For the application of advanced hydrogel-based artificial muscle systems, conventional polymeric hydrogels usually suffer from various limitations such as structural inhomogeneity and poor mechanical strengths. Thus, improving the mechanical strength of a specific hydrogel system while maintaining its other useful properties become increasingly important. In this project, three different approaches were employed to improve the mechanical properties of hydrogels though microstructural control, including physical cross-links, copolymerisation, and interpenetrating systems. Analytical tools such as FTIR and XRD were used to confirm the success of sample preparation. Morphological SEM characterisations were applied to reveal direct graphic information on hydrogels microstructures. Equilibrium water swelling tests as well as uniaxial compression measurements were conducted to evaluate the influences of various experimental parameters on the hydrogels water-holding and mechanical properties. The physical cross-linker approach was proved to be successful since comparable swelling capacities and dramatically enhanced mechanical strength were achieved in nanocomposite systems in comparison with conventional chemically cross-linked gel systems, due to the presence of flexible cross-linking points and the multifunctional cross-linker role played by clay. The copolymerisation approach, both between two neutral monomers and between one neutral and the other ionic monomer, was unsuccessful in terms of mechanical property enhancement due to the low cross-linking density as a result of the dominate competition of copolymerisation rather than cross-lining kinetics. The interpenetrating approach was concluded as successful since hugely improved mechanical toughness and slightly reduced swelling capacities were observed in most IPN gel systems.

The main aim of the diploma thesis is to investigate the influence of incorporated polyelecrolyte additives on the mechanical and transport properties of hydrogel. Hydrogels, based on polyvinylalcohol, were selected for these experiments. Gelation of polyvinylalcohol can be induced physically or chemically. The aim was to investigate the influence of sodium alginate, sodium polystyrene sulfonate and sodium polyglutamate. Mechanical properties were studied by rheology, through viscoelastic properties. Transport properties were analyzed by using two methods: diffusion pair and fluorescence correlation spectroscopy.

This Diploma thesis deals with optimization of the hydrogel preparation with various additions of substances affecting adhesion, studying the adhesion of prepared hydrogel systems and modifying their adhesion properties. Prepared hydrogels were agarose, alginate and gellan polymer systems with additions of acrylic acid, acrylamide, calcium chloride and Tween 20. The experimental part of the diploma thesis focuses first on optimizing the preparation of individual hydrogels, from which, according to certain criteria, suitable representatives were selected to study adhesion and its controlled modification. Agarose and gellan hydrogels were selected as suitable representatives, which were then used in rheological measurements. Based on these measurements, the effect of the adhesive force and the adhesive work of individual materials was evaluated. It was found that the best adhesion properties of the materials used are unadjusted hydrogels, in the case of hydrogels with the addition of another substance, a negative effect on adhesion was observed, when the adhesion force was reduced and also the adhesion work was reduced.

Currently, many drugs are preclinically tested on two-dimensional cell cultures. However, this method does not adequately replicate the cellular interactions or diffusion gradient that occur in three-dimensional tissues, leading to poor indicators of how a drug may affect human tissues. The objective of this project was to use bioprinted pancreatic cancer cell cultures as a platform for three-dimensional drug testing. Various bioink formulations of cellulose, gelatin, and alginate were evaluated to determine which provided the best printability and cell viability. A cellulose nanocrystal and alginate hydrogel showed superior printability due to its shear thinning properties. Additionally, initial cell viability was nearly 80%, and it remained above 60% over four days. Use of a custom spinning bioreactor at 50 rpm resulted in no improvements to cell viability. Overall, the system shows potential as a drug testing platform to evaluate the effectiveness of various drug formulations on three-dimensional pancreatic cancer cell cultures.

