Multilayer nanocoatings capable of separating gases, killing bacteria and stopping fire

Layer-by-layer (LbL) assembly is a conformal coating “platform” technology capable of imparting a multiplicity of functionalities on nearly any type of surface in a relatively environmentally friendly way. At its core, LbL is a solution deposition technique in which layers of cationic and anionic materials (e.g. nanoparticles, polymers and even biological molecules) are built up via electrostatic attractions in an alternating fashion, while controlling process variables such as pH, coating time, and concentration. Here we are producing nanocomposite multilayers (50 – 1000 nm thick), having 10 – 96 wt% clay, that are completely transparent and exhibit oxygen transmission rates below 0.005 cm3/m2•day. This exceptional oxygen barrier makes these coatings interesting for food, consumer products and flexible electronics packaging. These same ‘nanobrick wall’ assemblies are very conformal and able to impart flame resistance to highly flammable foam and fabric by uniformly coating the complex three-dimensional geometries. I’ll also describe how all-polymer thin films can separate H2 from N2 (or CO2) with selectivity greater than 2000, which exceeds other commonly used gas separation membranes (including zeolites). These films can also be produced with graphene oxide to generate high barrier and low sheet resistance. If there’s time, our work on antimicrobial and UV-resistant films will also be described. All of these nanocoatings are water-based and processing occurs under ambient conditions in most cases. Furthermore, these nanocoatings can be deposited in a commercially-feasible manner. Our work in these areas has been highlighted in C&EN, ScienceNews, Nature, Smithsonian Magazine, Chemistry World and various scientific news outlets worldwide. For more information, please visit my website: http://nanocomposites.tamu.ed

Fine control of carbon nanotubes-polyelectrolyte sensors sensitivity by electrostatic layer by layer assembly (eLbL) for the detection of volatile organic compounds (VOC)

International audienceVolatile organic compounds (VOC) sensors have recently extended their field of application to medical area as they are considered as biomarkers in anticipated diagnosis of diseases such as lung cancer by breath analysis. Conductive polymer nanocomposites (CPC) have already proved their interest to fabricate sensors for the design of electronic noses (e-noses) but, for the first time to our knowledge, the present study is showing that electrostatic layer by layer assembly (eLbL) is bringing an interesting input to tailor the sensitivity of carbon nanotubes (CNT)-polyelectrolyte sensors. By this technique transducers are progressively built in 3D alternating dipping into sodium deoxycholate (DOC)-stabilized SWNT and poly(diallyldimethyl-ammonium chloride) [PDDA] solutions, respectively anionic and cationic. The precise control of transducers thicknesses (between 5 and 40 nm) resulting from this process allows a fine tuning of multilayer films resistance (between 50 and 2 kΩ) and thus of their sensitivity to VOC. Interestingly the surfactant used to disperse CNT into water, DOC is also found to enhance CNT sensitivity to vapors so is it for the polyelectrolyte PDDA. Finally it is found that transducers with 16 bilayers of PDDA/DOC-CNT provide optimum chemo-resistive properties for the detection and discrimination of the eight vapors studied (chloroform, acetone, ethanol, water, toluene, dichloromethane, tetrahydrofuran and methanol)

Enzymatic Modification of Polyamide for Improving the Conductivity of Water-Based Multilayer Nanocoatings

Enzymatic modification, using a protease from Bacillus licheniformis (Subtilisin A), was carried out on polyamide 6.6 (PA6.6) fabric to make it more amenable to water-based nanocoatings used to impart electrical conductivity. The modified PA6.6 fibers exhibit a smoother surface, increased hydrophilicity due to more carboxyl and amino groups, and larger ζ-potential relative to unmodified polyamide. With its improved hydrophilicity and surface functionality, the modified textile is better able to accept a water-based nanocoating, composed of multiwalled carbon nanotubes (MWCNT) stabilized by sodium deoxycholate (DOC) and poly(diallyldimethylammonium chloride) (PDDA), deposited via layer-by-layer assembly. Relative to unmodified fabric, the enzymatically modified fibers exhibit lower sheet resistance as a function of PDDA/MWCNT-DOC bilayers deposited. This relatively green technique could be used to impart a variety of useful functionalities to otherwise difficult-totreat synthetic fibers like polyamid

Micropatterning of Poly (N-isopropylacrylamide) (PNIPAAm) Hydrogels: Effects on Thermosensitivity and Cell Release Behavior

