medium. Hence, the PCL nanofibers show potential to be further explored as scaffolds for cartilage tissue engineering. In a more recent study, Li et al have further explored the PCL nanofibers for cartilage tissue engineering. In this study, the authors used adult bone marrow-derived MSCs along with PCL nanofibers to test if the nanofibrous scaffolds supported in vitro MSC chondrogenesis. Their results indicated that PCL nanofibers in the presence of a member of the transforming growth factor-" family caused the differentiation of MSCs to chondrocytes that was comparable to that caused by cell aggregates or pellets (Li et al 2005c). However,

since the PCL nanofibrous scaffolds possess better mechanical properties than cell pellets, they show potential to be developed as a scaffolding system for MSC delivery and hence cartilage tissue engineering. Kisiday et al (2002) developed a self-assembling peptide hydrogel scaffold for cartilage repair. They used the peptide KDK-12 that had a sequence of (AcN-KLDLKLDLKLDL-CNH2) (where K is lysine, D is aspartic acid, and L is leucine). This peptide was seeded with bovine chondrocytes and then allowed to self assemble into a hydrogel. The chondrocyte-seeded hydrogels were then studied for their ability to support chondrocyte proliferation, ECM production, and phenotype maintenance. Their results demonstrated that the chondrocytes were able to produce cartilage-like ECM which was rich in proteoglycan and type II collagen (phenotypic markers of chondrocytes). Further, the authors observed that the mechanical properties continuously increased with time, which was indicative of the continuous deposition of glycosaminoglycanrich matrix by the chondrocytes. In addition, the ability to design the peptide may offer advantages in controlling scaffold degradation, cell attachment, and growth factor delivery. Therefore, the self-assembling peptide hydrogel scaffold may be a suitable candidate for cartilage tissue engineering. Nanofibers for ligament tissue engineering Ligaments are bands of dense connective tissue responsible for joint movement and stability. Ligament ruptures result in abnormal joint kinematics and often irreversible damage of the surrounding tissue leading to tissue degenerative diseases, which do not heal naturally and cannot be completely repaired by conventional clinical methods (Lin et al 1999; Goulet et al 2000). Recently, tissue engineering methods involving nanofibers have been successfully employed to meet this challenge (Lin et al 1999). In particular, aligned nanofibers enhanced cell response and hence were explored as scaffolds for ligament tissue engineering. Lee et al studied the effects of PU nanofiber alignment and direction of mechanical stimuli on the extracellular matrix generation of human ligament (anterior cruciate) fibroblasts (HLF) (Lee et al 2005). Conventional electro-spinning produces randomly oriented nanofibers; however, the authors made use of a rotating target to achieve electrospun fibers that were aligned. The fibers were then seeded with HLFs to study the influence of alignment on HLF behavior. Their results demonstrated that HLFs were spindle shaped, oriented in the direction of nanofibers, and showed enhancement in the synthesis of ECM proteins (collagen) on aligned nanofibers when compared with randomly oriented nanofibers. In addition, the authors also studied the effect of direction of mechanical stimuli on the ECM produced by HLFs. For this study the authors seeded HLFs on parallel aligned, vertically aligned to the strain direction, and randomly oriented PU nanofibers. The results demonstrated that HLFs were more sensitive to strain in the longitudinal direction. Therefore, this study concluded that aligned nanofibrous scaffolds showed promise for use in ligament tissue engineering (Lee et al 2005). Nanofibers for skeletal muscle tissue engineering Skeletal muscles are responsible for voluntary movement of the body and once damaged (by disease or trauma) are difficult to regenerate in adults (DiEdwardo et al 1999). Therefore, tissue engineering of skeletal muscle, although challenging, is an exciting alternative to surgical techniques for skeletal muscle regeneration. Riboldi et al (2005) have explored the use of electrospun microfibers made from degradable polyester urethane (PEU) as scaffolds for skeletal muscle tissue engineering. Based on their preliminary studies using primary human satellite cells (biopsy from a 38-year-old female), C2C12 (murin myoblast cell

line), and L6 (rat myoblast cell line), their results indicated that the electrospun microfibers of PEU showed satisfactory mechanical properties and encouraging cellular response in terms of adhesion and differentiation. Based on these studies, the electrospun microfibers of PEU show potential to be further explored as a scaffolding system for skeletal muscle tissue engineering. Nanofibers for skin tissue engineering Skin wounds normally heal by formation of epithelialized scar tissue rather than by regeneration of full skin (Clark and Singer 2000). Of the two layers of skin, epidermis and dermis, the epidermis has less capacity to heal; however, when large areas of the epidermis need to be replaced, normal regeneration is lacking. Further, the dermis has an enormous capacity to regenerate. The scar tissue that forms in the absence of dermis lacks elasticity, flexibility, and strength of the normal dermis (Clark and Singer 2000;Parenteau et al 2000). Consequently, scar tissue limits movements, causes pain, and is cosmetically undesirable. Therefore, engineered skin tissue would be an excellent alternative, not only to close the wound but also to stimulate the regeneration of the dermis. Along with collagen, several other natural and synthetic polymers have been explored for skin tissue engineering (Matthews et al 2002); however, the use of these biomaterials as nanofibers has been very limited. Min et al (2004) developed nonwoven silk fibroin nanofibers by electrospinning for skin tissue engineering. Due to their high porosity and high surface area to volume ratio, fibroin nanofibers coated with type I collagen were found to promote keratinocytes/fibroblast adhesion and spreading. Therefore, the silk fibroin nanofibers show potential to be developed as a scaffold for skin tissue engineering. Khil et al (2003) studied PU electrospun nanofiber membranes for the purpose of wound dressings. The PU nanofiber membranes provided excellent oxygen permeability and controlled water evaporation. By virtue of these properties, the nanofiber membranes allowed fluid from the wound to exude out while preventing dehydration of the wound. Further, the ultra-fine porosity of the PU nanofiber membranes disallowed invasion by exogenous microorganisms. These results indicated that the PU nanofiber membranes showed potential to be developed as wound dressing materials. Go to: Nanofibers for blood vessel tissue engineering From the days of research on developing vascular grafts using materials that produce minimal interaction with the inflowing blood and adjacent tissues, researchers have come a long way to develop constructs at the nanoscale that interact with cells and cause blood vessel formation. Conventional electrospinning produces randomly oriented nanofibers; however, Mo et al developed an aligned biodegradable PLLA-CL (75:25) nanofibrous scaffold using a rotating collector disc for collection of aligned electrospun nanofibers (Mo and Weber et al 2004). These aligned nanofibers were explored to fabricate tubular scaffolds that could be used for engineering blood vessels. Their results demonstrated that the nano-sized fibers mimic the dimensions of natural ECM, provide mechanical properties comparable to human coronary artery, and form a well defined architecture for smooth muscle cell adhesion and proliferation (Mo and Weber 2004; Mo et al 2004; Xu et al 2004b). Aligned fibers not only give structural integrity but also maintain vasoactivity as they provide necessary mechanical strength needed to sustain high pressure of the human circulatory system (Xu et al 2004a).Xu et

al (2004a) studied the response of endothelial cells along with smooth muscle cells (SMCs) on the aligned nanofibers of PLLA-CL, and their results demonstrated that both the cell types showed enhanced adhesion and proliferation rates on the nanofibrous scaffold. In addition, it was observed that the SMCs cytoskeleton organization was along the direction of the nanofibers. These results suggested that aligned nanofibers may provide for a good scaffolding system for vascular tissue engineering. It is now established that there is a significant effect of nanoscale-textured surface roughness on cell response in terms of cell adhesion and proliferation (Webster et al 2001). It is also known that cells attach and organize very well around fibers with diameters smaller than them (Xu et al 2004a). Therefore, Ma et al processed a conventional polymer, PET, into a nonwoven nanofibrous mat by electrospinning, and modified its surface by grafting gelatin (Ma et al 2005b). Their study demonstrated enhanced spreading and proliferation of endothelial cells on the modified PET nanofiber mats, while preserving their phenotype. Based on this study, gelatin-modified PET nanofibers could be potential candidates for the engineering of vascular grafts. Boland et al (2004) developed electrospun micro and nanofibrous scaffolds from natural polymers such as collagen and elastin with the goal of developing constructs for vascular tissue engineering. Their results demonstrated that electrospun collagen and elastin nanofibers were able to mimic the complex architecture required of vascular constructs and were able to provide good mechanical properties that are desired in the environment of the blood stream. Their study indicated that micro and nanofibrous scaffolds synthesized from natural polymers such as collagen and elastin could be useful in the engineering of artificial blood vessels. Nanofibers for neural tissue engineering In the nervous system, degeneration of neurons or glial cells or any unfavorable change in the extracellular matrix of neural tissue can lead to a wide variety of clinical disorders. Neural tissue repair is a daunting challenge because almost all neural injuries lead to an irreversible loss of function (Fine et al 2000). Neural tissue engineering aims to repair neural tissue by employing biological tools such as normal or genetically engineered cells and ECM equivalents along with potent synthetic tools such as biomaterials for scaffold design and/or drug delivery systems. Yang et al have studied the potential of poly(l-lactic acid) (PLLA)-based electrospun nanofibrous scaffolds for the purpose of neural tissue engineering. Their study involved understanding the influence of the nanofibrous scaffolds on neural stem cells (NSCs). Their results indicated that randomly oriented nanofibers (150350 nm) not only supported neural stem cell adhesion but also promoted NSC differentiation (Yang et al 2004, 2005). The authors attributed the aforementioned findings to higher surface area and roughness of the nanofibers. Yang et al have recently reported another study wherein they tried to understand the role of aligned nanofibers in neural tissue engineering. They obtained aligned nanofibers by collecting nanofibers on the edge of a rotating disc. The 3D scaffolds were fabricated to desired thickness by adjusting the collecting time; however, after approximately 30 minutes, residual charges on the collecting fibers led to random collection of the fibers on top of the scaffold. The scaffolds with oriented nanofibers were then studied with NSCs to determine the influence of nanofiber orientation on NSCs. The results demonstrated that NSCs elongated and their neurites outgrew along the direction of the fiber orientation of the aligned nanofibers. Further, it was observed that the NSCs show increased rate of differentiation on aligned

