Understanding cell migration is a key step in unraveling many physiological phenomena and predicting several pathologies, such as cancer metastasis. In particular, confinement has been proven to be a key factor in the cellular migration strategy choice. As our insight in the field improves, new tools are needed in order to empower biologists’ analysis capabilities. In this framework, microfluidic devices have been used to engineer the mechanical and spatial stimuli and to investigate cellular migration response in a more controlled way. In this work, we will review the existing technologies employed in the realization of microfluidic cellular migration assays, namely the soft lithography of PDMS and hydrogels and femtosecond laser micromachining. We will give an overview of the state of the art of these devices, focusing on the different geometrical configurations that have been exploited to study specific aspects of cellular migration. Our scope is to highlight the advantages and possibilities given by each approach and to envisage the future developments in in vitro migration studies under spatial confinement in microfluidic devices.

Silicone oils (polysiloxane) and elastomers are a class of hydrophobic polymers with an extensive range of uses. While the high hydrophobicity can be beneficial in a variety of applications, it is not universally the case. Modification strategies for both fluid and elastomeric polydimethylsiloxane (PDMS) must be employed to create silicones with the appropriate properties for a given application, including enhanced hydrophilicity. Derivatization of PDMS leads to functional silicones with unique properties and added value. Strategies have been developed to modify both fluid and elastomeric PDMS, however, they all have varying degrees of drawbacks: the use of sophisticated equipment or expensive catalysts, restrictions to certain types of solvents, cumbersome multi-step synthetic procedures and surface reversion are some of the challenges faced. There is an opportunity to develop a simple and generic method for the controlled functionalization of PDMS. The Sharpless concept of ‘Click’ chemistry was an ideal approach to solving some of these challenges. Following nature’s lead, these reactions that are modular, wide in scope, high yielding, have simple reaction conditions and generate inoffensive byproducts. Herein, a synthetic method to functionalize silicones using the thermal Huisgen 1,3-dipolar cycloaddition of azides to alkynes is described. Initial exploration focused on the creation of inherently reactive elastomers that could be modified with a model hydrophilic moiety, poly(ethylene glycol). This was extended to the creation of amphiphilic multi-functional polysiloxanes and amphiphilic networks. Furthermore, the ‘Click’ approach was used to solve challenges faced in applications where silicones find use. The method described overcomes silicone modification challenges. The cycloaddition reaction is tolerant to many reaction conditions, is orthoganol to a variety of chemical reactions, does not require the use of a catalyst, the starting functional groups and bonds formed are stable and the reaction is high yielding, positioning the Huisgen ‘click’ reaction is an exceptional synthetic tool for the silicone chemist. / Dissertation / Doctor of Philosophy (PhD) / Polydimethylsiloxane (PDMS or silicone) fluids and elastomers are materials that find use in many applications owing to the many desirable properties they possess; personal care products, electrical insulators, sealants and biomedical are examples of products containing silicone. Native PDMS is highly hydrophobic (water repellent) and certain applications require silicones that are more compatible in environments containing water. Methods have been developed to modify both fluid and elastomeric silicones; incorporation of different molecules or polymers can enhance the properties of silicone for various applications or create unique materials. However, many of these methods have certain drawbacks: the use of sophisticated equipment, expensive ingredients, or a lack of permanence. For this reason, a new method to modify fluid and elastomeric silicones has been developed. The new method is based on the concept of ‘Click’ chemistry and has overcome some of challenges associated with other modification methods.

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