Bhupender S. Gupta

Co‐axial Electrospinning for Nanofiber Structures: Preparation and Applications

Preparation of nanofibers in a core‐sheath configuration, using two dissimilar materials, via a novel technique of co‐axial electrospinning has presented unusual potential for use in many novel applications. The studies have addressed issues related to the technology involved and examined the suitability of the technique for producing unique nanoscale morphologies involving variety of materials. In this first major review of co‐axial electrospinning, we provide details of the manufacturing and material factors affecting the process, the conditions needed for preparing desired uniform morphologies, and the different types of structures that have been successfully produced.

Grafting of vinyl monomers to cellulose by ceric ion initiation

Cinetique et mecanisme. Conditions affectant le greffage. Caracterisation des produits greffes. Proprietes des produits greffes

Biomechanics of human common carotid artery and design of novel hybrid textile compliant vascular grafts

The mechanical properties and structure of a human common carotid artery were studied in order to develop criteria for designing and manufacturing compliant textile vascular grafts. The arterial wall comprised a composite of elastin and collagen fibers with the collagen fibers crimped. This structure led to a unique pressure-circumferential stretch ratio curve, the slope of which increased with an increase in strain. The increase in slope was particularly rapid at a stretch ratio above 1.4 or pressure above 120 mmHg. Based on the knowledge gained, a criteria for the design of biomechanically compliant arterial grafts was developed. An elastomeric prestretched polyurethane monofilament yarn with a low modulus of elasticity and a bulked polyester multifilament yarn with a high modulus of elasticity were combined and used as threads in the manufacture of grafts. Tubular structures of diameters in the range 4-6 mm were made by weaving. Transverse compliance and morphological and permeability properties of these grafts were determined and compared with those of a currently available woven commercial grafts and human carotid arteries. Results indicated that the compliance values of the hybrid grafts were comparable with those of the human carotid artery. Preliminary in vivo studies in dogs showed promising results: a thin, stable neointima developed within 6 months of implantation on the flow surface.

Friction in Fibrous Materials Part I: Structural Model

The classical laws of friction adequately describe the behavior of materials that deform plastically but fail to do so in fibers that deform viscoelastically. This paper presents a structural model that characterizes friction in fibrous materials. The theory is general and can account for the behavior of a wide range of materials. The model provides a theoretical base for the empirical equation F = aNn, which has been fitted successfully to experimental data from previous investigations. It gives theoretical meaning to the indices a and n, which heretofore were empirical constants, and brings out the factors, structural as well as procedural, that affect their values. The factors affecting friction in fibers are shown to fall in two main groups, one governing the morphology of contact and the other the mechanical properties of the junctions. A detailed discussion of these factors is given in this paper. The results of an experimental investigation, where acrylic and polypropylene yarns varying systematically in structure were the materials, will be submitted for publication later. Friction is measured in dry and wet media using both line and point contact methods. The effects of structural factors are examined and interpreted in light of the model.

Effect of blend ratio on bulk properties and matrix-fibril morphology of polypropylene/nylon 6 polyblend fibers

Ternary blends of polypropylene (PP), nylon 6 (N6) and polypropylene grafted with maleic anhydride (PP/N6/PP-g-MAH) as compatibilizer with up to 50 wt% of N6 were investigated. PP-g-MAH content was varied from 2.5 to 10%. Blends of the two polymers PP/N6 (80/20) without the compatibilizer were also prepared using an internal batch mixer and studied. The ternary blends showed different rheological properties at low and high shear rates. The difference depended on the amount of N6 dispersed phase. Co-continuous morphology was observed for the blend containing 50% N6. This blend also exhibited higher viscosity at low shear rate and lower viscosity at high shear rates than the value calculated by the simple rule of mixture. At higher shear rates, viscosity was lower than that given by the rule of mixture for all blend ratios. An increase in viscosity was observed in the 80/20 PP/N6 blend after the concentration of the interfacial agent (PP-g-MAH) was increased. Polyblends containing up to 30% N6 could be successfully melt spun into fibers. DSC results showed that dispersed and matrix phases in the fiber maintained crystallinity comparable to or better than the corresponding values found in the neat fibers. The dispersed phase was found to contain fibrils. By using SEM and LSCM analyses we were able to show that the N6 droplets coalesced during melt spinning which led to the development of fibrillar morphology.

Moisture Vapor Transport Behavior of Polyester Knit Fabrics

A test method that measures microclimate drying time is used to compare the ability of different knit materials to dissipate moisture vapor from a saturated clothing environment to the ambient atmosphere. The performance assessment provided by this novel method is compared with those from common test methods. The latter include measures of the moisture vapor transmission rate provided by the upright cup and the evaporative thermal resistance provided by the sweating guarded hot plate procedure. Upright cup and sweating hot plate measurements are shown to be predominately influenced by fabric thickness, but microclimate drying time, or the time-dependent dissipation of accumulated moisture vapor, assessed by the new method is most influenced by the pore characteristics of the fabric. Moisture vapor transmission through fabrics is assumed to be controlled mostly by fiber, yarn, and fabric variables that determine fabric thickness and porosity. Therefore, constructional variables that lead to thin knit structures, with unobstructed interyarn pores, are shown to be important considerations for designing fabrics with optimum moisture vapor dissipation properties.