nanofibers compared with microfibers. Therefore, the aligned PLLA nanofibrous scaffolds show potential to be developed for neural tissue engineering (Yang et al 2005). Semino et al (2004) developed a self-assembling peptide scaffold with a goal of studying 3D culture and cell entrapment. Hippocampal slice and neuroprogenitor cells from the dentate gyrus region were cultured on top of the self-assembled nanofibrous scaffold. At the interaction layer between the hippocampal slice and the nanofibrous scaffold, migrating cell populations were readily enriched and entrapped. After 1 week of culture, glial cells and neurons increasingly migrated into the peptide scaffold to an approximate depth of 400500 !m from the edge of the tissue slice. Entrapped cells collected from the migration zone were used to initiate new culture. A noteworthy observation from these experiments was that the mitotic activity of neural cells was maintained for 3 days after migration and the authors attribute this to the presence of the nanofibrous scaffold environment that is similar to the ECM of the cells in their native environment. The understanding gained in this study takes us one step closer to the development of a technology for neural progenitor cell isolation and enrichment in vitro. This technology once developed could greatly enhance the ability of scientists to isolate neural progenitor cells and hence engineer neural tissue. Go to: Nanofibers for controlled drug delivery Controlled delivery systems are used to improve the therapeutic efficacy and safety of drugs by delivering them to the site of action at a rate dictated by the need of the physiological environment. A wide variety of polymeric materials have been used as delivery matrices, and the choice of the delivery vehicle polymer is determined by the requirements of the specific application (Heller and Hoffman 2004). Polymeric nanofibers have recently been explored for their ability to encapsulate and deliver bioactive molecules for therapeutic applications. Kenawy et al (2002) studied PEVA, PLA, and their 50:50 blend-based electrospun nanofibrous scaffolds for the delivery of tetracycline hydrochloride in periodontal applications. Their results demonstrated that the initial rate of release of tetracycline hydrochloride from the scaffold is high during the first 1012 hours, most likely due to release of drug sequestered on the nanofiber surface. Electrospun PEVA showed a higher release rate when compared with the electrospun nanofiber meshes of pure PLA or 50/50 PLA/PEVA. Electrospun PEVA released 65% of its drug content within 120 hours, whereas a 50/50 blend of PLA and PEVA gave about 50% release of tetracycline hydrochloride for the same duration. These results indicated that the rate of release of tetracycline hydrochloride can be controlled by modulating the ratio of PLA and PEVA in the polymeric blend. Therefore, the nanofibrous delivery system showed potential to be employed in the treatment of periodontal diseases. In another study, Verreck et al (2003b) have demonstrated the use of (nonbiodegradable polymer scaffolds) PU nanofibrous scaffolds produced by electro-spinning for the delivery of water-insoluble drugs such as intraconazole and ketanserin. In their study, the authors obtained an amorphous nanodispersion of the waterinsoluble drug on the nanofibrous scaffold. The large surface area of the nanofibrous scaffold allowed fast and efficient solvent evaporation that gave limited time for crystallization of incorporated drug, and favored the formation of an amorphous dispersion (Verreck et al 2003a). These studies demonstrated that the release of poorly water-soluble drugs from water-insoluble polymers is possible and that the rate of release can be tailored by altering the concentration of the polymer. Another study by Kim et al (2003, 2004) demonstrated

the potential use of PLGA nanofibrous scaffolds for controlled release of hydrophilic antibiotics. The authors incorporated Mefoxin (cefotoxin sodium) into PLGA nanofibers during the process of electrospinning. Inhibited growth of Staphylococcus aureusindicated that the bioactivity and structure of the antibiotic drug is not affected by the process of electrospinning. The above studies elucidate that nanofibrous scaffolds are suitable carriers for both hydrophilic and hydrophobic drugs, and that the drug release rate can be tailored by modulation of the nanofibrous scaffolds morphology, porosity, and composition. Nanofibers for DNA, protein, and enzyme delivery With the availability of multiple gene delivery systems, the selection of the most appropriate gene delivery vehicle to meet the needs of a particular therapeutic application can be challenging. Viral- and plasmid-based delivery vehicles are currently used for the production of therapeutic proteins to elicit a desired biological response (Fradkin et al 2000). This would especially be useful in the field of tissue engineering, wherein it would be possible to cause the production of a desired protein (growth factor) that can enhance the process of tissue regeneration. Therefore, gene delivery systems have been explored for applications in the engineering of a variety of tissues. The most commonly used carrier-based systems for gene delivery are cationic liposomes and condensing agents such as poly(ethyl-enimine), and poly (l-lysine). More recently, biomaterial-based gene delivery systems have been explored and are proving to be a promising approach. Various biomaterials such as poly(ethylene glycol) (PEG), PLGA, and PLA-PEG copolymers are currently being investigated for gene and protein delivery (Funhoff et al 2005). Scaffolds for gene delivery need to provide structural stability and site specific delivery of genes along with protection of genes from the biological system until it is released. Further, the released DNA needs to retain its structural integrity until it is taken up by the desired cells. Luu et al studied PLGA and PLA-PEG block copolymer based nanofibrous scaffolds for plasmid DNA delivery (Fang and Reneker 1997; Luu et al 2003). Their results indicated that the electrospun nanofibrous scaffolds delivered the gene in a controlled manner at the targeted site and consequently caused cell transfection and desired bioactivity. This approach showed higher transfection efficiency when compared with naked DNA added directly to the culture medium. Increasing the amount of DNA during scaffold fabrication increased transfection efficiency of the nanofiber DNA system. The architecture and material properties of the nanofibrous scaffold affect the rate at which the DNA is released. Therefore, the release profile of the DNA can be controlled by tailoring scaffold parameters like nanofiber diameter, pore size of scaffold, and degradation rate of the polymer. Through these modifications it is possible to sustain the delivery of DNA over a longer duration. Overall, this system seems ideally suited for the sustained/controlled delivery of intact DNA over a period of several months. Jia et al (2002) used alpha-chymotripsin attached to electrospun polystyrene nanofibers (120 nm) as a catalytic system and examined its catalytic efficiency in biotransformations. Their results indicated that the nanofibrous enzyme system had a higher hydrolytic activity (65%) than immobilized enzyme, and three times more nonaqueous activity than immobilized alpha-chymotrypsin in organic solvents. The authors proposed that covalent binding of the enzyme to the nanofiber increased enzyme stability or decreased structural denaturation. They believe that this increased stability may be the reason for enhanced activity of

the enzymes attached to the nanofibers. Therefore, the nanofibers show potential to be developed as catalytic systems to be used in biotransformations. In a recent study, Zeng et al (2005) developed poly(vinyl alcohol) (PVA) electrospun nanofibers for protein delivery. PVA nanofibrous scaffolds were loaded with bovine serum albumin or luciferase proteins. The PVA nanofibers were then coated with poly(p-xylylene) (PPX) using chemical vapor deposition. The coated and uncoated PVA nanofibrous scaffolds were then studied for release kinetics and bioactivity of the released proteins under physiological conditions. The results demonstrated that intact protein/enzyme was continuously released from both the nanofiber types and their bioactivity was preserved after release from the nanofibrous scaffolds. However, the PPX-coated nanofibers exhibited significantly retarded release rates compared with the uncoated PVA nanofibers. Therefore, this study showed that the nanofibrous scaffold could be a good candidate material for controlled enzyme/protein delivery. All the above studies demonstrated the potential of nanofibers as controlled delivery systems, and hence demand exploration at greater depth to enable this technology to benefit the patient. Go to: Application of carbon nanofibers in tissue engineering Apart from having nanoscale fiber dimensions similar to HA and collagen fibers present in bone, carbon nanofibers have exceptional mechanical properties (three times that of bone tissue), thereby giving a strong rationale to investigate them for application in orthopedic or dental tissue engineering (Elias et al 2002). Further, carbon nanofibers have also been shown to exhibit excellent conductivity, which might make them potential candidates for neural tissue engineering applications. The carbon-nanofiber-based implants can surpass in some ways the conventional metal alloy implants used in orthopedics, as they have excellent cytocompatibility properties (Price et al 2003b) and complications associated with leachables in the form of metal ions released from implants do not arise. In terms of mechanical properties, carbon nanofibers possess a Youngs modulus of 2 TPa, which is significantly higher than that of bone, whereas the tensile strength of carbon nanofibers almost equals that of bone (Elias et al 2002). Therefore, Price et al explored the possibility of using carbon nanofibers for bone tissue engineering. They compared osteoblast adhesion on carbon nanofibers with that of conventional carbon fibers (Elias et al 2002; Price et al 2004) and showed greater osteoblast adhesion on carbon nanofibers. To determine the properties that caused enhanced adhesion on carbon nanofibers, the authors studied osteoblast adhesion on PLGA-coated carbon nanofibers. Their results indicated that PLGA-coated carbon nanofibers also showed enhanced osteoblast adhesion compared with conventional carbon fibers. The authors attributed this behavior to increased surface energy (due to high surface area of the nanofibers), nanometer topography, and surface chemistry of the fibers (Price et al 2004) (see Figure 4).

Figure 4 High magnification scanning electron micrograph of carbon nanofiber compacts. The carbon nanofibers were prepared using a chemical vapor deposition technique with a pyrolitic aromatic hydrocarbon outer layer (PR-1 AG [nanophase]). The resulting carbon ...

Due to their electrical conductivity, carbon nanofibers were initially explored as electrically conducting fibers, in nanoelectronic devices, field emitters, and also in reinforcement (Wal et al 2002; Hammel et al 2004). More recently, due to their conductivity, carbon nanofibers are being explored as potential candidates for neural tissue engineering. To determine the cytocompatibility of carbon nanofibers as neural implants, McKenzie et al (2004) studied the interaction of astrocytes (glial scar tissue-forming cells) and carbon nanofibers in terms of adhesion and proliferation. Their studies demonstrated that functions of astrocytes were minimized on nanoscale fibers and led to reduced scar tissue formation. Based on these observations, the authors concluded that minimized glial scar tissue formation and positive interaction with neurons are properties that would strongly support the success of a neural implant. Therefore, carbon nanofibers need to be investigated further to establish their potential use in neural tissue engineering. Go to: Applications of alumina nanofibers in tissue engineering Osteointegration is a major requirement for bone and dental implantation. It has been demonstrated that a decrease in surface feature size can enhance osteointegration (Webster 2001). Alumina, titania, HA, and their composites are the most well studied materials for both dental and orthopedic applications. Due to similarity between physical geometry of HA and aluminum nanofibers, Price et al hypothesized that alumina nanofibers may enhance osteointegration (Price et al 2003a). They studied the influence of alumina nanofibers on the behavior of osteoblast cells. Their results demonstrated that the alumina nanofibers enhanced cell adhesion and synthesis of osteoblastic phenotypic markers such as alkaline phosphates and calcium (Webster et al 2005). The above studies elucidate that carbon and aluminum nanofibers can be promising materials for orthopedic/dental tissue engineering applications.

