Juan Rodríguez-Hernández

Fabrication of Honeycomb-Structured Porous Surfaces Decorated with Glycopolymers

We prepared breath figure patterns on functional surfaces by the surface segregation of a statistical glycopolymer, (styrene-co-2-(D-glucopyranosyl) aminocarbonyloxy ethyl acrylate (S-HEAGl). The synthesis of the statistical glycopolymer is prepared in a straightforward approach by conventional free radical copolymerization of styrene and the unprotected glycomonomer. Blends of this copolymer and high-molecular-weight polystyrene were spin coated from THF solutions, leading to the formation of surfaces with both controlled functionality and topography. AFM studies revealed that both the composition of the blend and the relative humidity play key roles in the size and distribution of the pores at the interface. Thus, the topographical features obtained on the polymer surfaces during film preparation by the breath figure methodology varied from 200 to 700 nm. Moreover, this approach leads to porous films in which the hydrophilic glycomonomer units are oriented toward the pore interface because upon soft annealing in water the holes are partially swelled. The self-organization of the glycopolymer within the pores was additionally confirmed by the reaction of carbohydrate hydroxyl groups with rhodamine isocyanate. Equally, we demonstrate the bioactivity of the anchored glycopolymers by means of the lectin binding test using concanavalin A (Con A).

Honeycomb patterned surfaces functionalized with polypeptide sequences for recognition and selective bacterial adhesion

We report on the preparation of functional polymer surfaces with controlled topography by using the breath figures approach. The resulting surfaces prepared from a mixture of a PS-b-PAA diblock copolymer and a homopolymer (PS) exhibit pores that are mainly composed of diblock copolymer whereas the rest of the surface is formed by homopolymer. The formation of a hexagonal assembly of pores was achieved by controlling several parameters during the casting process including relative humidity, composition of the blend and polymer concentration. A selective modification of the pore inner part by using appropriate polypeptide sequences permitted the use of these surfaces as scaffolds for pattern and display of active biomolecules, as ordered templates for specific recognition processes and finally for the micropatterning of bacterial cells.

Hybrid materials achieved by polypeptide grafted magnetite nanoparticles through a dopamine biomimetic surface anchored initiator

Herein we report the preparation of well-defined hybrid materials based on magnetite nanoparticles coated with a polypeptide shell attached covalently through dopamine. Highly crystalline and hydrophobic magnetite nanoparticles have been modified at the surface using a biomimetic adhesive, dopamine, which provides the magnetite particles with primary amine groups. Hybrid magnetite–polypeptide systems have been, then, obtained by ring opening polymerization (ROP) of γ-benzyl-L-glutamate N-carboxyanhydride. These core–shell nanoparticles, magnetite–polypeptide, constitute an interesting alternative to other magnetite–polymer structures (PEG or dextran) because they present the following advantages: (1) the stability provided by a polypeptide shell covalently bonded to the magnetite surface through a dopamine anchor molecule instead of other non-covalent interactions; (2) the posterior chain deprotection of a poly(γ-benzyl-L-glutamate) (PBLG) shell transforms the system into magnetite–poly(glutamic acid) nanoparticles (PLGA), with high stability in aqueous solutions and a large amount of carboxylic acid groups; and (3) the easiness to incorporate compounds with biological activity into the PBLG structure, for instance, by loading procaine by aminolysis reaction. Therefore, the magnetite–PBLG nanoparticles depicted herein can be potentially employed as magnetic drug carriers or as scaffolds to engineer more complex hybrid materials. The structure and composition of these systems have been extensively characterized.

Hierarchically structured multifunctional porous interfaces through water templated self-assembly of ternary systems.

Herein, a facile water-assisted templating approach, the so-called breath figures method, has been employed to prepare multifunctional and hierarchically structured porous patterned films with order at different length scales (nano- and micrometer). Tetrahydrofuran solutions of ternary blends consisting on high molecular weight polystyrene, an amphiphilic block copolymer, polystyrene-b-poly[poly(ethylene glycol) methyl ether methacrylate] (PS(40)-b-P(PEGMA300)(48)), and a fluorinated copolymer, polystyrene-b-poly(2,3,4,5,6-pentafluorostyrene) (P5FS(21)-b-PS(31)), have been used to obtain films varying the proportion of the three components. Confocal micro-Raman spectroscopy and atomic force microscopy demonstrated the preferential location of the different functionalities in the films. Because of the breath figures mechanism, the amphiphilic copolymer yield pores enriched in hydrophilic functionality while the fluorinated copolymer remained mixed with the PS matrix and eventually also forming self-assembled nanostructures at the surface. As a consequence, two levels of order can be observed, i.e., micrometer size pores with nanostructured domains due to the block copolymer self-assembly. In addition, the distribution of the amphiphilic copolymer within the holes is not regular being located principally on the edges of the cavities. This can be attributed to the coffee stain phenomenon occurring in the water droplets as a consequence of the segregation of the block copolymers to the droplets and their self-assembly.