Les matériaux polymères multi stimulables sont d’ores et déjà utilisés dans différents domaines d’applications, tels que le relargage de principes actifs sur commande, l’ingénierie tissulaire, les matériaux auto réparants ou les senseurs. Depuis une vingtaine d’années, la chimie supramoléculaire s’est révélée être un outil de choix pour créer ce type de matériaux dits « intelligents ». Elle permet en effet de moduler voir de programmer les propriétés des matériaux en contrôlant le caractère dynamique des interactions supramoléculaires via l’application de stimuli adaptés. Les travaux réalisés dans le cadre de cette thèse financée par l’ANR (projet STRAPA) avaient pour principal objectif d’exploiter des complexes à base de cyclobis paraquat paraphénylène (CBPQT4+) et d’entités riches en électrons (tétrathiafulvalène, naphtalène) pour concevoir des hydrogels supramoléculaires multi-stimulables. Deux types d’hydrogels ont été développés : des hydrogels physiques (réticulés de manière supramoléculaire) capables de présenter une transition sol-gel sous stimuli (température, ajout de molécules compétitrices) et des hydrogels chimiques (réticulés de manière permanente) dotés de motifs de reconnaissance moléculaire riches en électrons dont les propriétés de gonflement peuvent être finement contrôlées. En particulier, nous avons montré que celles-ci pouvaient être manipulées très facilement via le nombre d’unités riches en électrons présents au sein des hydrogels, en contrôlant le pourcentage de complexes formés, ainsi qu’en appliquant divers stimuli (température, red/ox, macromolécules compétitrices, tensioactifs). / Multistimuli-responsive polymer materials play an important role in various fields of applications, (drug delivery system, tissue engineering, and self-healing materials. In the last past decades, supramolecular chemistry has emerged as a powerful tool to build such smart materials. Indeed, thanks to the inherent and/or induced dynamic behavior of supramolecular interactions, materials properties can be potentially tuned or even programmed. The main objective of this thesis, that have been carried out in the framework of the STRAPA ANR project, was to exploit host-guest interactions formed from the cyclobis paraquat paraphenylene (CBPQT4+) host molecule and electron-rich entities (tetrathiafulvalene, naphthalene) to conceive multi-stimuli responsive hydrogels. Two kind of smart hydrogels have been developed : physical hydrogels in which the sol-gel transition can be controlled upon heating or by adding competitive molecules, and chemical hydrogels with programmable swelling properties. In the last case, we have notably shown that the actuating behavior of hydrogels could be finely triggered by applying various environmental stimuli (T, red/ox, competitive macromolecules and surfactants).

No description available.

No description available.

No description available.

3D bioprinting is an emerging field with the potential to reform the process of organ transplantation. The ability to 3D print new organs and tissues would supplement the organ donor shortage and decrease the risk associated with organ rejection. One of the current areas of research focuses on printing cells using hydrogels composed of methacrylated compounds as a scaffolding. One of the chemical means of crosslinking the hydrogels is using the photoinitiator lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP) to crosslink with light. The 3D bioprinter in the lab currently has an attachment for a 365nm lamp, however this is cytotoxic to cells. A 405nm laser was designed to mount on the hot tool of the BioAssemblyBot by Advanced Solutions and flash at a specific frequency when sent a signal from the bioprinter. This tool was then tested to determine effective flash frequencies for crosslinking hydrogels.