Catalytic nanofibers Chemical reactions employing enzyme catalysts are important in chemical processes due to their high selectivity and mild reaction conditions.70 Immobilized enzymes are used largely due to easiness of catalyst separation, enzyme stability, and their availability for continuous operations. The efficiency of these immobilized enzymes depends mainly on the pore structure and diffusion limitations of the substrate material. Nanomaterials are of recent interest as catalyst substrates due to their large surface area per unit mass and the feasibility for high catalyst loading.70 Nanofibrous catalysts could substitute catalytic nanoparticles in order to overcome the limitations of catalyst recovery.68 Jia et al. prepared bioactive polystyrene (PS) nanofibers by chemical attachment of #-chymotrypsin on PS and observed a high catalytic activity with improved enzyme stability over other forms of immobilized enzymes.70 Fibrous catalysts offer advantages, such as feasibility of adapting to any geometry and low resistance to the flow of liquids and gases.71Though catalyst loading and mechanical properties limit the usage of fibrous catalysts, the advent of nanofibrous materials as catalytic substrates alters the scope of its application. The activity of the catalyst supported on a substrate depends on its large active surface area. Nonporous substrates can be coated with a high surface area material like nanofibers to increase the surface area,

thereby enhancing reactivity.71 Carbon nanofiber supports loaded with iron particles have shown high conversion of hydrocarbons in comparison with active carbon and $-alumina.72 It has been shown that the intrinsic catalyst effect is more pronounced when loaded in smaller diameter fibers such as nanofibers.72 Filtration The control over airborn and waterborn contaminants, hazardous biological agents, allergens and pollutants is a key issue in food, pharmaceuticals and biotechnology processes. The particle size of particulate matter is determined by the process that generates the particles. For instance, combustion particles are usually in the 1050 nm size range, but when they combine with other particles and agglomerate form larger particulates. The existing high efficiency air filters effectively filter particles of 0.3 !m and above. However, they are not sufficient for filtration of smaller pathogenic agents like viruses. Air and water are the bulk transportation medium for transmission of particulate contaminants. The contaminants during air filtration are complex mixtures of particles. The most of them are usually smaller than 1000 !m in diameter. Chemical and biological aerosols (particulates) are frequently in the range of 1 10 !m. The particulate matters may carry some adsorbed gaseous contaminants. The removal of particulate and biological contaminants is an important step in water purification process. Particulate contaminants if not removed tend to foul reverse osmosis membranes and severely reduce the throughput of the final purification step. The filtration industry is looking for energy efficient high performance filters for filtration of particles smaller than 0.3 !m and adsorbed toxic gases. Nanofibrous media have low basis weight, high permeability and small pore size that make them appropriate for a wide range of filtration applications. In addition, nanofiber membrane offers unique properties like high specific surface area (ranging from 1 to 35 m2/g depending on the diameter of fibers), good interconnectivity of pores and potential to incorporate active chemistry or functionality on nanoscale. Therefore, nanofibrous membranes are extensively being studied for air and liquid filtration. Scanning electron microscopic picture of nanofibrous filtering media is shown in Fig. 1. (Polymeric nanofibers have been used in air filtration applications for more than a decade since their surface area is substantially greater and have smaller micropores than melt blown (MB) webs. Electrospun fibers have diameters three or more times smaller than that of MB fibers. This leads to a corresponding increase in surface area and decrease in basis weight. High porous structure with high surface area makes them ideally suited for many filtration applications. Nanofibers are ideally suited for filtering submicron particles from air or water. Due to poor mechanical properties of thin nanowebs, they were laid over a substrate suitable enough to be made into a filtration medium. The small fiber diameters cause slip flows at fiber surfaces, causing an increase in the interception and inertial impaction efficiencies of these composite filter media. The enhanced filtration efficiency at the same pressure drop is possible with fibers having diameters less than 0.5 micron. The potential for using nanofiber webs as a filtering medium is highly promising. The highly porous electrospun membrane surfaces help in moisture vapor transmission. The airflow resistance, filtration efficiency, and pore sizes of nonwoven filter media could be easily altered by coating with the lightweight electrospun nanofibers.

Nanofiber combined with other nonwoven products have potential uses in a wide range of filtration applications such as aerosol filters, facemasks, and protective clothing. At present, military fabrics under development designed for chemical and biological protection have been enhanced by laminating a layer of nanofiber between the body side layer and the carbon fibers

Energy Researchers have been investigating clean energy opportunities such as, using solar energy more efficiently and cost effectively for generation of electricity, electrolysis of water to generate hydrogen and into electricity with reduced emissions via fuel cells . Efficient use of energy is often connected with energy conservation. Once the electricity is generated it must be efficiently stored during low demand periods, or for use in portable applications. This highlights the need for electrochemical energy storage devices, via high energy density batteries and/or super capacitors. Then, the storage of hydrogen becomes of interest, particularly when considering the use of hydrogen as fuel for electric vehicles or as a clean burning fuel for vehicles with combustion engines. While in the broadest sense, processes involved in energy and environmental treatment technology, can be considered in one way or the other, charge generation, transport and collection, as well as diffusion. Common challenges are improved performance, conversion efficiency, energy/power density, discharge rate and extended life with reversibility, and reduced production and operation costs. In particular, rapid e%, Li+, and H+ transport are essential for achieving desired performance in high efficiency solar cells , high energy density batteries and high efficiency fuelcells , respectively. A potential solution to overcome the shortage of water is to tap alternative sources of water, such as seawater, rainwater, wastewater effluent etc. However, contaminants in these waters have to be removed and water quality improved, before the water can be fit for usage. Indoor and outdoor air have to be purified; it was estimated that the global market for filtrationand separation products reached US$37.3 billon in 2007/8.4 Thus, both water and air quality systems have to be controlled to ensure a safer environment by implementing efficient technology. The demand for such high performance devices or efficient technology has led to increasing attention in advanced functional nanosized materials. It is only recently that attention has been given to the 1dimensional (1D) morphology that is used for high technology applications. 1D semiconducting nanowires , nanofibers and nanotubes and also patterning of materials can be used to enhance charge transport and as building blocks in energy and electronic devices because of their confinement effects. Water and air purification or removal of contaminants can be effectively achieved using nanofiber membranes . Though nanofiberous materials can be prepared by methods such as: template-directed,5 vapor-phase approach6 solution-liquid-solid (SLS ) technique,7solvothermal synthesis ,8 solution-phase growth based on capping reagents,9 and self-assembly ,10 electrospinning (ES ) has become more popular because of its easiness and low cost.Electrospinning (ES ) is a physical process and moreover, one of the available inexpensive industry viable technologies, which can truly produce 1D fibers of !m to nm size ranges in

diameter.11The broad applications of electrospinning technology are summarized in Table 1. A quick analysis of nanofibers use for advanced functional applications over the past 10 years (Fig. 1) has indicated that their impact has been substantial. In particular, the impact of nanofibers in energy conversion (solar cells and fuel cells ), and also in water and air treatment applications have been realized well and is encouraging (Fig. 2). This review highlights the potential and application of electrospun fiberous materials for energy and environmental treatment applications.

2. Principle of electrospinning Electrospinning of materials involves the application of a strong electric field to a droplet of a fluid, such as a melt or blend solution. A schematic of an electrospinning set up is shown in Fig. 3. The set up mainly consists of a spinneret, collector and high voltage power supply. A potential (in kV) is applied between the spinneret and a collector; both are electrically conducting and separated at an optimum distance between the two. The interactions of the electrical charges in the polymer fluid with the external electric field causes the pendant droplet to deform into a conical structure called the Taylor cone (Fig. 3(a)) and a critical voltage is attained. When the applied voltage surpasses the critical value at which repulsive electrostatic forces overcome the surface tension, a fine charged jet is ejected from the tip of the Taylor cone. These charged jets undergo a whipping motion and elongate continuously via electrostatic repulsion until they are deposited onto a grounded collector; resulting in the formation of fine fibers. Instability can occur if the applied external electrostatic field is not above the critical value, which would cause the jet to break up into droplets. Such phenomena is called Rayleigh instability. Therefore, the formation of nanofibers is a function of operating parameters viz. applied voltage, solution feeding rate and solution properties, mainly conductivity, viscosity and surface tension. Consequently, these electrospinning process parameters can be tuned to produce a wide range of fiber diameters.

In general, two types of 1D nanostructures can be formed using electrospinning : aligned and non-aligned nanofibers (Fig. 4). Electrospinning by simple methodology produces nonwoven form nanofiber layers or mats, which can be useful for applications such as filtration , tissue scaffolds, and implant coating films. Electrospinning with improved design or additional set up, such as a rotating disc or cylinder, could produce aligned nanofibers (Fig. 3(c)) or uniaxial fiber bundles that can be more useful in energy conversion devices. Geometry and rotating speed of a disc, or optimization of the electric field enable one to obtain the aligned electrospun nanofibers. The rotation of a cylinder collector at a very high speed, up to thousands of revolutions per minute, could result in electrospun nanofibers being oriented circumferentially.12
14

Researchers have also introduced insulators to influence the electrostatic forces acting on a charged fiber

and force them to align the fibers uniaxially.15,16 Controlling the distance between the electrodes should also form aligned fibers, however, which is to be determined by the molecular weight of the polymer . For instance, Sundaray et al.17 obtained aligned polymethylmethacrylate (PMMA, Mw = 120 000) polymer fibers, with separation between the fibers in the range of 5100 mm by controlling the distance between the electrodes at about 13 cm, whereas 15 cm is the distance between the electrodes needed to obtain an aligned high molecular weight of polystyrene (PS) fibers. Core-shell nanofibers can be fabricated by co-electrospinning two different polymer solutions through a spinneret comprising two coaxial capillaries as shown in Fig. 3(b).18,19 Uniform nanofibers ofconjugated polymers have also been prepared via a coaxial electrospinning technique.20,21

