Gabriel P. Lopez

Rapid prototyping of patterned functional nanostructures

Living systems exhibit form and function on multiple length scales and at multiple locations. In order to mimic such natural structures, it is necessary to develop efficient strategies for assembling hierarchical materials. Conventional photolithography, although ubiquitous in the fabrication of microelectronics and microelectromechanical systems, is impractical for defining feature sizes below 0.1 micrometres and poorly suited to pattern chemical functionality. Recently, so-called ‘soft’ lithographic approaches have been combined with surfactant and particulate templating procedures to create materials with multiple levels of structural order. But the materials thus formed have been limited primarily to oxides with no specific functionality, and the associated processing times have ranged from hours to days. Here, using a self-assembling ‘ink’, we combine silica–surfactant self-assembly with three rapid printing procedures—pen lithography, ink-jet printing, and dip-coating of patterned self-assembled monolayers—to form functional, hierarchically organized structures in seconds. The rapid-prototyping procedures we describe are simple, employ readily available equipment, and provide a link between computer-aided design and self-assembled nanostructures. We expect that the ability to form arbitrary functional designs on arbitrary surfaces will be of practical importance for directly writing sensor arrays and fluidic or photonic systems.

Multiplex lateral-flow test strips fabricated by two-dimensional shaping.

We have fabricated paper- and nitrocellulose-based lateral-flow devices that are shaped in two dimensions by a computer-controlled knife. The resulting star, candelabra, and other structures are spotted with multiple bioassay reagents to produce multiplex lateral-flow assays. We have also fabricated laminar composites in which porous nitrocellulose media are sandwiched between vinyl and polyester plastic films. This minimizes evaporation, protects assay surfaces from contamination and dehydration, and eliminates the need for the conventional hard plastic cassette holders that are typically used to package commercial lateral-flow diagnostic strips. The reported fabrication method is novel, low-cost, and well-suited to (i) fabrication and adoption in resource-poor areas, (ii) prototype development, (iii) high-volume manufacturing, and (iii) improving rates of operator error.

3D Printing of Highly Stretchable and Tough Hydrogels into Complex, Cellularized Structures

A 3D printable and highly stretchable tough hydrogel is developed by combining poly(ethylene glycol) and sodium alginate, which synergize to form a hydrogel tougher than natural cartilage. Encapsulated cells maintain high viability over a 7 d culture period and are highly deformed together with the hydrogel. By adding biocompatible nanoclay, the tough hydrogel is 3D printed in various shapes without requiring support material.

The Influence of Surface Wettability on the Adhesion Strength of Settled Spores of the Green Alga Enteromorpha and the Diatom Amphora

Abstract In this paper we report on the effect of surface wettability on surface selection and adhesion properties of settled (adhered) spores of the biofouling marine alga Enteromorpha and cells of the diatom Amphora, through the use of patterned self-assembled monolayers (SAMs). The SAMs were formed from alkanethiols terminated with methyl (CH3) or hydroxyl (OH) groups, or mixtures of the two, creating a discontinuous gradient of wettability as measured by advancing water contact angle. In the case of Enteromorpha, primary adhesion, as measured by the transition from a motile spore to a settled, sessile organism, is strongly promoted by the hydrophobic surfaces. On the other hand, adhesion strength of the settled spores, as measured by resistance to detachment in a turbulent flow cell, is greatest on a hydrophilic surface. In the case of Amphora, there is little influence of surface wettability on the primary adhesion of this organism, but motility is inhibited at contact angles ≥60° and the cells are more strongly adhered to hydrophobic surfaces. Adhesion strength of Enteromorpha spores is also influenced by group size, spores in groups being more resistant to detachment than single spores.

Use of Self-Assembled Monolayers of Different Wettabilities To Study Surface Selection and Primary Adhesion Processes of Green Algal (Enteromorpha) Zoospores

ABSTRACT We investigated surface selection and adhesion of motile zoospores of a green, macrofouling alga (Enteromorpha) to self-assembled monolayers (SAMs) having a range of wettabilities. The SAMs were formed from alkyl thiols terminated with methyl (CH3) or hydroxyl (OH) groups or mixtures of CH3- and OH-terminated alkyl thiols and were characterized by measuring the advancing contact angles and by X-ray photoelectron spectroscopy. There was a positive correlation between the number of spores that attached to the SAMs and increasing contact angle (hydrophobicity). Moreover, the sizes of the spore groups (adjacent spores touching) were larger on the hydrophobic SAMs. Video microscopy of a patterned arrangement of SAMs showed that more zoospores were engaged in swimming and “searching” above the hydrophobic sectors than above the hydrophilic sectors, suggesting that the cells were able to “sense” that the hydrophobic surfaces were more favorable for settlement. The results are discussed in relation to the attachment of microorganisms to substrata having different wettabilities.

