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Year 2019, football, rugby, netball and skiing had most occurring ACL injuries, listed by United Kingdom National Ligament Report (NLR). The standard procedure treatment of complete laceration of the ACL, is performed by tissue autograft implantation designed from a patellar tendon, for replacement of damaged tissue using orthopaedic surgery. The aim of this thesis is to design and fabricate an ACL graft, attempting to mimic the natural ACL, for the purpose of tissue reconstruction. The desired graft analogues exhibited properties imitating native connective tissue, reducing pain through drug delivery with great biocompatibility and enhance suture mechanical strength. Various biomaterials were implemented into this study, utilising strategies; polymer solution fabrication, electrospinning, hydrogel synthesis, mechanical braiding and graft assembly to fabricate an ACL graft. The polymeric material poly (E- caprolactone) (PCL) was researched, utilising its ability to fabricate scaffolds. Results showed, three analogue ACL grafts (Braided PCL-BP, Braided PCL + Hydrogel-BPH & Braided PCL + Sutures-BPS) created utilising the properties of braiding, hydrogels and sutures, ultimately improving the versatility of electrospinning for tissue engineering and reconstruction. Graft analogues were tested and compared against patellar tendons producing similar tensile properties. Poly vinyl alcohol (PVA) hydrogels successfully held ibuprofen, revealing drug delivery characteristics, polyester threads improved mechanical properties of electrospun grafts and dry degradation showed that PCL did not lose significant mass over two months. Conclusion, tensile strength of patella tendon was 395x, 790x & 56x of analogue grafts (BP, BPH & BPS) respectively, having potential for improvement of tensile parameters for ligament reconstruction.

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Indiana University-Purdue University Indianapolis (IUPUI) / Purpose: Dental sealant forms a physical barrier to prevent pit and fissure caries; therefore, the retention rate becomes a main factor of the sealant’s effectiveness. Electrospun nylon-6/N6 nanofibers have shown good mechanical properties, such as high tensile strength and fracture toughness. Chitosan/CH has received significant attention due to properties such as antibacterial activity. The purpose of this study was to synthesize and evaluate the effect of incorporating N6 and CH electrospun nanofibers on the physical-mechanical and antibacterial properties of an experimental resin-based sealant. Methods and Materials: Nanofiber synthesis: N6 pellets were dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol at a concentration of 10wt%. Practical-grade chitosan was dissolved in trifluoroacetic acid and dichloromethane (60:40 TFA/DCM) at 7 wt%. Electrospinning parameters were optimized in order to fabricate defect-free N6 and chitosan nanofiber mats. Morphological and chemical characterizations were performed by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy, respectively after vacuum drying the mats for 48 h. The average fiber diameter was determined from SEM images by measuring the diameter of 120 fibers using ImageJ software. Experimental Sealant: N6 and CH electrospun mats (3×3cm2) were immersed into a resin mixture of BIS-GMA/TEGDMA. Once no bubbles were seen, the resin-modified N6 and CH mats were put on a glass plate, light-cured (“TRIAD 2000”) for 2 min and then submitted to a cryomilling process to obtain a fine micron-sized powder. Three different filler levels (1 wt%, 2.5 wt%, 5 wt%) were used to prepare the N6 and CH incorporated resin-based sealants. Additionally, a commercially available resin-based sealant and the experimental resin mixture (unfilled) were used as controls. Three-point flexural testing, Vickers microhardness testing, and agar diffusion testing were performed on the experimental sealants and the commercial sealant. Data were analyzed by one-way ANOVA and Fisher's Protected Least Significant Differences Pair-wise comparisons between groups (5%). Results: The average fiber diameter for N6 was found to be 503±304 nm and 595±411 nm for CH. No significant difference was found between fiber diameter (p = 0.0601). FTIR confirmed the characteristic peaks for N6 ((CO-NH and [-(CH2)5-].) and CH (N-H and C2F3O2-). CH-5% group had significantly higher (p = 0.0000) FS (115.3±4.5 MPa) than all other groups. CH-1% and CH-2.5% groups had significantly higher FS than the control (unfilled) (p = 0.0016 and p = 0.0033 respectively); Helioseal Clear (p = 0.0000), and nylon groups. N6-5% had significantly higher flexural strength than Helioseal Clear (p = 0.0013) and N6-2.5% (p = 0.0250). CH-1% had significantly higher hardness values than all other groups, and CH-5% (p = 0.0414) had significantly higher values than N6-2.5%. No antibacterial inhibition was seen in any of the tested groups. Conclusions: CH and N6 nanofibers were successfully prepared via electrospinning and used to modify the experimental resin-based dental sealants. The overall results indicated that CH-containing sealants presented the highest flexural strength and hardness; however, none of the CH groups displayed antimicrobial properties. Further investigation is needed to enhance the physico-mechanical properties of the experimental resin-based sealants using nylon-6 and CH.

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No description available.