3. Energy conversion devices 3.1 Dye -sensitized solar cells Electrical energy is the most versatile energy for the 21st century world. Technologies are under development to obtain electrical energy from renewable sources, such as sun, wind, tidal etc. Photovoltaics is one of these technologies, it converts solar light directly into electrical energy, has reached several stages of development and is promising because solar energy is, almost, considered as an inexhaustible supply of energy. For the first time Regan et al.22 showcased the potential of nanotechnology to obtain electricity by constructing a dye -sensitized solar cell(DSSC). DSSC technology is an artificial photosynthesis process using an electrolyte, a film of metal oxide nanoparticulate as the electrode and a dye sensitizer sandwiched between conducting glasses. In a DSSC, a light harvesting material (dye ) generates excitons (bound electron-hole pairs) upon absorption of photons , and undergoes dissociation to release them as free electrons and holes. The free electrons are injected into the metal oxide nanoparticulate and transported for collection at the electrode . The more the electrons collected, the higher the efficiency. Researchers have used spin coating ,2325 screen-printing,26 doctorblading,27 and chemical vapour deposition 28 to form titania nanofilms as a photoelectrode. Researchers recently have realized that grain boundaries diminish the efficiency of electron conduction in nanoparticulate matrix intemperately, and lead to chargecarrier recombination. The 1D morphology of the metal oxide fibers is believed to contribute to better charge conduction, because of their reduced grain boundaries compared to those of sintered nanoparticles , and also provides high specific surface area for the increased adsorption of dye sensitizers.29 Polymers such as polystyrene (PS), polymethylmethacrylate (PMMA), polyvinylpyrrolidone (PVP) and polyvinyl acetate (PVAc) have been used to prepare such metal oxide nanofibers. Compared with other polymers , PVP is readily soluble in safe solvents , such as water, and produces a prolific amount of electrospun material, suggesting that it has the potential for large-scale ceramic fiber production.30 While replacing the liquid electrolytes with solid or semi-solid type electrolyte in order to attempt for flexible solar cells , imperfect filling of the electrolyte in

the cells has been an issue. Nanofiberous metal oxide fabricated by the electrospinning method has larger pores than metal oxide as nanoparticles ,29 this is expected to enhance the penetration of viscous polymer gel electrolyte. The solarelectric energy conversion efficiency which has been obtained from electrospun TiO2 electrodes with a poly(vinylidenefluoridecohexafluoropropylene) (PVDFHFP) gel electrolyte is over 90% of that from a liquid electrolyte system,31,32 which confirms the effective penetration of viscous gel electrolyte due to the porous morphology. The major problem of using nanofiberous inorganic electrodes in DSSCs is their poor adhesion to substrates after calcination , which is carried out to remove binder polymers . Due to the high temperature used for the calcination process, strong stresses are generated, and lead to the shrinkage of the fibrous mats. Such shrinkage has limited the application of electrospun ceramic nanofibers film, especially for metal oxide electronic devices TiO2 webs which were found to peel off substrates. Song et al.33 have used hot press pre-treatment to improve the adhesion of the TiO2 nanofibers onto the substrate. Onozuka et al.29 introduced solvent vapour to relax the nanofiber mats that, also, resulted in improved adhesion between TiO2nanofibers and the conducting substrate. Fujihara et al.34 transformed electrospun nanofibers into nanorods by mechanical grinding in order to eliminate the adhesion difficulties of longer nanofibers developed by the electrospinning technique with the conductive glass plate (Fig. 5 and 6). DSSCs fabricated using such nanorods under air mass 1.5 global filter (AM1.5 G) condition delivered a current density 13.6 mA cm%2, open circuit voltage 0.8 V, fill factor 51% and energy conversion efficiency 5.8%. Recently, our group introduced an ultra-thin surface treatment layer (STL) on the conducting substrate before the deposition of the electrospun TiO2 nanofibers, which retained adhesion of nanofibers on the conductive substrate even after calcination .160 Aftercalcination , the STL acted as an adhesive and thus bettered the adhesion of TiO2 nanofibers.

Doping of materials has also been successful in advancing the function of materials.3538 For example, strontium doped TiO2 (SrTiO3) has reduced the chargecarrier recombination in DSSCs.39 Doping the TiO2 with erbia showed emitting property in the near-infrared emission spectra range 60007000 cm%1 and, therefore, is used as a selective emitter for thermophotovoltaic applications. Tomer et al.40 prepared the erbia-containing titania electrospun nanofibers using erbium(III) oxide particles, tetraisopropyl titanate and 10% solution of PVP as precursors at 1 kV. They obtained mechanically stable nanofibers and also noticed that the large surface to volume ratio characteristics of nanofibers allowed gases to pass through with a lower pressure drop than materials made from micron-sized fibers. 3.2 Organic solar cells Organic photovoltaic (PV) devices based on blends of conjugated polymers and inorganic nanostructures are currently objects of intense research for low cost solar energy conversion. Organiccells utilize a bulk heterojunction of donor and acceptor materials to provide a large internal surface area for the efficient charge

separation of photo-generated excitons. However, such devices are limited by inefficient charge transport because of the highly folded, discontinuous topology of the donoracceptor (DA) interface. Annealing could improve the transport process, however, may not be compatible with the use of most of the polymers , which have a low glass transition temperature. Therefore, alternative processing procedures that yield the same nanomorphology without thermal treatment are necessary for the development of efficient and flexible solar cells . Replacing the disordered phase with an aligned array of nanowires could improve charge transport and increase power conversion efficiencies without any thermal post treatment.41 However, most of the conjugated polymers are difficult to electrospin because of their lower molecular weight andsolvent limitation. For instance, polypyrrole (PPy), a conducting polymer , has attracted more attention because of its unique electrical, optical, and photoelectric properties as molecular wires and molecular devices42 but exerts poor solubility in common solvents , due to its strong inter- and intra-chain interactions. Recently, methods have been developed to produce the fibers from such lower or solvent sensitive polymers using electrospinning . Chronakis et al.43 have improved the processability of PPy by mixing with poly(ethylene oxide) (PEO) and electrospinning to form ultrafine fibers. By increasing the PPy content of the PPy /PEO nanofibers, a higher electrical conductivity has been achieved. Also, the higher concentration of PEO in the initial solution could allow for easy stretching of fibers; that provides higher conductive pathways or chargecarrier mobility of PPy molecules along the fibers.44 The resulting nanofibers showed better electrical conductivity of approximately 3.5 & 10%4 S cm%1 for 50 wt% PPy precursor [PPy(SO3H)DEHS] and 1.1 & 10%4 S cm%1 for 37.5 wt% of PPy precursor. 3. 3 Hybrid solar cell Hybrid materials such as inorganicpolymer composites, or encapsulated functional materials have shown promise in achieving the higher performance of energy and electronic devices.45Polymer metal oxide nanoscale composites play a role in photovoltaic cells .46 Recently, 1D nanostructures of organicinorganic hybrid composites have been successfully made viaelectrospinning .47 3.3.1 Metal oxide /P3HT interface. Using inorganic nanofibers in solar cells increase the donoracceptor interfacial area, dissociation of the photo-generated excitons, and also creates high electron mobility. When a blend of P3HT : PCBM was added to the ZnO nanofibers, a dramatic increase in the external quantum efficiency (EQE) was observed to a value over 57% at 515 nm. This increase is likely to be due to enhanced excitons' dissociation in the film. It has been demonstrated that the interface of nanofiberous ZnO/P3HT : PCBM produces the conversion efficiency (!) of 2.03%.48 Solar cells fabricated with

vertically aligned nanowire morphology are expected to deliver very high performance by suppressing electronhole recombination and effectively improving the transport , however, it has not yet done so and is even inferior than random fibers.4951 This may be due to uncontrolled spacing of vertically aligned nanofibers obtained by the solution grown method, which is usually in the range of 100 nm. It is to be noted

that the typical exciton diffusion length of polymer P3HT is about 10 nm or even lower. Hence, closer nanofibers spacing must be necessary to increase the excitons' dissociation and achieve larger short circuit current (Isc). Electrospinning has not been engineered, so far, to produce the vertically aligned nanofibers. Nonetheless, such a breakthrough can be expected in the near future to solve such a critical issue. 3.3.2 Quantum dots interface. Quantum dots (QDs) are crystals of size 210 nm in diameter, made up of compounds from periodic groups IIVI, IIIV, or IVVI. Multi-excitons generation (MEG) can be achieved in QDs upon absorption of one photon . For example, crystalline Si generates 1.3 excitons52 whereas PbSe QDs exhibit seven excitons, upon absorption of a singlephoton .53 Efficient dispersion of QDs within the polymer to form a QDpolymer interface should provide a large area interface.54 1D QD nanostructures have been found to be effective in developing a QDorganicinorganic system for solar devices as they can facilitate unidirectional electrical transport .55 Wendy et al.55 used surfactant to attain the different size and shape of CdSenanorods , and then washed with pyridine to remove surfactant coating, to retain charge transfer capabilities of the QD nanorods . They observed that the dimension of CdSe nanorods had some flexibility in absorbing the solar spectrum , as such 3 nm diameter 60 nm long nanorods show its onset at a wavelength of 650 nm, whereas, 7 nm diameter nanorods show at 720 nm. Enhancement of carrier mobility was accomplished by improving the CdSe nanorod polymer interface by aligning the nanorods perpendicularly to the substrate. Wendy et al.56 noticed that the CdSe nanorods increased the dissociation of excitons in a CdSe P3HT system and, thereby, more electron hole pairs. Interfacing nanofiberous electrodes and QDs could result in structural integrity that increases the mechanical, as well as chemical strength and systematically increases the overall electronic transport and thus the solarcurrent conversion efficiency (Fig. 7).

3. 4 Fuel cells Fuel cells are devices where electrochemical oxidation of hydrogen or hydrogen-rich fuel is converted in the presence of a metal catalyst into electrical current. As they produce clean energy in the form of current, they do not need recharging or replacing, so the research for higher efficiency and high capacity fuel cells has been intensified in recent years.5761 A fuel cell consists of an electrolyte sandwiched between anode and cathode materials. The type of electrolyte distinguishes that fuel cell from other types of fuel cells . Polymer electrolyte membrane (PEM ) and methanolfuel cells are being developed for automobile propulsion and as portable electronic devices, such as personal digital assistants (PDAs ), cell phones, and notebook computers. The direct methanolfuel cell (DMFC) is very attractive since it operates at room temperature, uses liquid methanol as the fuel , and has the potential to deliver high energy density.62 In DMFCs, aqueous methanol is electrooxidized by metal catalysts , Pt63 or PtRu,64,65 to produce electrical current. The schematic of PEM is shown in Fig. 8.