Control of the chemistry outside the pores in honeycomb patterned films

We report the selective functionalization of the external surface in honeycomb structured porous films while maintaining the functionality of the pores. For this purpose, we describe the preparation of polymer films from blends of polystyrene (PS) and polystyrene-b-poly(2,3,4,5,6-pentafluorostyrene) (PS-b-P5FS) by the breath figures approach. The diblock copolymer resulted to be homogeneously distributed along the whole surface of the films as a consequence of the reorientation towards the solution–air interface. The porous films obtained have a wetting behavior that can be described by the Cassie–Baxter state equations. This particular effect allowed us to modify the chemical composition of the film surface whilst the interior of the pores does not vary. As a proof of concept, we report the modification of the surface using “click” chemistry. Thiolated glucose molecules were attached specifically to the poly(2,3,4,5,6-pentafluorostyrene) domains via thiol-para fluorine “click” reaction. The kinetics of this reaction and the possibility to participate in recognition processes have been evaluated by contact angle measurements, X-ray photoelectron spectroscopy and fluorescence microscopy.

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.

Constructing robust and functional micropatterns on polystyrene surfaces by using deep UV irradiation

We report the preparation of different surface patterns based on the photo-cross-linking/degradation kinetics of polystyrene (PS) by using UV light. Upon exposure to UV light, PS can be initially cross-linked, whereas an excess of the exposure time or intensity provokes the degradation of the material. Typically photolithography employs either positive or negative photoresist layers that upon removal of either the exposed or the nonexposed areas transfer the pattern of the mask. Herein, we present a system that can be both negative and positive depending on several aspects, including the irradiation time, intensity, or presence of absorbing active species (photoinitiators) using a general setup. As a result of the optimization of the time of exposure and the use of an appropriate cover or the incorporation of an appropriate amount of photoinitiator (in this particular case IRG 651), different tailor-made surface patterns can be obtained. Moreover, changes of the chemical composition of the polystyrene using, for instance, block copolymers can lead to surface patterns with variable functional groups. In this study we describe the formation of surface patterns using polystyrene-block-poly(2,3,4,5,6-pentafluorostyrene) block copolymers. The introduction of fluorinated moieties clearly modifies the wettability of the films when compared with that of the same structures obtained with PS. As a consequence we present herein a patterning methodology that can simultaneously vary not only the morphology but also the surface chemical composition.

Fabrication and Superhydrophobic Behavior of Fluorinated Microspheres

We describe the preparation of fluorinated microspheres by precipitation polymerization and their use to fabricate superhydrophobic surfaces. For that purpose, two different approaches have been employed. In the first approach, a fluorinated monomer (either 4-fluorostyrene or 2,3,4,5,6-pentafluorostyrene) was added to the initial mixture of monomers constituted by styrene (S) and divinylbenzene (DVB). The second approach is based on the encapsulation of a block copolymer, polystyrene-b-poly(2,3,4,5,6-pentafluorostyrene), during the polymerization of the monomers (S and DVB), thus enabling the formation of particles with perfluorinated chains instead of single functional groups at the interface. Both approaches led to narrow polydisperse particles with fluoro-functional groups at the interface as demonstrated by scanning electron microscopy (SEM), infrared (IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Surface array of particles obtained by simple solvent casting presented superhydrophobic behavior with contact angles of water droplets of ca. 160-165°.

Immobilization of Stimuli-Responsive Nanogels onto Honeycomb Porous Surfaces and Controlled Release of Proteins

In this article, we describe the formation of functional honeycomb-like porous surfaces fabricated by the breath figures technique using blends of either amino-terminated poly(styrene) or a poly(styrene)-b-poly(acrylic acid) block copolymer with homopoly(styrene). Thus, the porous interfaces exhibited either amino or acid groups selectively located inside of the holes, which were subsequently employed to anchor stimuli-responsive nanogels by electrostatic interactions. These nanogels were prepared from poly(N-isopropylacrylamide) (PNIPAM) cross-linked with dendritic polyglycerol (dPG) and semi-interpenetrated with either 2-(dimethylamino)ethyl methacrylate (DMAEMA) or 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) to produce positively and negatively charged nanogel surfaces, respectively. The immobilization of these semi-interpenetrated networks onto the surfaces allowed us to have unique stimuli-responsive surfaces with both controlled topography and composition. More interestingly, the surfaces exhibited stimuli-responsive behavior by variations on the pH or temperature. Finally, the surfaces were evaluated regarding their capacity to induce a thermally triggered protein release at temperatures above the cloud point temperature (T(cp)) of the nanogels.

Formation of multigradient porous surfaces for selective bacterial entrapment

Herein we describe the preparation of multigradient porous platforms by using the breath figures approach. In a single and straightforward step, we prepared porous surfaces in which three different parameters vary gradually from the edge of the sample to the center in a radial manner. Thus, we evidenced the gradual variation of the pore size and the shape of the pores that can be varied, depending on the sample concentration, but also depending on their radial position within the same sample. In addition, we succeeded in the control over the chemical composition inside and outside the pores as well as the variation of the concentration of block copolymer inside the pores as a function of their radial position. Moreover, the chemical composition and the variable cavity size of porous surfaces have been evaluated to analyze the influence of these variables on the selective bacterial immobilization. To the best of our knowledge this is the first example in which, by using a simple one-step strategy, a multigradient surface can be obtained. These initial results can be the base to construct platforms for selective immobilization and isolation of bacteria.