Electrospun nanofibers have been researched extensively in the culturing of stem cells to understand their behavior since electrospun fibers mimic the native extracellular matrix (ECM) in many types of mammalian tissues. Here, electrospun nanofibers with defined structure (orientation/alignment) and pore size could significantly modulate human mesenchymal stem cell (hMSC) behavior. Controlling the fiber membrane pore size was predominantly influenced by the duration of electrospinning, while the alignment of the fiber membrane was determined by parallel electrode collector design. Electric field simulation data provided information on the electrostatic interactions in this electrospinning apparatus.hMSCs on small-sized pores (~3-10 µm²) tended to promote the cytoplasmic retention of Yes-associated protein (YAP), while larger pores (~30-45 µm²) promoted the nuclear activation of YAP. hMSCs also displayed architecture-mediated behavior, as the cells aligned along with the fiber membranes orientation. Additionally, fiber membranes affected nuclear size and shape, indicating changes in cytoskeletal tension, which coincided with YAP activity. The mechanistic understanding of hMSC behavior on defined nanofiber structures seeks to advance their translation into more clinical settings and increase biomanufacturing efficiencies.

Les polymères conjugués semi-conducteurs sont des matériaux prometteurs pour des applications en optoélectronique et pour la fabrication de dispositifs de conversion d'énergie flexibles. Ils sont toutefois difficilement mis en forme en raison de la rigidité de leur structure. Le poly(3-hexylthiophène) (P3HT) est souvent utilisé comme polymère conjugué organique modèle. Sa mise en forme et ses propriétés peuvent être optimisées en l'incorporant dans une matrice polymère et en favorisant l’orientation moléculaire de ses chaînes. Cette orientation peut être induite dans un matériau lors de sa mise en forme, notamment lors de la préparation de fibres par électrofilage. Le projet vise à préparer des matériaux optimisant l'orientation du P3HT et à développer des outils pour caractériser l'organisation moléculaire du P3HT dans ces matériaux. Plus spécifiquement, la première étude consiste à comprendre l'effet de la matrice polymère sur le comportement du P3HT dans des nanofibres électrofilées. Celles-ci sont préparées en mélangeant le P3HT à une matrice polymère amorphe de poly(méthacrylate de méthyle) (PMMA) atactique ou fortement cristalline de poly(oxyde d'éthylène) (POE), et l’orientation des chaînes de P3HT est mesurée par spectroscopie Raman. Les résultats montrent que la capacité du POE à cristalliser, contrairement au PMMA, contraint les chaînes du P3HT à s'orienter le long de l’axe de la fibre, ce qui devrait améliorer ses propriétés de transport de charge. La calorimétrie différentielle à balayage et la microscopie optique et électronique à balayage permettent respectivement d'analyser les propriétés thermiques et d'imager la morphologie des nanomatériaux. La seconde étude est de développer une approche pour identifier la transition vitreuse du P3HT dans des nanofibres électrofilées et des impressions 3D composées d’un mélange P3HT-POE. Nous suivons alors l'évolution de l’état d'agrégation du P3HT par spectroscopie de fluorescence et le déplacement de sa bande Raman associée au mode d’élongation C=C sur une gamme de températures afin d'observer sa transition de phase vitreuse à l'échelle du nanoobjet individuel. Une preuve de concept est réalisée par des analyses sur des films minces à base de P3HT pour ensuite analyser les échantillons d’intérêt. Les résultats de spectroscopie Raman et de fluorescence sur les nanomatériaux de P3HT sont comparés aux analyses DSC sur les matériaux macroscopiques. Le projet améliorera d'une part notre capacité à caractériser les nanomatériaux de P3HT et, d'autre part, à en optimiser les propriétés. De manière plus générale, nos résultats conduiront à terme à une meilleure compréhension des relations structure-mise en forme-propriété-fonction des polymères conjugués, contribuant à la préparation de nouveaux matériaux électroniques organiques plus performants. / Conjugated polymers are promising semiconducting materials for applications in flexible optoelectronic and energy conversion devices. However, they are difficult to process because of the rigidity of their polymer backbone. Poly(3-hexylthiophene) (P3HT) is often used as a model organic conjugated polymer. Its processing and its properties can be improved by incorporating it into a polymer matrix and by favoring the molecular orientation of its chains. This orientation can be induced in a material during its processing, notably during the preparation of fibers by electrospinning. The project aims to prepare materials optimizing the orientation of P3HT and to develop tools to characterize the molecular organization of P3HT in these materials. More specifically, the first study consists of understanding the effect of the polymer matrix on the behaviour of P3HT in electrospun nanofibers. These nanofibers are prepared by mixing P3HT with an amorphous atactic poly(methyl methacrylate) (PMMA) or highly crystalline poly(ethylene oxide) (PEO) polymer matrix, and the orientation of the P3HT chains is measured by Raman spectroscopy. The results show that the capability of POE to crystallize, unlike PMMA, constrains the chains of P3HT to orient themselves along the fiber axis, which could improve its charge transport properties. Differential scanning calorimetry and optical and scanning electron microscopy make it possible, respectively, to analyze the thermal properties and to image the morphology of the nanomaterials. The second study is to develop an approach to identify the glass transition temperature of P3HT in electrospun nanofibers and 3D prints composed of a P3HT-PEO blend. We then follow the evolution of the aggregation state of P3HT by fluorescence spectroscopy and the shift of the Raman band associated with the C=C elongation mode over a range of temperatures to observe its glass transition temperature at the scale of the individual nanoobject. A proof of concept is first realized by carrying out analyses on thin films based on P3HT, followed by the analysis of the samples of interest. Raman and fluorescence spectroscopy results on P3HT-containing nanomaterials are compared to DSC analyses on macroscopic materials. The project will improve our ability to characterize P3HT nanomaterials and to optimize their properties. More generally, our results will ultimately lead to a better understanding of the structure-processing-property-function relationships of conjugated polymers, contributing to the preparation of new, more efficient organic electronic materials.