Fuel cells typically need higher platinum (Pt) content (2060 wt% Pt) as the anode catalyst and in a thin layer to minimize the ohmic resistance and mass transfer limitations.66 Recent research in fuel cells has been aimed at reducing the amount of catalyst used, to even as low as 0.1 mg Pt cm%2 or below because of the expense of noble metal catalysts , but still maximizing anode catalystutilization. To improve the anode catalyst performance, catalytic supporting materials must be stable and dispersed uniformly. To achieve the uniform dispersion, porous nanomaterials having a larger surface area are used as electrode materials. For stability, supporting materials have been considered for the catalyst . Polymers such as polyaniline nanofibers (PANI) have been considered as the most promising matrix for dispersing the Pt nanoparticles .67 The porous network structure of PANI has been effective for dispersion of Pt particles (about 1020 nm) and facilitates easy access of precursor (fuel ) to the catalytic sites.68 Moreover, PANI has a high accessible surface area, and is a good electron conductor.69 Nanowires of conducting polymer are promising support matrices for the dispersion of Pt particles, as they provide conducting pathways and surface interactions between the nanoparticles and conducting polymers . Nanostructured PANI prepared by hard templates such as the alumina membrane method increases catalyst cost and makes scale-up difficult. Electrospinning techniques can be used to disperse the nanoparticles onto the nanofibers uniformly (Fig. 9) and moreover without the involvement of a surfactant or template. The large surface area in the nanofibrillar PANI has enabled the dispersion of catalyst particles with less time for the deposition of Pt particles.68 The electrocatalytic performance of methanol oxidation for PANI nanowires supported Pt composite has been found to be much higher than at bulk Ptelectrodes .70

Proton exchange membrane fuel cells 69,71,72 and direct methanol fuel cells 73,74 have been found to deliver better performance when CNTs or CNFs were used as the support for the Pt catalystin the fuel cell systems65,75,76 because of their high electrical conductive nature.77 Different approaches have been reported for introducing a porous structure into the bulk of an electrospun nanofiber such as selective dissolution,78 selective thermal degradation 79 and liquid nitrogen freezing processes.80 Also, porous sizes can be successfully obtained by controlling process parameters such as the potential applied or drawing rate during the electrospinning process.8183 Yuan et al.84 have suggested that the fuel cell performance using twisted CNFs as the anode was better than that of straight CNFs due to its specific surface conformation, which helps to disperse the Pt more homogeneously. The twist or alignment of CNTs in a polymer matrix can be achieved by applying and varying the electric potential which is possible during electrospinning . Nanofibers containing both SWCNTs and MWCNTs can be electrospun from a polymer -based solution. Sundaray et al.17 have obtained controlled preparation of long and aligned CNT nanofibers. Yasuda et al.85 have noted that increases in the carbon nanofiber content resulted in a random orientation, and increased Young's modulus but decreased hardness. It indicates that the mechanical properties can be influenced by the content of carbon nanofibers for electrospinning and therefore it should be the focus of more attention.

Researchers have also paid attention to developing green catalysts viz. enzymes or biomolecules instead of synthetic catalysts in order to reduce the cost or increase the performance. The geometrical effect i.e. the number of molecules per unit area (or volume) plays a predominant role when immobilizing biomolecules onto the materials as the actual size of such molecules is quite large. As such, the number per unit area (or volume) will not be so high for the nanoparticle layer, and therefore attempts to cross link or immobilize the enzyme onto the nanoparticulate layers may limit or even lose bio(enzyme) activity. Therefore, 1D structure of materials can be emphasized, not only to obtain more enzyme or biomolecule binding but also for controlled electrontransport . Electrospun nanofibers have been used to bind or immobilize the catalytically active enzymes.86 Recently, Patel et al.86 have demonstrated horseradish peroxidase (HRP) enzymeimmobilized mesoporous silica fibers. The silica nanofibers were prepared from tetramethyl orthosilicateglucoseenzyme solution by electrospinning with an electric field of 20 kV and at a distance of 15 cm. D-glucose has also been used, not only to function as a non-surfactant template for controlling mesoporosity, but also to help spinning of the solution by increasing viscosity. In general, the activity of free enzymes decreases rapidly with increases in temperature because of thermal denaturation whereas Patel et al.86 noticed that the immobilized enzymes in silica nanofibers showed an increase in activity even up to 60 C. This improved thermal stability has been suggested to be due to the space confinement in the host fiber matrix, which prevents protein unfolding . Furthermore, the activity of enzyme immobilized silica nanofibers with mesoporosity has shown 4-fold greater activity than conventional templated silica samples and 3-fold greater activity than HRP immobilized silica powders.86 Such dramatically improved features and the versatility of this electrospinning technique are a boon to biocatalytic applications in biofuel cells . 4. Energy storage devices 4. 1 Hydrogen storage Concerns about global climate change and the need for sustainable development have renewed interest in hydrogen as a fuel because using hydrogen zero-carbon emission vehicles can be produced. A future that depends on hydrogen is inevitable and hence, efficient methodologies for producing hydrogen and storing hydrogen have been under investigation. Hydrogen can be stored in materials effectively in the form of metal hydrides . The hydrogen is adsorbed into the spaces or interstices between the atoms in the metal. Hydrogen adsorption strongly depends on the materials' porosity. The smallest pores provide the highest storage capacity and therefore hydrogen storage is dominated by small pores . Small pores (1 nm or below) are the most efficient forhydrogen sorption. Activated carbon, exfoliated graphite and fullerenes have promise for high storage capacity and, more over, they are preferred due to their low cost and easy availability in large amounts. The hydrogen uptake is proportional to surface area and pore volume. As such, nanostructured carbon materials such as carbon nanotubes and carbon nanofibers have shown highhydrogen storage capacity.87 Nanofiberous materials can be prepared for the desired pore size ranges using electrospinning by optimizing process parameters to make materials with attractive morphology

for hydrogen storage . Furthermore, electrospinning could develop high performance hydrogen storage materials as it can produce well structured, highly ordered, and high aspect ratio nanoscale dimensions. 4. 2 Supercapacitors Lithium-transition-metal-oxides include LiCoO2, LiNiO2, LiMn2O4, LiMnO2, and LiV3O8, all are high performance cathode materials for lithium-ion batteries.88,89 LiCoO2, in particular, is one of the most promising cathode materials for commercial applications, such as lithium-ion rechargeable batteries due to its good capacity, high specific energy, good power rates, low self-discharge, and excellent life cycle.90,91 Even if lithium-ion batteries, which combine high power and energy density, appear as the most promising system, there is still a need to improve the performance ofelectrode materials to achieve the highest capacity. High surface area conducting nanofibers make electrospun materials attractive as electrodes for batteries or in electrochemical supercapacitor applications. Gu et al.92 have demonstrated that LiCoO2 nanofibers could exhibit a high initial charge and discharge capacity of up to 216 and 182 mA h g%1, respectively. The traditional method for preparing LiCoO2 can result in inhomogeneity and irregular grain growth , whereas, the solgel method provides pure material with good crystallizability, homogeneity and uniform size.Electrospinning techniques have been very successful for making inorganic nanofibers utilizing the solgel method. Lithium-ions (Li+) are transported between electrodes through the electrolytic medium during charge and discharge. Compared to conventional film based morphology, nanotubes and nanofibers are expected to have improved electrode properties due to their high surface areas and 1D nanostructure properties, and therefore should provide higher rates of electron transfer . In addition, their entangled network allows easy access of the ions to the electrode /electrolyte interface. Lithium chloride (LiCl1H2O), cobalt acetate (Co(CH3COO)24H2O) and 10 wt% PVA have been used as precursors in the preparation of nanofibers of LiCoO2. A voltage of 12 kV was used to provide a dense web of LiCoO2 fibers, dried for 5 h at 701 C under vacuum, followed by calcination at 400700 C. The electrospun nanofibers of LiCoO2 demonstrated improvedelectrode properties as the result of high surface area.93 This method may also be used to synthesize other cathode materials for lithium-ion batteries and, therefore, has good prospects for commercialization.93 The capacitance of the electrical double-layer capacitor is a function of the specific surface area, pore volume, and resistivity of the sample. Researchers, in order to enhance the specific energy and power of supercapacitors, have been trying to develop materials, such as conducting polymers by modifying their structures and controlling pore size distribution. Polybenzimidazol (PBI), a candidate polymer exhibits excellent thermal/mechanical stability, is durable to chemicals, and gives a high carbon yield. Also, PBIbased electrospun fiber does not require stabilization because of its thermosetting property that originates from the high rigidity of the polymer chains. Therefore, researchers expect that PBI should provide a high carbon yield and cost savings. Recently, carbon nanofiber webs have been prepared94,95 through the electrospinning technique and offered the prospect of accelerating the application of these materials in

electrical energy-storage systems. Researchers, therefore, have been investigating methodologies to develop PBI-based activated carbon nanofiber webs as a novel electrode material for electric double layer supercapacitors. Kim et al.96 have prepared homogeneously distributed PBI-based nanofibers with a diameter of about 250 nm from a solution of 20 wt% PBI in dimethyl acetamide using electrospinning . The resulting electrospun nanofiber web electrodes have a large BET specific surface area in the range of 5001220 m2 g%1 which has exhibited higher capacitance.96 Pico et al.97 have investigated electrospun ruthenium oxidecarbon nanofiber composites as an electrode material for capacitor application. RuO2xH2OCNF composite fibers are simple composites, which require neither an inert binder nor an electric conductor to be added to show high electric conductivity, nevertheless, Ru is a rare-earth metal, which is toxic and expensive.97Researchers recently have paid much attention to conducting polymers as electrode materials for supercapacitor applications as they are lower in cost compared with ruthenium oxide. Of these, polyaniline (PANI) has been most promising due to its low cost, high conductivity and stability. Sivakumar et al.98 have prepared electrospun PANI nanofibers and found that the higher surface area of nanofibers led to higher charge storage ability. In addition, the nanofibers morphology could permit rapid access of the electrolyte to the electrode which should result in high chargestorage and fast chargedischarge processes. 5. Optoelectronics Nanoscale gallium oxide (Ga2O3) with a large surface area to volume ratio provides special conduction and optical properties that find potential applications in optoelectronic devices including flat-panel displays and optical limiters for ultraviolet region.99,100 However, conventional methods to make nanostructures of these electronic materials usually need complex equipment, catalysts , and hence, prepared "-Ga2O3 using such a method could face contamination issues due to the presence of residues of the catalyst . Electrospinning , an alternative and cost-effective method for making nanofiberous metal oxides, should eliminate the possibility of contamination. Zhang et al.101 have prepared Ga2O3 nanoribbons by electrospinning using a solgel containing Ga(NO3)38H2O and PVP. Polymers , such as oligo- and polyfluorene as well as their derivatives are also excellent candidates for optoelectronic applications because they exhibit excellent fluorescence quantum yields, high thermalchemical stability, and significant charge carrier mobility.102 The prepared electrospun nanofibers of polyfluorenenonconjugated polymer with a poresize of 50150 nm has exhibited better luminescence efficiency. Strong stretching forces exerted during electrospinning is involved in the orientation of polymer chains along the long axis of fiber.20 Such oriented electrospun nanofibers of conjugated polymers have exhibited higher chargecarrier mobility15,103,104 and photoluminescence.105 107 Aggregation of polyfluorene in the electrospun fibers has also been found to be smaller than that of spin coated films due to the geometrical confinement of the electrospinning process and, consequently, resulted in higher luminescence efficiency.102 The electrospinning induces orientation along the axis of a fiber by strong stretching forces associated with electric potential.102