The thermally driven, reversible change in the surface properties of poly (N-isopropylacrylamide) (PNIPAAm) hydrogels from a hydrophilic (water-swollen) state to a hydrophobic (deswollen) state when heated above the volume phase transition temperature (VPTT, ~35 oC) makes them useful in inducing controlled cell release. To improve the kinetics of swelling and deswelling, we have prepared microstructured (i.e., micropillared) thermoresponsive surfaces comprising pure PNIPAAm hydrogel and nanocomposite PNIPAAm hydrogel embedded with polysiloxane colloidal nanoparticles (~220 nm diameter, 1 wt%) via photopolymerization. The thermosensitivity (i.e., degree and rate of swelling/deswelling) of these surfaces and how it can be regulated using different micropillar sizes and densities were characterized by measuring the dynamic size changes in micropillar dimensions in response to thermal activation. Our results show that the dynamic thermal response rate can be increased by more than twofold when the micropillar size is reduced from 200 to 100 μm. The temperature-controlled cell release behaviors of pure PNIPAAm and nanocomposite PNIPAAm micropatterned surfaces were successfully characterized using mesenchymal progenitor cells (10T1/2). This study demonstrates that the thermosensitivity of PNIPAAm surfaces can be regulated by introducing micropillars of different sizes and densities, while maintaining good temperature-controlled cell release behavior

Adding some Dirt to Clean energy: Applying clay nanocomposites in solar cells

Polymer clay nanocomposite (PCN) thin films have found application across a number of applications, ranging from oxygen barriers to flame retardants, where their resistance to molecular gas diffusion has proven remarkably effective, even in films only a few hundred nanometers thick. Deposited using a layer-by-layer processing approach that takes advantage of self-assembly of the constituent components, these composite thin films comprise highly organized, alternating molecular layers of functional polymers and exfoliated clay platelets, commonly montmorillonite or vermiculite. Here, we explore the potential application and utility of PCN thin films in solar cells, where they serve as conformal, transparent barrier films with the potential to impact solar cell lifetime, reliability, and safety. Solar cell failures commonly result when environmental moisture and corrosive or reactive gases penetrate a cell’s encapsulant. Moreover, such cell degradation can manifest as a gradual decline in solar cell performance or, in the case when degradation leads to significantly damaged electrical elements, much more dramatic arc-faults that can lead to complete and dramatic module failure, even igniting module fires. Here, we describe how the unique nanostructure, materials chemistry, and gas barrier properties of PCNs offer promise toward addressing these challenges. Applying the PCN coatings to various elements of a solar cell module, we demonstrate the efficacy of PCNs as gas barriers, corrosion inhibitors, and arc-fault flammability mitigators. I will discuss here not only the results of our studies but also potential mechanisms for effective PCN function and present some apparent limitations of select approaches to PCN integration. These results reveal significant potential for PCNs to impact photovoltaic and other energy-related technologies, and our work highlights how these diverse, highly functional thin films may offer tremendous new opportunities for other next generation materials advances. Please click Additional Files below to see the full abstract

PDMS\u3csub\u3estar\u3c/sub\u3e-PEG Hydrogels Prepared Via Solvent-Induced Phase Separation (SIPS) and Their Potential Utility as Tissue Engineering Scaffolds

Inorganic-organic hydrogels based on methacrylated star polydimethylsiloxane (PDMSstar-MA) and diacrylated poly(ethylene glycol) (PEG-DA) macromers were prepared via solvent-induced phase separation (SIPS). The macromers were combined in a dichloromethane precursor solution and sequentially photopolymerized, dried and hydrated. The chemical and physical properties of the hydrogels were further tailored by varying the number average molecular weight (Mn) of PEG-DA (Mn = 3.4k and 6k g mol-1) as well as the weight percent ratio of PDMSstar-MA (Mn = 7k g mol-1) to PEG-DA from 0:100 to 20:80. Compared to analogous hydrogels fabricated from aqueous precursor solutions, SIPS produced hydrogels with a macroporous morphology, a more even distribution of PDMSstar-MA, increased modulus and enhanced degradation rates. The morphology, swelling ratio, mechanical properties, bioactivity, non-specific protein adhesion, controlled introduction of cell adhesion, and cytocompatibility of the hydrogels were characterized. As a result of their tunable properties, this library of hydrogels is useful to study material-guided cell behavior and ultimate tissue regeneration

