Tamara Elzein

Toward Cell Selective Surfaces: Cell Adhesion and Proliferation on Breath Figures with Antifouling Surface Chemistry

We report the preparation of microporous functional polymer surfaces that have been proven to be selective surfaces toward eukaryotic cells while maintaining antifouling properties against bacteria. The fabrication of functional porous films has been carried out by the breath figures approach that allowed us to create porous interfaces with either poly(ethylene glycol) methyl ether methacrylate (PEGMA) or 2,3,4,5,6-pentafluorostyrene (5FS). For this purpose, blends of block copolymers in a polystyrene homopolymer matrix have been employed. In contrast to the case of single functional polymer, using blends enables us to vary the chemical distribution of the functional groups inside and outside the formed pores. In particular, fluorinated groups were positioned at the edges while the hydrophilic PEGMA groups were selectively located inside the pores, as demonstrated by TOF-SIMS. More interestingly, studies of cell adhesion, growth, and proliferation on these surfaces confirmed that PEGMA functionalized interfaces are excellent candidates to selectively allow cell growth and proliferation while maintaining antifouling properties.

Adsorption of Alkanethiols on Gold Surfaces: PM-IRRAS Study of the Influence of Terminal Functionality on Alkyl Chain Orientation

The present paper focuses on a simplified method to study the orientation and the anisotropy of two different alkanethiols self-assembled monolayers on gold surfaces. The alkanethiols of interest vary only by their terminal functionalities (COOH and COOCH3), thus allowing one to highlight the influence of these ending chemical groups on the final orientation of the adsorbed molecules. 11-Mercaptoundecanoic acid [HS-(CH2)10-COOH] and the methyl-11-mercaptoundecanoate [HS-(CH2)10-COOCH3] were grafted under adequate conditions to obtain a high grafting density on gold substrates. These latter, before and after the alkanethiol adsorption, were analyzed mainly by the polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) technique to access orientation angles, and by atomic force microscopy (AFM) to check the homogeneity of the grafted layer. By applying an original PM-IRRAS simplified method, the results showed an orientation closer to the normal of the surface plane in the case of the acid thiol compared with the ester one, which is probably because of the lateral hydrogen bonds established between the adjacent COOH functions. This method offers a direct and simple way to quantify the orientation angles in the alkanethiol nanofilms.

Surface initiated supplemental activator and reducing agent atom transfer radical polymerization (SI-SARA-ATRP) of 4-vinylpyridine on poly(ethylene terephthalate)

Poly(ethylene terephthalate) (PET) substrates were modified by means of surface-initiated supplemental activator and reducing agent atom transfer radical polymerization (SI-SARA-ATRP) of 4-vinylpyridine (4VP). Substrates were pretreated in order to graft chloromethylbenzene (CMB) units capable of initiating the radical polymerization reaction of 4VP units. Surface characterization techniques, including Water Contact Angle (WCA), Attenuated Total Reflection (ATR), X-ray photoelectron spectroscopy (XPS), Atomic Force Microscopy (AFM) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) showed a successful grafting of a stable, smooth and homogenous layer of p4VP. This process offers the advantages of a rapid, simplified and low cost strategy to chemically modify polymer substrates with covalently bonded layer of the pH responsive p4VP for different applications. Moreover, by using TOF-SIMS profiling, we were able to track a density gradient along the z-axis generated by the interpenetrating phases of the different layers of the final modified surface. Fact that we correlated to the various positions of initiation sites within the polyethylenimine (PEI) used for PET aminolysis prior to CMB grafting. Our strategy will be used in future work to graft other polymers for different applications where industrial scale viable options are needed.

Surface Morphology and Crystallinity of Polyamides Investigated by Atomic Force Microscopy

The surface composition of a solid substrate is able to strongly the crystallization of a semicrystalline polymer adsorbed on the substrate. Interfacial interaction between polymer and substrate is indeed able to govern adsorbed chains conformation and consequently crystalline organization.The aim of this chapter is to illustrate the role of the substrate surface chemistry on the crystalline structure of polyamides. Different polyamides were adsorbed onto chemically controlled surfaces, such as thiol self-assembled monolayers (terminated by different chemical functions) grafted on gold substrates. The crystalline morphology of polyamide nanofilms adsorbed on grafted gold is analyzed by atomic force microscopy. Results show that the crystalline organization directly depends on the surface chemistry. Explanations based on interactions between the polyamide chains and the chemical groups present on the substrate are proposed.

Hydrophobization of chitosan films by surface grafting with fluorinated polymer brushes

Chitosan with its surface-properties and biodegradability is a promising biomaterial for green packaging applications. Till now, this application is still limited due to chitosan high sensitivity to water. Some existing studies deal with the incorporation of hydrophobic additives to enhance water-proof performances of chitosan films. As these additives may impair the film properties, our study focuses on chitosan efficient hydrophobization by means of simple and successful surface grafting reactions. Chitosan films prepared by solvent casting were modified by means of surface-initiated activators regenerated by electron transfer atom radical polymerization (SI-ARGET-ATRP) of 2-hydroxyethyl methacrylate (HEMA) followed by esterification reaction with fluorinated acyl compound. X-ray photoelectron spectroscopy (XPS), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and Time-of-Flight Secondary Ion Mass Spectroscopy (ToF-SIMS) highlighted the surface chemical changes after each step. Surface properties were investigated by contact angle measurements and surface energy calculations. Hydrophobic surfaces with low surface energy and good water-repellent properties were obtained using a simple handling polymerization procedure. This is the first study in applying ARGET ATRP to prepare hydrophobic biopolymer films offering potential applications in packaging.