Another metal oxide tantalum pentoxide (Ta2O5) has been widely investigated because of its promising application in MOM or MOS capacitors108,109 wave-guides.110 Dharmaraj et al.111 have recently demonstrated that tantalum pentoxide nanofibers can be conveniently prepared by electrospinning . The precursor, tantalum isopropoxide with PVAc (11.5 wt%) is electrospun into nanofibers by applying a high voltage of 16 kV and keeping 17 cm as the distance. Calcined nanofiber mats lead to the formation of porous and pure tantalum oxide nanofibers.111 6. Transistors The electrospun nanofibers of binary blends of conjugated polymers have tunable, composition-dependent, optical, and electronic properties that can be exploited in field-effect transistors (FET). Tunable luminescence characteristics can be demonstrated on the electrospun nanofibers of conducting polymers . Recently, the morphology and photophysical properties of electrospun nanofibers based conducting polymers have been studied for field effect transistor devices. Babel et al.20 have investigated the electronic properties of electrospun nanofibers of MEHPPV with regioregular P3HT (Mw = 19 400),

which were prepared by electrospinning using a coaxial two-capillary spinneret arrangement. For MEH PPVP3HT blend fibers, the P3HT is dispersed in the nanofiberous matrix of MEHPPV as particles. The study demonstrated that MEHPPVPHT blend nanofibers exhibit p-channel transistor characteristics with hole mobility in the range of (0.051) & 10%4 cm2 (Vs)%1 as nonwoven mats.20 Efficient energy transfer and enhanced red emission from P3HT have been observed in MEHPPVPHT blend nanofibers which clearly indicate that stronger interaction occurs when compared to bulk thin films due to confined nanofiberous structures. Davies et al.30 have shown that yttria stabilized zirconia can be successfully electrospun from a solgel precursor (ZrOCl28H2O and PVP) and that annealing at 1500 C for 1 h resulted in a nanofiberous structure of pure zirconia. The fiber diameter was found to decrease with increases in annealing temperatures, and when average grain size increased the conversion of tetragonal to monoclinic structure occurred.30 Similarly, the anatase to rutile phase transition temperature observed by Kumar et al.112 for TiO2 nanofibers was found to be dependent on the nanoparticles ' size and packing density (Fig. 10). The lower the fiber diameter, the higher the surface area would be, which suggests that interaction between the surface charges and the forces that hold the particle are higher for fibers of smaller diameter. The absorption spectra of the fibers showed a red shift with an increase in fiber diameter. The excitonic peak showed a shift of 15 nm when the diameter of the fiber increased from 60 to 150 nm.112 Thus, the diameter should determine the electronic property in electrospun nanofiberous metal oxide ceramics.

Fig. 10 X-ray diffraction (XRD) patterns of electrospun TiO2 nanofibers showing the formation of anatase and rutile phases upon heat treatment.

7. Environmental applications It can be inferred that membrane or filtration systems offer a potential solution for a wide range of environmental issues. Therefore, it is no surprise that membrane technology and its industrial applications have expanded considerably in the last 50 years. Environmental purposes, such as water and wastewater treatment, as well as air purification exert the greatest demand on membraneusage. Slightly more than half of membrane usage is presently for water and wastewater applications.113 Membrane processes are valued as a significant technological advancement for ensuring a sustainable future for mankind.114 A membrane is defined as a semi-permeable barrier that allows only certain molecules and compounds access through it and denies passage to others. This is illustrated in Fig. 11 where only fluid is allowed to pass through the membrane and the contaminants in the fluid are prevented. The transport of these molecules or compounds across a membrane takes place by a sieving mechanism, or by diffusion of materials through it. Essentially, membranes are also referred to as filters that result in the separation of materials in a mixture. Rejected molecules or compounds can be prevented from passing through the membrane because of the tight pores at its surface. In this case the membrane functions as a screen filter. Alternatively, the molecules and compounds can also be rejected by being adsorbed or entrapped within the porous structure of the membrane in which case the membrane is referred to as a depth filter.

Membrane processes are now well established technologies for remediation of environmental problems such as water and air treatment. However, membrane technologists are constantly striving to push the envelope of membrane performance i.e. to get more output with less input. To serve as an effective environmental technology or solution it is imperative that the process be as energy efficient as possible, since energy and environment are inexplicably linked. It is anticipated that the future of membrane technology lies in the development of more efficient and energy saving membranes . Nanofiber membranes made from electrospinning are potentially advanced membrane systems that can offer removal of pollutants from the environment at lower energy and hence cost. In the following sections we review some of the applications of nanofiber membranes for the environment, focusing on air purification and water treatment applications. 7. 1 Air filtration applications

Environmental applications of nanofiber membranes for air filtration started in the early eighties and has expanded in the last three decades. With industrialization, air quality has deteriorated in some places, requiring a regeneration of air through filtration and other processes. Furthermore, stricter emission limits have also contributed to the need for better quality filtration media. Airfiltration spans a wide range of applications. From the removal of particulate materials from work environments, such as high dust loading industrial facilities to specialized applications, such as providing protection to individuals from toxic agents in the air. Today, nanofiber mats are used in numerous air filtration applications, either on their own or in combination with other filtration media. The growth in use of nanofibers for air filters have been pioneered by a few companies. These companies have been highlighted in previous reviews.115,116 Compared to conventional filtration media, nanofibers are of much smaller dimensions. The nanofibers used in filtration can be up to 800 times smaller than conventional filtration fibers. Smaller fibers generally provide better efficiency due to inertial impaction and interception, which makes up for the increased pressure drop when compared to bigger fibers.117 In addition, for nanometre sized fibers, the consideration of slip flow at the fiber surface implies a decrease in drag force on the fiber and therefore a reduced pressure drop. The occurrence of slip flow also results in more contaminants passing near the surface of the fibers, which increases the inertial impaction and interception efficiencies of the fibrous mat. Overall, this results in nanofiber mats that can achieve much higher efficiency for the same pressure drop as compared with conventional fiber mats. The cut-off diameter of the fiber for slip flow consideration at its surface is approximately 500 nm.118 This advantage and huge surface area to adsorb contaminants from air, have made nanofiber membranes an increasingly popular choice in air filtration applications. Below, we highlight some of the work that has been carried out or is being looked at in the application of nanofibers for air filtration . 7. 2 Dust capture applications Dust refers to solid materials found in air with diameters smaller than 500 mm. Dust can come from natural sources such as soil swept up due to wind, from volcanic eruption or can be due to pollution. In most cases dust is a respiratory allergen but in some prolonged cases of exposure can even result in death , such as with the dust from coal mines. Dust capture is therefore an important process, to protect the individual particularly in enclosed spaces and is commonly incorporated in the ventilation system. Nanofibers based filters are increasingly being used in tandem with conventional filter media for dust capture purposes. Conventional filter media such as glass fibers exhibit depth loading characteristics when exposed to industrial dust environments. These media become clogged up over time and there is reduced airflow through the media as a result. When a nanofiber web is used, due to its smaller pore sizes, it is able to capture the dust particles on its surface. These particles can then be removed by back flushing or through other mechanical means. This implies that nanofiber based or nanofiber composite filters have a higher shelf

life when compared with conventional filters. In comparison, other composite media do not exhibit as high permeability as the nanofiber filters.119 7. 3 Vehicle cabin filters Contamination by airborne contaminants or particulates in enclosed places where personnel work and operate in is an important concern. Examples of such places include cabins in machinery and equipment such as in mining work, airplane cabins, etc. Often wet-laid cellulose filter media is used to minimize the cabin dirt concentration, hence providing a safe environment for people in these areas. The effectiveness of nanofiber media in reducing the cabin contaminant concentration has been investigated using a composite cellulose/nanofiber filter and comparing it with a standard (wet-laid cellulose) filter.120 The filters have been tested independently on a Caterpillar 992G wheel loader, mounted with two particle sampling devices, one inside the cabin and the other outside. With the standard cellulose filter, a reduction in sub-micron and respirable (>1 !m) dust of 68% and 86%, respectively, has been noted. However, with the nanofiber composite filter a higherreduction of approximately 92% has been observed for both the sub-micron and respirable dust. Further tests revealed that the nanofiber filter life and initial pressure drop were comparable with the standard filters.121 7. 4 Building filters Indoor air filtration is another important environmental concern. This is especially so, since we spend a large part of our lives in an indoor environment. From residential homes, to work offices, to hospitals, air filtration is an important requirement for ensuring a safe and refreshing environment to be in. Contaminants which can be circulated in these enclosed buildings can lead to severe health effects, the most common known as sick building syndrome. This is where occupants of a building, usually an office block, feel nauseous when inside the building. In hospitals where diseases are treated, the circulation of air can be tricky and filters which are able to prevent viruses and germs from spreading through the air circulation system are essential. If not prevented this could cause disease to spread throughout the hospital. Nanofiber membranes are a potential solution for indoor air filtration applications. Due to their high surface area and porosity, they not only capture the contaminants in the building circulation system but also allow more air to pass through. This implies that less energy is required to pump the air through the filters resulting in a sustainable solution. In addition, nanofibers can be functionalized to increase their capture efficiency or for specific applications, and to improve their properties e.g. make the filters antimicrobial. This will be discussed subsequently. 8. Personal respiratory protection from biological and chemical agents

Nanofibers are also increasingly being used for individual protection purposes. Their use in breathing masks has increased greatly in the last couple of years. Besides ensuring better breathability, they are also capable of removing very small particles such as viruses.122 With further functionalization of the nanofibers, improved performance can result from these materials. Our researchgroup is engaged in the functionalization of the membranes for removal of certain persistent contaminants in the air. Some of these applications are highlighted below. Protection from biological and chemical agents is commonly achieved through protective suits and face masks. These are extremely important for the many personnel who are exposed to these agents on a frequent basis, such as personnel from the military, fire and rescue services and law enforcement. The major limitations of current protective materials are weight and moisture retention, which reduces the wearers' comfort during periods of prolonged usage. The use of nanofiber webs in place of current materials e.g. activated carbon could reduce these problems. Firstly, nanofibers are light-weight materials, which can be easily embedded into current suits and face masks.123 Secondly, the nanofiber membranes can provide protection against aerosols and other liquid penetration. This is pertinent because chemical agents are commonly delivered as aerosols. In addition, through functionalization of the nanofiber membranes it is also possible to not only adsorb the biological and chemical agents but to decompose and detoxify the contaminants as well. This will potentially eliminate the tedious tasks of handling the hazardous used masks and suits. Ramakrishna et al.124 have demonstrated that it is possible for functionalized nanofibers to be produced that can provide protection and detoxification of chemical warfare stimulants. To mimicenzyme functionalities, a chemical compound (3-carboxy-4-iodosobenzyl) oxy-"-cyclodextrin has been synthesized and electrospun with polyvinylchloride (PVC) into nanofibers. The functionalized nanofibers have been found to outperform activated carbon and even powerful nucleophiles e.g. iodobenzoic acid and "-cyclodextrin in detoxifying paraoxon an organophosphorous (acute neurotoxin ) model.124,125 In another study, it has been found that ceramic zinc titanate nanofiber had a decomposition efficacy of between 7791% for paraoxon (nerve agent) and 6469% for CEES (2-chloroethyl ethyl sulfide) (mustard agent). 9. Liquid filtration applications Nanofiberous media or membranes are increasingly being looked at as a solution for providing water at lower energy costs. Nanofibers due to their higher porosities and interconnected porestructures offer a higher permeability to water filtration over conventional materials being used. Below, some examples of nanofibers being used in liquid filtration are explored. 9. 1 Removal of micron sized particles and suspended solids Removal of micron sized and other suspended solid particles such as flocs, bacteria etc. is important in both water and wastewater treatment applications. Cryptosporidium parvum and Giardia lamblia are

