Paul Zavala-Rivera

Collective osmotic shock in ordered materials

Osmotic shock in a vesicle or cell is the stress build-up and subsequent rupture of the phospholipid membrane that occurs when a relatively high concentration of salt is unable to cross the membrane and instead an inflow of water alleviates the salt concentration gradient. This is a well-known failure mechanism for cells and vesicles (for example, hypotonic shock) and metal alloys (for example, hydrogen embrittlement). We propose the concept of collective osmotic shock, whereby a coordinated explosive fracture resulting from multiplexing the singular effects of osmotic shock at discrete sites within an ordered material results in regular bicontinuous structures. The concept is demonstrated here using self-assembled block copolymer micelles, yet it is applicable to organized heterogeneous materials where a minority component can be selectively degraded and solvated whilst ensconced in a matrix capable of plastic deformation. We discuss the application of these self-supported, perforated multilayer materials in photonics, nanofiltration and optoelectronics.

Photo-oxidative enhancement of polymeric molecular sieve membranes

High-performance membranes are attractive for molecular-level separations in industrial-scale chemical, energy and environmental processes. The next-generation membranes for these processes are based on molecular sieving materials to simultaneously achieve high throughput and selectivity. Membranes made from polymeric molecular sieves such as polymers of intrinsic microporosity (pore size<2 nm) are especially interesting in being solution processable and highly permeable but currently have modest selectivity. Here we report photo-oxidative surface modification of membranes made of a polymer of intrinsic microporosity. The ultraviolet light field, localized to a near-surface domain, induces reactive ozone that collapses the microporous polymer framework. The rapid, near-surface densification results in asymmetric membranes with a superior selectivity in gas separation while maintaining an apparent permeability that is two orders of magnitude greater than commercially available polymeric membranes. The oxidative chain scission induced by ultraviolet irradiation also indicates the potential application of the polymer in photolithography technology.

Low intensity sonosynthesis of iron carbide@iron oxide core-shell nanoparticles

Here we demonstrate a simple method for the organic sonosynthesis of stable Iron Carbide@Iron Oxide core-shell nanoparticles (ICIONPs) stabilized by oleic acid surface modification. This robust synthesis route is based on the sonochemistry reaction of organometallic precursor like Fe(CO)5 in octanol using low intensity ultrasonic bath. As obtained, nanoparticles diameter sizes were measured around 6.38 nm ± 1.34 with a hydrodynamic diameter around 25 nm and an estimated polydispersity of 0.27. Core-Shell structure of nanoparticles was confirmed using HR-TEM and XPS characterization tools in which a core made up of iron carbide (Fe3C) and a shell of magnetite (γ-Fe2O3) was found. The overall nanoparticle presented ferromagnetic behavior at 4 K by SQUID. With these characteristics, the ICIONPs can be potentially used in various applications such as theranostic agent due to their properties obtained from the iron oxides and iron carbide phases.

Evaluation of a combined emulsion process to encapsulate methylene blue into PLGA nanoparticles

The delivery of photosensitizer compounds using biodegradable nanoparticles could improve dosage, controlled release and its bioavailability. In this study, methylene blue (MB) loaded PLGA nanoparticles (MB-PNP) are prepared by a new approach combining single and double emulsification techniques. Comparisons of MB-PNP obtained with the combined and the individual techniques are presented. Nanoparticles are characterized by dynamic light scattering, laser Doppler electrophoresis and scanning electron microscopy. Particles prepared by the combined technique presented hydrodynamic diameters of 186 nm. The sizes of MB-PNP obtained from the single emulsion technique are similar to the combined technique, while the diameter of particles prepared by double emulsion increased from 201 nm to 287 nm as the TDL increased. MB-PNP displayed an average zeta potential between −21 mV and −28 mV for all formulations. MB loading ranges between 0.3–1.4%, while the encapsulation efficiency ranges from 8–14%, both depending on the TDL and the preparation technique. In vitro release studies show a monophasic release profile that was analyzed by considering the mechanisms of initial burst, drug diffusion and a combination of them. Experimental results could be better described using a mathematical model of release that simultaneously combines the mechanisms of initial burst and drug diffusion. The approach presented to encapsulate MB and also to analyze the drug release could be extended to other drugs with partial solubility.

Poly(N-isopropylacrylamide)-coated gold nanorods mediated by thiolated chitosan layer: thermo-pH responsiveness and optical properties

Abstract A core-shell of colloidal metal-responsive polymer provides an innovative model in functional materials. These core-shell nanocomposites offer the possibility to control some properties, such as particle size, surface plasmon resonance and morphology. In this research, we demonstrate the successful synthesis and functionality of gold nanorods (GNR) coated with the polymers chitosan (Ch) and poly(N-isopropylacrylamide) (PNIPAM). The polymer coatings are performed using a two-step method. First, GNR were coated with a thiolated chitosan (GNR-Ch) by replacing hexadecyltrimethylammonium bromide with a chitosan thiomer. Structural modification of GNR-Ch was monitored by Fourier transform infrared spectroscopy. Then a second polymeric coating was done by in situ free radical polymerization of N-isopropylacrylamide (NIPAM) on GNR-Ch to obtain the nanocomposite GNR-Ch-PNIPAM. The nanocomposite average size was analyzed by dynamic light scattering. The evolution of ζ potentials during the coatings was measured using electrophoretic mobility. GNR-Ch-PNIPAM presented a collapsed structure when heated above the lower critical solution temperature. The particle size of GNR-Ch-PNIPAM was manipulated by changing the pH. Plasmonic properties were evaluated by UV-Vis spectroscopy. Results showed an important blue shift due to the PNIPAM coating thickness. Thermo- and pH-responsive properties of the nanocomposite GNR-Ch-PNIPAM could be used as a drug delivery system.