PLE presents an alternative or complementary probe-based tool to DPN, PPL, and NFL. Unlike most scanning probe techniques, where patterning by deposition is usually employed, PLE is unique because it is capable of deposition and removal in one or multiple steps. Therefore, PLE allows rectification of patterning errors, and it can be employed for both additive and subtractive patterning through molecular deposition and chemical and electrochemical etching, respectively. PLE is a technique that exploits the intrinsic porosity of hydrogels like agarose and polyacrylamide. The probes are made by polymerizing a liquid mixture of agarose or acrylamide monomers in a conical or pyramidal master. The polymeric probe is hydrated in deionized water or ink of interest after polymerization. For deposition, PLE has shown promising results in the selective deposition of fluorescent inks on bare or functionalized glass substrates. Erasing via PLE has been done in two ways: the first method involves selectively erasing the fluorescent molecules using a probe loaded with deionized water by bringing the probe in contact with the area of interest. Thus, solvation and transportation of the molecules into the polymeric probes render selective removal of materials (fluorescent inks) from a substrate. On the other hand, erasing or removal of metals deposited on a substrate was demonstrated using redox reactions. Here, the probe is loaded with an etchant, which is selectively delivered onto the substrate by bringing the probe close to or in contact with the surface. Thus, the etchant molecules passively diffuse from the probe to the substrate through a meniscus formed at the probe-substrate interface. Removal of molecules occurs after the redox reaction between the ink, and the substrate is completed. Many in-length microscale complex patterns can be easily made by translocating the probe over the substrate while the probe’s tip is in contact with the surface. Since the probes used in PLE are made of polymers, the probe-substrate contacting area can be easily modulated, and damage to the substrate by the probe is minimum. Moreover, it has been shown that the probes can be used multiple times, a hurdle frequently faced by probes made of hard materials such as silicon-based probes. We explored the capabilities of a polymeric probe made of PAAM to selectively deliver and remove (erase) material deposited on a surface. PLE, pioneered by our group, takes advantage of the hydrophilic and porous nature of polyacrylamide. In addition, the conformability of PAAM hydrogels was exploited to make patterns of various sizes and to the pattern on non-planar surfaces. The main advantage of PLE is removing materials from various substrates. Additionally, selective delivery of material to planar and non-planar substrates was demonstrated. Whereas DPN and sister techniques require multiple steps for patterning through the etching process, PLE can perform etching in one step. Therefore, using PLE, microscale patterning on surfaces can save considerable time, labor, and cost. Further, chemical and supplies waste are minima in PLE. Notably, the deposition and etching at the microscale level can be simultaneously achieved in one single step, providing an extremely high throughput patterning rate (on the order of 1000 mm2/s). The PLE patterning rate is two to three orders larger than DPN-based patterning. However, PLE inherently deposits and removes materials with features much larger (microscale) than that can be achieved with DPN (sub-nanoscale). Therefore, PLE is an alternative to DPN, PPL, and related probe-based deposition and erasing techniques, and in some cases, PLE provides enhanced capabilities than its contemporary techniques. In this dissertation, I intend to demonstrate the potential of PLE for fabricating working devices at a lower cost as an alternative to contemporary fabrication. Chapter 2 involves the fabrication of micro-electrodes on rigid and flexible substrates by selectively removing copper and ITO from a glass and a PET substrate. As proof of concept, substrates coated with the PLE patterned surfaces were used to fabricate a photodetector, and LEDs were assembled on the electrodes made on ITO-PET substrates. Chapter 3 describes a series of experiments involving the evaluation of ink withholding capacity, large area patterning, and the effect of modification of substrate surface energy on PLE patterning. These experiments an increased understanding of processes involved in PLE editing and microscale patterning. A potential pitfall of PLE-based etching was also observed in these experiments, where a thin layer of material was left behind after subtractive editing with a PLE probe. EDS analysis indicated that the material was composed of iron, chlorine, and copper ─ components of the etchant solution and the copper film. The ring structure was attributed to the coffee-ring effect pinning the water meniscus to the substrate. By understanding the potential causes of the formation of the coffee-ring possible solutions to this problem were formulated. Chapter 4 describes the physical and mechanical properties of the hydrogel PAAM probes at the nanoscale. ESEM and AFM were employed to investigate the structural and mechanical properties of the probes after impregnation with metal etchants of various concentrations. The effect of local RH on PLE patterns was also investigated. More importantly, these experiments show critical structural differences of PAAM hydrogels composed of various monomer and crosslinker concentrations. ESEM showed the significant influence exerted by RH on meniscus size and its interaction with the substrate. The behavior of the water meniscus observed in ESEM shows that large RH promotes water spreading on the substrate generating larger patterning features. Chapter 5 describes the capability of PLE to selectively deliver metallic inks on a non-linear curved substrate to fabricate a microscale battery. PLE was used to deposit silver nitrate onto a non-planar flexible substrate which was used to grow a thin electrically conductive copper film via copper electroless deposition. Electrodeposition of zinc on the copper substrate was accomplished. By coupling a zinc electrode to a manganese oxide-graphite composite cathode, we demonstrated a working Zn-MnO2 aqueous microscale battery.