pathogenic protozoans whose symptoms include severe diarrohea, stomach cramps, nausea and vomiting. Following past outbreaks of diseases due to these protozoans and the lack of an effective treatment their removal from waters is now made compulsory in many countries.126 Membrane processes such as microfiltration and ultrafiltration are well known to achieve high rejection rates of micron sized and other suspended solids from waters. These have become a popular means to achieve not only purification but disinfection of water to remove these pathogenic bacteria. Presently, MF and UF membranes are still being produced by the phase-inversion method 127 and by dry formed methods for fibrous membrane media such as spun bonded and melt blown techniques.128 Electrospun membranes are another method through which these MF and UF membranes can be obtained and is postulated to grow significantly in the coming years. Kaur et al.129 have compared the filtration performance of a commercial MF membrane with an electrospun nanofiber membrane of the same polymeric material. The electrospun nanofibermembrane (ENM) had a water flux several times higher than the commercial membrane at the same applied pressure. However, the pore size of the ENM has been found higher when compared to the commercial membrane , therefore although it will produce a higher flux, it will also result in a smaller rejection for the same feed water through both membranes . To test if the nanofiber architecture could contribute to higher filtration flux at the same pore size, grafting has been carried out on the ENM to reduce its pore size. Graft-copolymerization with methacrylic acid has been carried out on the ENM , such that only the top layer of the nanofiber membrane has been modified and the nanofiber architecture maintained. The grafting reduced the average membrane poresize and bubble point to that of the commercial MF membrane . In addition, the contact angles of both the commercial and grafted ENM have also been found to be similar. The water flux of the grafted ENM has been found to be approximately 150200% higher than the commercial membrane . This showed that the nanofiber architecture is better than the phase inverted and could result in energy saving membranes . Gopal et al.130 have also explored the removal of micron sized particles using nanofiber membranes made from polysulfone. The membrane pore sizes could be adjusted by altering theelectrospinning conditions. For comparison a nanofiber membrane of fixed pore size has been filtered for different polystyrene particles of various sizes under the same operating conditions. The rejection of the particles by the membranes decreased with the size of the particle. A clear change from the operation of the membrane as a screen filter to a depth filter has been noted as the particle size decreased during the experiments. More significantly, membrane fouling was the most severe when the particle sizes separated were close to the mean pore size of the membrane . This is likely to be due to the occurrence of pore blocking mechanisms. Fig. 12 shows a clean PSU nanofiber membrane and a fouled PSU nanofiber membrane after filtering particles of approximately 1 !m. The nanofiber membrane was able to effectively capture most of the particles passing through.

10. Heavy metal ion adsorption

Heavy metals are a serious biological problem in aquatic systems. Adsorption and filtration are the commonly used methods for removal of these contaminants. The advantage of nanofibermembranes is that they can offer both adsorption and filtration . Therefore, nanofiber membranes offer an attractive solution to the removal of heavy metals from water. In a recent study,131 silk fibroin and a blend of silk fibroin with wool keratose was electrospun into membranes and tested for the removal of heavy metal ions. It has been noted that the adsorption capacity was significantly enhanced when nanofibers (1.652.88 mg g%1) were used, as compared to conventional materials like wool silver (0.71 mg g%1) and filter paper (0.23 mg g%1) tested for removal efficiency of heavy metals. The higher adsorption has been attributed to the larger surface area of the nanofiber membrane . In another study to investigate the impact of impregnating boehmite nanoparticles into electrospun nanofibers, it has been found that a removal efficiency of approximately 0.20 mg g%1 forcadmium(II) in water could be achieved.132 It is anticipated that further optimization of the nanoparticles ' concentration and the polymer could potentially achieve higher removal efficiency for heavy metal ions. 11. Adsorption of organic compounds Organic materials in water can pose health hazards and need to be removed from drinking water. Functionalized nanofiber membranes offer a promising solution for the removal of organic molecules in water. Kaur et al.133 have studied the removal of phenolphthalein as a model organic molecule from water using a poly(methylmethacrylate) (PMMA) nanofiber membranefunctionalized with phenylcarbomylated and azidophenylcarbomylated "-cyclodextrins. The membranes have been functionalized with the oligosaccharides by blending them in the PMMA solution and then electrospinning . The membranes were able to capture the phenolphthalein molecules, but could be further optimized to increase the adsorption capacity. Nevertheless, this exemplifies how nanofiber membranes can be used for the adsorption and removal of organic molecules in water systems. Humic acid is a commonly encountered natural organic matter in water. These compounds are considered to be polydisperse, structured polyelectrolytes of an amphiphilic nature.134 Our groupattempted to utilize nanofiber membranes for the removal of humic substances from water. Nanofiber membranes on their own are able to adsorb some of the humic materials from water. However, the adsorption capacity and removal could be increased by functionalizing the membrane . In unpublished data, we blended surface modifying macromolecules with PVDF and electrospun them into nanofiber mats. We found that through this, humic acid rejection of 92% could be achieved at a pressure of only 0.25 psi. Further work is being carried out to functionalize the nanofiber membranes for removal of humic and other organic substances. Another local group has explored using titanium dioxide nanofibers for the removal of humic acids.135 The advantage of TiO2 nanofibers is that they can function both as a filtration membraneand as a photocatalyst. Their results indicate that TiO2 membranes when used as a photocatalyst can achieve almost 100% removal efficiency.

Oil is another organic material that is sometimes present in water sources due mostly to industrial discharge. The removal of oil has been investigated using a 3-tier membrane stack, with the middle tier composed of polyacrylonitrile (PAN) nanofibers.136 It has been found that the membrane system has been able to remove a high percentage of soyabean oil at a higher permeation rate compared with conventional ultrafiltration membranes . Proteins are another group of commonly encountered organic compounds, particularly in wastewater applications. The removal of proteins has been achieved using polysulfone nanofibermembrane surfaces modified with carboxyl groups . The nanofiber membranes had an adsorption capacity of 17 !g mg%1 for bovine serum albumin (BSA), a model protein .137 Disinfection by-products (DBPs), which form due to the reaction between chlorine and organics, are potential carcinogens. Their removal is important in potable water. Our group have been focusing on the development of hydrophobic based nanofiber mats for the removal of these DBPs. Preliminary results have suggested that such high filtration flux nanofibers can achieve approximately 2030% removal of DBPs. Further tests are being carried out to increase the rejection performance of the membranes . 12. Functionalized nanofibers with bactericidal effects Nanofibers can also be functionalized to serve as potential antimicrobial filters in air and liquid filtration . In addition, the antimicrobial property of nanofibers is also desired when these are used in protective clothing and wound dressing applications. Silver ions and silver compounds have long been recognized as potent antimicrobial agents . Silver nanoparticles are increasingly being used in various antimicrobial applications, due to their increased surface area.138 The incorporation of silver nanoparticles into nanofibers offers synergies of two nanotechnologies. The silver nanoparticles can be incorporated onto the nanofiber membranes by several methods. Silver nanoparticles can be electrosprayed onto the surface of the nanofiber membrane , thus producing a layer of antimicrobial protection on it. The silver nanoparticles can also be blended with polymers and then electrospun. However, this can result in most of the silver nanoparticles being embedded into the polymer fibers. Growing nanoparticles on the surface of fibers is perhaps the most effective method for producing nanofibers with antimicrobial properties. This can be achieved by mixing a silver salt or sol with a polymer in a solvent and electrospinning the mixture. The collected mat containing silver ions on the fiber surface is subsequently reduced by subjecting the membrane to heat treatment, photoreduction e.g. UV irradiation or both.139,140 Lala et al.141 have successfully developed silver impregnated antimicrobial filters using a number of different polymers , and have tested their antimicrobial effectiveness using two gram-negative bacterial groups : E. coli and P. aeruginosa. The membranes showed good antimicrobial activity when incubated with bacteria, consistent with other reported data in the literature. Fig. 13shows (a) an SEM image of nanofibers collected with antimicrobial properties and (b) the TEM image of a single fiber with silver nanoparticles on its surface.

No study has so far been carried out to test the filtration performance and disinfection efficiency of the silver impregnated nanofiber membranes in a flow through system. Our group is presently studying this aspect. There is potential for the membranes to be used as an alternative to conventional disinfection methods such as chlorination and UV disinfection in water treatment orwater reuse. Besides silver nanoparticles , antibacterial polymers have also been incorporated into electrospun fibers to enhance their bactericidal properties. Commonly, quaternary ammonium salts or their derivatives or polymers with biguanide groups have been blended with polymers to provide antibacterial properties.142 Fan et al.143 have tested the bactericidal properties of alginate andcarboxymethyl chitosan blended nanofibers, when (a) untreated, (b) treated with N-(2-hydroxy)-propyl-3-trimethylammonium chitosan chloride (HTCC) and (c) treated with silver nitrate. They have found that silver nitrate treated nanofibers had the best reduction rate (>99.99%) of Staphylococcus aureus, when compared with HTCC (8690%). However, this was still much higher than the untreated nanofibers which had a bacterial reduction rate of 510%. In another work, quaternary ammonium salts generated on electrospun diblock copolymers by N-alkylation of tertiary amine groups were tested for their antibacterial efficiency.144 The nanofibers were found to exhibit high antibacterial characteristics with 95% of E. coli and 97% S. aureus killed within 10 min of contact with 50 mg of fibers. 13. Ion exchange The use of nanofibers in ion exchange is still in its infancy. A study conducted using polystyrene nanofibers was able to achieve a maximum ion-exchange capacity of 3.74 mmol g%1.145 This value is comparable with commercially available ion-exchange membranes . The research suggests that ion-exchange membranes can be produced using nanofibers and there is good potential to increase its performance further. 14. Membrane distillation Membrane distillation is a filtration process that uses thermal energy as a driving force. The membrane usually separates two liquids that are of different temperatures, with transport of liquid taking place from the higher temperature side (feed) to the lower temperature side (permeate).146 Currently, membrane distillation processes employ commercially available hydrophobicmicrofiltration membranes . Nanofiber membranes can be used in membrane distillation directly, because the nanofiber mats generally exhibit high surface hydrophobicity. In addition, the high porosity and interconnected open pore structure characteristics of the nanofiber membrane could potentially enhance the membrane distillation process. Feng et al.147 have studied the use of poly(vinylidene fluoride) PVDF nanofiber membrane in an air-gap membrane distillation system.