Effect of Substratum Surface Chemistry and Surface Energy on Attachment of Marine Bacteria and Algal Spores

ABSTRACT Two series of self-assembled monolayers (SAMs) of ω-substituted alkanethiolates on gold were used to systematically examine the effects of varying substratum surface chemistry and energy on the attachment of two model organisms of interest to the study of marine biofouling, the bacterium Cobetia marina (formerly Halomonas marina) and zoospores of the alga Ulva linza (formerly Enteromorpha linza). SAMs were formed on gold-coated glass slides from solutions containing mixtures of methyl- and carboxylic acid-terminated alkanethiols and mixtures of methyl- and hydroxyl-terminated alkanethiols. C. marina attached in increasing numbers to SAMs with decreasing advancing water contact angles (θAW), in accordance with equation-of-state models of colloidal attachment. Previous studies of Ulva zoospore attachment to a series of mixed methyl- and hydroxyl-terminated SAMs showed a similar correlation between substratum θAW and zoospore attachment. When the hydrophilic component of the SAMs was changed to carboxylate, however, the profile of attachment of Ulva was significantly different, suggesting that a more complex model of interfacial energetics is required.

Anisotropic Wetting Surfaces with One-Dimesional and Directional Structures: Fabrication Approaches, Wetting Properties and Potential Applications

This review article provides a brief summary of recent research progress on anisotropic wetting on one-dimensional (1D) and directionally patterned surfaces, as well as the technical importance in various applications. Inspiration from natural structures exhibiting anisotropic wetting behavior is first discussed. Development of fabrication techniques for topographically and chemically 1D patterned surfaces and directional nanomaterials are then reviewed, with emphasis on anisotropic behavior with topographically (structurally) patterned surfaces. The basic investigation of anisotropic wetting behavior and theoretical simulations for anisotropic wetting are also further reviewed. Perspectives concerning future direction of anisotropic wetting research and its potential applications in microfluidic devices, lab-on-a-chip, sensor, microreactor and self-cleaning are presented.

Monodisperse mesoporous silica microspheres formed by evaporation-induced self-assembly of surfactant templates in aerosoles

The present invention provides for evaporation induced self-assembly (EISA) within microdroplets produced by a vibrating orifice aerosol generator (VOAG) for the production of monodisperse mesoporous silica particles. The process of the present invention exploits the concentration of evaporating droplets to induce the organization of various amphiphilic molecules, effectively partitioning a silica precursor to the hydrophilic regions of the structure. Promotion of silica condensation, followed by removal of the surfactant, provides ordered spherical mesoporous particles.

Light-Induced Biocidal Action of Conjugated Polyelectrolytes Supported on Colloids

A series of water soluble, cationic conjugated polyelectrolytes (CPEs) with backbones based on a poly(phenylene ethynylene) repeat unit structure and tetraakylammonium side groups exhibit a profound light-induced biocidal effect. The present study examines the biocidal activity of the CPEs, correlating this activity with the photophysical properties of the polymers. The photophysical properties of the CPEs are studied in solution, and the results demonstrate that direct excitation produces a triplet excited-state in moderate yield, and the triplet is shown to be effective at sensitizing the production of singlet oxygen. Using the polymers in a format where they are physisorbed or covalently grafted to the surface of colloidal silica particles (5 and 30 microm diameter), we demonstrate that they exhibit light-activated biocidal activity, effectively killing Cobetia marina and Pseudomonas aeruginosa. The light-induced biocidal activity is also correlated with a requirement for oxygen suggesting that interfacial generation of singlet oxygen is the crucial step in the light-induced biocidal activity.

Nanopatterned Smart Polymer Surfaces for Controlled Attachment, Killing, and Release of Bacteria

Model surfaces with switchable functionality based on nanopatterned, thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm) brushes were fabricated using interferometric lithography combined with surface-initiated polymerization. The temperature-triggered hydration and conformational changes of nanopatterned PNIPAAm brushes reversibly modulate the spatial concealment and exposure of molecules that are immobilized in the intervals between nanopatterned brushes. A biocidal quaternary ammonium salt (QAS) was used to demonstrate the utility of nanopatterned PNIPAAm brushes to control biointerfacial interactions with bacteria. QAS was integrated into polymer-free regions of the substrate between nanopatterned PNIPAAm brushes. The biocidal efficacy and release properties of these surfaces were tested against Escherichia coli K12. Above the lower critical solution temperature (LCST) of PNIPAAm, desolvated, collapsed polymer chains facilitate the attachment of bacteria and expose QAS moieties that kill attached bacteria. Upon a reduction of the temperature below the LCST, swollen PNIPAAm chains promote the release of dead bacteria. These results demonstrate that nanopatterned PNIPAAm/QAS hybrid surfaces are model systems that exhibit an ability to undergo noncovalent, dynamic, and reversible changes in structure that can be used to control the attachment, killing, and release of bacteria in response to changes in temperature.