Nanoparticle-based photothermal heating to drive chemical reactions within a solid: using inhomogeneous polymer degradation to manipulate mechanical properties and segregate carbonaceous by-products.

Photothermal heating via metal nanoparticles is utilized to degrade polyethylcyanoacrylate (PECA), which undergoes a thermally-driven depolymerization process, resulting in (i) monomer loss from the sample, (ii) repolymerization to form shorter chains (oligomer), and (iii) formation of carbonaceous by-products which are graphene-like and luminescent. These unique PECA properties are used to demonstrate the heterogeneous temperature distribution present during photothermal processing and the results are compared to degradation via conventional methods where a uniform temperature is present. Photothermal heating results in formation of pockets of depolymerized material around each nanoscale heating site. The characteristic size of these photothermally-generated mechanical defects is determined from changes in the material's tensile strength. Changes in mass loss and molecular weight are utilized to determine the fraction of the sample that has depolymerized: distributing this volume equally to each heating site (based on the nanoparticle concentration) results in a volume that matches the defect size from independent mechanical measurements. In this way, macroscopic measurements elucidate the mesoscopic pattern of photothermal degradation. Sample morphology on scales from millimeters to nanometers is assessed via optical and electron microscopy. The carbonaceous by-products of degradation form in the hot region around each nanoparticle during photothermal heating, as revealed by transmission electron microscopy studies. Heterogeneous heating is also evident from optical images where starch granules, employed as an inert dilute additive to enhance PECA mechanical properties, also become luminescent due to degradation in "hot spots" created by the overlap of warm regions from nearby nanoparticle sites. Beyond the fundamental knowledge gained by these studies, the results demonstrate the ability to manipulate the connection between mechanical properties and chemical degradation which is important for developing new strategies for management of polymeric waste.

Fabrication and characterization of electrospun chitosan nanofibers formed via templating with polyethylene oxide.

Chitosan is an abundantly common, naturally occurring, polysaccharide biopolymer. Its biocompatible, biodegradable, and antimicrobial properties have led to significant research toward biological applications such as drug delivery, artificial tissue scaffolds for functional tissue engineering, and wound-healing dressings. For applications such as tissue scaffolding, formation of highly porous mats of nanometer-sized fibers, such as those fabricated via electrospinning, may be quite important. Previously, strong acidic solvents and blending with synthetic polymers have been used to achieve electrospun nanofibers containing chitosan. As an alternative approach, in this work, polyethylene oxide (PEO) has been used as a template to fabricate chitosan nanofibers by electrospinning in a core-sheath geometry, with the PEO sheath serving as a template for the chitosan core. Solutions of 3 wt % chitosan (in acetic acid) and 4 wt % PEO (in water) were found to have matching rheological properties that enabled efficient core-sheath fiber formation. After removing the PEO sheath by washing with deionized water, chitosan nanofibers were obtained. Electron microscopy confirmed nanofibers of approximately 250 nm diameter with a clear core-sheath geometry before sheath removal, and chitosan nanofibers of approximately 100 nm diameter after washing. The resultant fibers were characterized with IR spectroscopy and X-ray diffraction, and the mechanical and electrical properties were evaluated.

In situ collagen polymerization of layered cell-seeded electrospun scaffolds for bone tissue engineering applications.

Electrospun scaffolds have been studied extensively for their potential use in bone tissue engineering applications. However, inherent issues with the electrospinning approach limit the thickness of these scaffolds and constrain their use for repair of critical-sized bone defects. One method to increase overall scaffold thickness is to bond multiple electrospun scaffolds together with a biocompatible gel. The objective of this study was to determine whether multiple human adipose-derived stem cell (hASC-seeded electrospun, nanofibrous scaffolds could be layered via in situ collagen assembly and whether the addition of laser-ablated micron-sized pores within the electrospun scaffold layers was beneficial to the bonding process. Pores were created by a laser ablation technique. We hypothesized that the addition of micron-sized pores within the electrospun scaffolds would encourage collagen integration between scaffold layers, and promote osteogenic differentiation of hASCs seeded within the layered electrospun scaffolds. To evaluate the benefit of assembled scaffolds with and without engineered pores, hASCs were seeded on individual electrospun scaffolds, hASC-seeded scaffolds were bonded with type I collagen, and the assembled ∼3-mm-thick constructs were cultured for 3 weeks to examine their potential as bone tissue engineering scaffolds. Assembled electrospun scaffolds/collagen gel constructs using electrospun scaffolds with pores resulted in enhanced hASC viability, proliferation, and mineralization of the scaffolds after 3 weeks in vitro compared to constructs using electrospun scaffolds without pores. Scanning electron microscopy and histological examination revealed that the assembled constructs that included laser-ablated electrospun scaffolds were able to maintain a contracted structure and were not delaminated, unlike assembled constructs containing nonablated electrospun scaffolds. This is the first study to show that the introduction of engineered pores in electrospun scaffolds assists with multilayered scaffold integration, resulting in thick constructs potentially suitable for use as scaffolds for bone tissue engineering or repair of critical bone defects.

Nanofibrous composites for tissue engineering applications.

Development of artificial matrices for tissue engineering is a crucial area of research in the field of regenerative medicine. Successful tissue scaffolds, in analogy with the natural mammalian extracellular matrix (ECM), are multi-component, fibrous, and on the nanoscale. In addition, to this key morphology, artificial scaffolds must have mechanical, chemical, surface, and electrical properties that match the ECM or basement membrane of the specific tissue desired. In particular, these material properties may vary significantly for the four primary tissues in the body: nerve, muscle, epithelial, and connective. In order to address this complex array of attributes with a polymeric material, a nanocomposite approach, employing a blend of materials, addition of a particle to enhance particular properties, or a surface treatment, is likely to be required. In this review, we examine nanocomposite approaches to address these diverse needs as a function of tissue type. The review is intended as a bridge between material scientists and biomedical researchers to give basic background information on tissue biology to the former, and on material processing approaches to the latter, in a general manner, and specifically review fibrous nanocomposite materials that have previously been used for cell studies, either in vivo or in vitro.

Characterization of electrospun nanocomposite scaffolds and biocompatibility with adipose-derived human mesenchymal stem cells.

Electrospun nanocomposite scaffolds were fabricated by encapsulating multi-walled carbon nanotubes (MWNT) in poly (lactic acid) (PLA) nanofibers. Scanning electron microscopy (SEM) confirmed the fabrication of nanofibers, and transmission electron microscopy identified the alignment and dispersion of MWNT along the axis of the fibers. Tensile testing showed an increase in the tensile modulus for a MWNT loading of 0.25 wt% compared with electrospun nanofibrous mats without MWNT reinforcement. Conductivity measurements indicated that the confined geometry of the fibrous system requires only minute doping to obtain significant enhancements at 0.32 wt%. Adipose-derived human mesenchymal stem cells (hMSCs) were seeded on electrospun scaffolds containing 1 wt% MWNT and 0 wt% MWNT, to determine the efficacy of the scaffolds for cell growth, and the effect of MWNT on hMSC viability and proliferation over two weeks in culture. Staining for live and dead cells and DNA quantification indicated that the hMSCs were alive and proliferating through day 14. SEM images of hMSCs at 14 days showed morphological differences, with hMSCs on PLA well spread and hMSCs on PLA with 1% MWNT closely packed and longitudinally aligned.