The preliminary results have been promising, with NaCl salt rejection rate of approximately 99.099.9% reported for various feed concentrations. The permeate flux of the nanofiber membrane ranged from approximately 1.5 L m%2 h%1 when the temperature difference between the liquids was 15 C to approximately 1112 L m%2 h%1 when the temperature difference between the liquids was 60 C. These values are comparable with commercial membrane distillation membranes . However, with further optimization of the nanofiber membrane improved performance is possible. 15. Membrane applications in bioengineering In the bioengineering area, there is strong potential for nanofiber membranes to be used. The purification of biomolecules, such as proteins is an important step in many bioengineering processes. For example, antibody purification is a critically important step in the preparation of biopharmaceuticals and in the application of immunodiagnostics and immunotheraphy. Protein purification is commonly carried out using several techniques such as ion-exchange chromatography , gel filtration , ultrafiltration , affinity chromatography , high resolution reversed-phase chromatography , hydrophobic interaction chromatography . Of these methods, affinity chromatography and in particular affinity membranes provide a promising means of protein purification . Affinity membranes generally consist of microfiltrationmembranes to which specific selectiveaffinity ligands are attached. In addition to the usual sieving mechanisms of membrane systems, affinity membranes also allow the capture of proteins on the adsorption sites due to the immobilized ligands. Current microfiltration membranes produced by the phase-inversion or spunbonded methods tend to have low porosity.148 This reduces the surface area of the membranes available to the ligands and therefore the protein binding . Additionally, a lower porosity also implies a higher pressure drop during operation. Hence, more energy efficientmembranes , with higher surface areas would greatly increase the performance and potential of the affinity membranes for biomolecule purification . Nanofiber membranes made fromelectrospinning offer these advantages and are of the same size range as microfiltration membranes . As a proof of concept, regenerated cellulose nanofiber membranes have been electrospun and functionalized with protein A/G.149 Immunoglobulin G (IgG) has been used to test the capture efficiency of the nanofiber membrane . It has been found that the electrospun nanofiber affinity membrane had an IgG binding capacity of 18 !g mg%1. The nanofiber affinity membrane has been reported to have a binding capacity almost double that of a commercial affinity membrane . 16. Sensors for environmental applications A key feature of an environmental management strategy is the detection of threats to the environment. Sensors are important tools that allow detection of contaminants in the environment. Nanofiber based sensors are gaining popularity. Below, some of the nanofiber based sensors which can be used to detect pollutants in the environment are highlighted.

16.1 Sensors in liquid applications The use of nanofiber templates for sensors in environmental applications is also gaining prominence. There are many pollutants in water that exist in small concentrations. These trace contaminants, such as pharmaceuticals , cosmetics, hormones etc. are potential carcinogens and can cause other health problems when present in water.150 Their detection is often difficult to achieve, because they occur in parts per billion concentrations. Nanofiber based membranes are now also offering potential means of detecting these compounds in water. Molecularly imprinted nanoparticles encapsulated in polymer nanofibers have been found to be capable of detecting trace amounts of propranolol (1 ng mL%1) in tap water. Interestingly, the encapsulated nanoparticles remain accessible and are chiral selective.151 Similar work has been carried out for theophylline and 17"-estradiol imprinted nanoparticles encapsulated in polymeric nanofibers, which allowed the detection of these compounds in water.152 The advantage of introducing molecularly imprinted nanoparticles into the nanofiber membrane rather than using them on their own is that the subsequent collection or recovery of the nanoparticles from water is no longer an issue. Additionally, the nanofibers have a huge surface area compared with conventionalmembrane materials, so the sensitivity can be increased. Working with molecule imprinted nanofiber membrane systems opens up interesting avenues, and opportunities for sensor development inwater and wastewater analysis. Consequently, it could also aid in the selective removal of various harmful pharmaceuticals e.g. endocrine disrupting compounds and contaminants in water. In cases where small concentrations of industrially important compounds are present in water, but which could result in severe problems to the environment, their detection could serve as a means of reclaiming these compounds for recycling in the manufacturing process. This will aid in limiting the increasing prevalence of trace contaminants in the environment due to the manufacturing process. 16.2 Sensors in gas applications Air pollution as a result of industrialization is a serious problem in many developed and developing countries. Gaseous nitrogen oxides (NOx) and sulfur oxides (SOx) produced primarily due to the coal combustion process and automobiles, cause severe environmental problems such as acid rain, smog, ground level ozone, acidic aerosols etc.. These have far reaching consequences on the ecosystem and in many cases direct toxicology effects on humans. Greenhouse gases e.g. carbon dioxide (CO2), methane (CH4) etc are another important class of air pollutants, which are widely regarded to be responsible for the global warming effect. Emission caps for these gases is widely regulated in most countries and with impending carbon emission regulations to be imposed globally, the detection and measurement of these gases by industries is an important area. Nanofibers could play an important role as gas sensors for the detection of acceptable emission limits for a variety of gases. Most nanofiber membranes used as gas sensors, tend to be of ceramic materials. These ceramic nanofibers can be produced by a combination of solgel and electrospinning techniques.125Gouma et al. have shown that

electrospun fibers from molybdic oxide (MoO3) and tungsten oxide (WO3) could be used for detection of NO2 and NH3 in air, respectively.153,154 The nanofiber gas sensors have been found to have superior characteristics in terms of response time and sensitivity when compared with thin-film structures of the same materials. The sensors have been capable of detecting concentrations of approximately 50 ppm of NO2 and 10 ppm of NH3 using the respective electrospun nanofibers, MoO3 and WO3. Medrignac-Conanec et al.155 fabricated a mixed metal oxide nanofiber membrane consisting of molybdenum and tungsten oxides using electrospinning . They reported that this combined material could simultaneously detect a number of gases e.g. ozone, nitrogen oxide and nitrogen dioxide. It is also possible to use other combinations of metallic compounds to detect the same gas analyte , e.g. electrospun lanthanum copper oxide (La2CuO4) nanofibers, which have been used to measure NO concentration.156 The advantage of using ceramic nanofibers as gas sensors, is that they can be operated to detect gases at higher temperatures. This is useful in many industrial applications, where effluent gases released are of a high temperature. The future gas sensors besides, having a quick response time would have to be more sensitive. This implies that they should be able to detect gases in the parts per billion range and not only the current parts per million ranges. In order to meet this goal, fiber diameter would have to reduce significantly. Electrospinning continues to be an attractive method to produce these nanofibers. Kimet al.157 have showed that TiO2poly(vinyl acetate) composite nanofiber produced using electrospinning followed by hot-pressing and calcination , resulted in a highly sensitive NO2 gas sensor. It has been reported that the detection limit of the sensor to NO2 was estimated to be below 1 ppb. In addition, indium oxide has been found to be a highly sensitive material for the detection ofseveral gases e.g. CO, NH3, O3, CO2, H2, NO2 and Cl2.158,159 Therefore the electrospinning of indium oxide nanofibers and/or composite materials would be extremely useful for future gas sensor applications. 17. Conclusions and prospects for electrospun nanofibers Energy and the environment are the most important factors that influence the shape of society in the 21st century. Nanosized fibers have great advantages due to their high surface area to volume ratio, electrospun nanofibers have potential applications in the field of clean energy (solar cells , fuel cells and batteries), electronics, health (biomedical scaffolds, artificial organs), and environment (filter membranes ). Current advances in electrospinning technology provide important evidence of the potential roles in energy conversion and storage as well as water, and air treatment applications. Though electrospinning has become an essential technique for generating 1D nanostructures , the research exploration is still young, but promising, in energy applications. One of the drawbacks of electrospinning is that, it has been difficult to obtain uniform nanofibers with diameters below 50 nm using electrospinning . Another drawback is the relatively low production rate. In the near future, it is likely that research efforts will be focused on engineering the electrospinning process, with the ultimate goal of producing nanofibers with diameters below 50 nm, and at a faster rate. In the long term, it is expected that vertical patterned nanofibers, an ideal morphology using electrospinning , should be possible to produce in order to achieve maximum

electron transport in energy and electronic devices and controlled pore sizes for environmental filtration . This will require dedication and research collaboration within electrospinningresearch communities around the world. Nanofiberous membrane processes represent a key technology that provides a solution to pollution in water and air environments. It is anticipated that the future of membrane technology lies in the development of more efficient and energy saving membranes . Furthermore, the development of clean energy and environment technology will provide enormous opportunities for the creation of high value added products and associated business development. Hence, interest in ES technology is not only restricted to academic research laboratories, but also world-renowned companies such as Dupont, Johnson & Johnson, Donaldson, Teijin and, eSpin Tech etc. have been involved to produce nanofiberous products for improved performance. Ultimately, for electrospinning technology to progress further, there is an essential need to move away from high cost and/or exotic materials to low cost, non toxic or pollution free materials. Current electrospinning processes involve the use of organic solvents , which are toxic, corrosive and detrimental to the environment. This may warrant further scale up for fullyfledged industrial production. Developing the electrospinning process using water based solvents or watersoluble reagents to produce nanofibers will make the process ecofriendly and open up the way for industrial production. Our research group is focused on such research under the theme of greenelectrospinning by developing and implementing water soluble but still spinnable polymers .

COMPOSITES Over the past six decades, engineered composite materials found wide ranging applications in land, sea and air transport vehicles, space exploration, military equipment and defense, storage, buildings and construction, chemical processing, electrical engineering, healthcare, and general engineering industries. Performance of engineered composites is tailored for a particular application by judiciously selecting the matrix and reinforcement materials, by modifying the fiber/matrix interface, and by controlling the architecture of fibers in the matrix. Most widely used reinforcement fibers are micron size diameter fibers. There is growing need for engineered composites with enhanced structural performance in newer applications as well as existing applications that are expected to meet higher functional requirements and enhanced safety requirements. Moreover, the global movement towards sustainable development is seeking engineered materials that are environmentally benign. Recently, the electrospinning process has emerged as a viable industrial process to produce nanofibers from a variety of materials including naturally occurring materials.

Nanofibers into the matrix

Recent studies regarding the incorporation of electrospun nanofibrous mats into CRFP laminates demonstrated that nanofibers are able to increase Mode I and Mode II fracture behaviors as well as they significantly influence the dynamic response of the laminate. In particular the free decay vibration test showed that the nanomodified laminates are characterized by an improved damping ratio respect to the virgin ones. Moreover, in the case of low velocity impact the presence of electrospun nanofibrous mats into laminates reduces the damage "extension" respect to the case of virgin laminates. The utilization of nanofibrous mats to produce hierarchical nanomodifed composites is the key to the development of a new class of cost effective composite material characterized by superior performances.