Multifunctional Cotton Impregnated with Multilayer Chitosan/Lignin Nanocoating and Ag Nanoparticles

he demand for clothes with antimicrobial and UV protective properties is continually growing. In an attempt to develop a simple and efficient treatment for cotton fabrics, layer-by-layer deposition of chitosan and magnesium lignosulfonate followed by in situ synthesis of Ag nanoparticles (NPs) was performed. Magnesium lignosulfonate acts as a stabilizing agent and UV blocker while NaBH4 is applied as a reducing agent. The influence of the number of bilayers (4 and 12) and the initial concentration of AgNO3 solution (10 mM and 20 mM) on UV protection factor (UPF) and antimicrobial activity against Gram-negative bacteria Escherichia coli, Grampositive bacteria Staphylococcus aureus and yeast Candida albicans was studied. The presence of nanocoating on the surface of cotton fabric is confirmed by FTIR and XPS analyses. XPS and FESEM analyses reveal a successful synthesis of Ag NPs on the surface of cotton fibers with an average dimension of 35 nm. A four bilayer coating is sufficient to reach maximum 50+ UV protection. Maximum reduction of all investigated microorganisms is achieved with 12 bilayers and application of 20 mM AgNO3 solution

SUSTRACCIÓN Y RESTITUCIÓN DE MENORES EN EL DERECHO INTERNACIONAL Y EN EL DERECHO CONSTITUCIONAL MEXICANO

El tema de la sustracción de menores, obliga a hacer referencia a la guarda y custodia, derivada de la figura de la patria potestad, la que vinculada a la organización de la familia, ha sufrido, como esta, importantes variaciones en las últimas décadas, ante lo vertiginoso de los desplazamientos de personas a lo largo y ancho del mundo, con fines laborales, profesionales, académicos, artísticos, financieros, turísticos, empresariales, energéticos, inclusive delincuenciales, -por ejemplo, los terroristas-, y un largo etcétera, provocando la creación de relaciones de todo tipo, en el ámbito familiar: conyugales, concubinarias, de filiación y parentesco, entre personas de diferente nacionalidad, con las consecuencias legales inherentesEl presente capítulo de libro titulado ¨SUSTRACCIÓN Y RESTITUCIÓN DE MENORES EN EL DERECHO INTERNACIONAL Y EN EL DERECHO CONSTITUCIONAL MEXICANO¨ desarrolla una explicación acerca de los menores, abarcando desde el momento en que adquieren la protección del orden jurídico, asi, como quienes lo protegerán en ese orden jurídico, es decir, los padres que ejercen la patria potestad, otorgando de estos últimos una descripción explicativa de la potestad jurídica que se les otorg

Controlling the dynamic percolation of carbon nanotube based conductive polymer composites by addition of secondary nanofillers: The effect on electrical conductivity and tuneable sensing behaviour

In this paper, the electrical properties of ternary nanocomposites based on thermoplastic polyurethane (TPU) and multi-walled carbon nanotubes (MWCNTs) are studied. In particular two nanofillers - differing in shape and electrical properties - are used in conjunction with MWCNTs: an electrically conductive CB and an insulating needle-like nanoclay, sepiolite. The ternary nanocomposites were manufactured in a number of forms (extruded pellets, filaments and compression moulded films) and their morphological and electrical properties characterised as function of time and temperature. The presence of both secondary nanofillers is found to affect the formation of a percolating network of MWCNTs in TPU, inducing a reduced percolation threshold and tuneable strain sensing ability. These ternary nanocomposites can find application as conductive and multi-functional materials for flexible electronics, sensing films and fibres in smart textiles. (c) 2012 Elsevier Ltd. All rights reserved

One-Step Multipurpose Surface Functionalization by Adhesive Catecholamine

Surface modification is one of the most important techniques in modern science and engineering. The facile introduction of a wide variety of desired properties onto virtually any material surface is an ultimate goal in surface chemistry. To achieve this goal, the incorporation of structurally diverse molecules onto any material surface is an essential capability for ideal surface modification. Here, a general strategy for surface modification is presented in which many diverse surfaces can be functionalized by immobilizing a wide variety of molecules. This strategy functionalizes surfaces by a one-step immersion of substrates in a one-pot mixture of a molecule and a catecholamine surface modification agent. This one-step procedure for surface modification represents a standard protocol to control interfacial properties.Armed Forces Institute of Regenerative Medicine (Award W81XWH-08-2-0034)National Institutes of Health (U.S.) (2R01DE016516-06