Friction in Fibrous Materials: Part II: Experimental Study of the Effects of Structural and Morphological Factors

In this part of the series, the effects of a number of structural and morphological factors on fiber friction are examined and rationalized on the basis of the structural model discussed in Part I. The factors are fiber cross-sectional shape, molecular ori entation, annealing, and fiber type. Friction tests have been conducted using techniques that allow measurements in both the point contact and line contact modes. Selected tests have also been done with the contact regions immersed in water. The results show that the coefficient of friction μ is higher for annealed than unannealed structures and increases with increasing molecular orientation. Circular fibers exhibit higher values than noncircular fibers. The value of the friction index a varies in the same fashion as the value of the coefficient of friction μ in all cases, except when fiber orientation is the variable. The friction index n increases with orientation and is higher for circular fibers than for noncircular ones. Wetting of the contact region or annealing of the structure has no effect on the value of n. Results are explained in light of the structural model presented in Part I.

Fabrication and Characterization of Poly(ε-caprolactone)/α-Cyclodextrin Pseudorotaxane Nanofibers.

Multifunctional scaffolds comprising neat poly(ε-caprolactone) (PCL) and α-cyclodextrin pseudorotaxanated in α-cyclodextrin form have been fabricated using a conventional electrospinning process. Thorough in-depth characterizations were performed on the pseudorotaxane nanofibers prepared from chloroform (CFM) and CFM/dimethylformamide (DMF) utilizing scanning electron microscopy (SEM), transmission electron microscopy (TEM), rheology, differential scanning calorimetry (DSC), thermogravimetric analyses (TGA), wide-angle X-ray diffraction (WAXD), and Instron tensile testing. The results indicate the nanofibers obtained from chloroform retain the rotaxanated structure; while those obtained from CFM/DMF had significantly dethreaded during electrospinning. As a consequence, the nanowebs obtained from CFM showed higher moduli and lower elongations at break compared to neat PCL nanowebs and PCL/α-CD nanowebs electrospun from CFM/DMF.

Poly(ε-caprolactone) Nanowebs Functionalized with α- and γ-Cyclodextrins

The effects of alpha- and gamma-cyclodextrins (α- and γ-CDs) on the thermal and crystal nucleation behavior of electrospun poly(ε-caprolactone) (PCL) nanofibers have been investigated. PCL/CD composite nanofibers were obtained for the first time by electrospinning the mixture from chloroform/N,N-dimethylformamide (60:40). Scanning electron microscopy analyses indicated that neat PCL nanofibers have an average diameter of 400 nm, which increases with the addition of CDs. The presence of CDs on or in the electrospun PCL fibers in the electrospun mats was investigated using Fourier transform infrared spectroscopy, thermogravimetric analysis, and wide-angle X-ray diffraction analysis. Differential scanning calorimetry showed that the PCL/CD composite fibers exhibit higher crystallization temperatures and sharper crystallization exotherms with increased CD loading, indicating the ability of CDs to nucleate PCL crystallization. Water contact angle (WCA) measurements indicate an inverse relationship between WCA and α- or γ-CD concentration up to 30% loading. Phenolphthalein absorption tests were performed to study the kinetics of their inclusion complex (IC) formation with CDs. Unexpectedly, γ-CD-functionalized nanowebs performed better than α-CD. This might be because at elevated loadings some α-CDs may have threaded over PCL chains and formed ICs, whereas γ-CD did not. With their encapsulation capabilities and their lowered hydrophobicity, PCL/CD composite fibers might have potential uses in medical applications, in particular as wound odor absorbants in dressings, because it is well known that CDs can form ICs with these odorants, thereby effectively removing them.

Collagen-PCL sheath-core bicomponent electrospun scaffolds increase osteogenic differentiation and calcium accretion of human adipose-derived stem cells.

Human adipose-derived stem cells (hASCs) are an abundant cell source capable of osteogenic differentiation, and have been investigated as an autologous stem cell source for bone tissue engineering applications. The objective of this study was to determine if the addition of a type-I collagen sheath to the surface of poly(ε-caprolactone) (PCL) nanofibers would enhance viability, proliferation and osteogenesis of hASCs. This is the first study to examine the differentiation behavior of hASCs on collagen–PCL sheath–core bicomponent nanofiber scaffolds developed using a co-axial electrospinning technique. The use of a sheath–core configuration ensured a uniform coating of collagen on the PCL nanofibers. PCL nanofiber scaffolds prepared using a conventional electrospinning technique served as controls. hASCs were seeded at a density of 20 000 cells/cm2 on 1 cm2 electrospun nanofiber (pure PCL or collagen–PCL sheath–core) sheets. Confocal microscopy and hASC proliferation data confirmed the presence of viable cells after 2 weeks in culture on all scaffolds. Greater cell spreading occurred on bicomponent collagen–PCL scaffolds at earlier time points. hASCs were osteogenically differentiated by addition of soluble osteogenic inductive factors. Calcium quantification indicated cell-mediated calcium accretion was approx. 5-times higher on bicomponent collagen–PCL sheath–core scaffolds compared to PCL controls, indicating collagen–PCL bicomponent scaffolds promoted greater hASC osteogenesis after two weeks of culture in osteogenic medium. This is the first study to examine the effects of collagen–PCL sheath–core composite nanofibers on hASC viability, proliferation and osteogenesis. The sheath–core composite fibers significantly increased calcium accretion of hASCs, indicating that collagen–PCL sheath–core bicomponent structures have potential for bone tissue engineering applications using hASCs.