Polyurea-Functionalized Multiwalled Carbon Nanotubes

An in situ polycondensation approach was applied to functionalize multiwalled carbon nanotubes (MWNTs), resulting in various linear or hyperbranched polycondensed polymers [e.g., polyureas, polyurethanes, and poly(urea-urethane)-bonded carbon nanotubes]. The quantity of the grafted polymer can be easily controlled by the feed ratio of monomers. As a typical example, the polyurea-functionalized MWNTs were measured and characterized in detail. The oxidized MWNTs (MWNT-COOH) were converted into acyl chloride-functionalized MWNTs (MWNT-COCl) by reaction with neat thionyl chloride (SOCl2). MWNT-COCl was reacted with excess 1,6-diaminohexane, affording amino-functionalized MWNTs (MWNT-NH2). In the presence of MWNT-NH2, the polyurea was covalently coated onto the surfaces of the nanotube by in situ polycondensation of diisocyanate [e.g., 4,4‘-methylenebis(phenylisocyanate)] and 1,6-diaminohexane, followed by the removal of free polymer via repeated filtering and solvent washing. The coated polyurea content can be controlled to some extent by adjusting the feed ratio of the isocyanato and amino groups. The structure and morphology of the resulting nanocomposites were characterized by FTIR, NMR, Raman, confocal Raman, TEM, EDS, and SEM measurements. The polyurea-coated MWNTs showed interesting self-assembled flat- or flowerlike morphologies in the solid state. The signals corresponding to that of the D and G bands of the carbon nanotubes were strongly attenuated after polyurea was chemically tethered to the MWNT surfaces. Comparative experiments showed that the grafted polymer species and structures have a strong effect on the Raman signals of polymer-functionalized MWNTs

IlsA, A Unique Surface Protein of Bacillus cereus Required for Iron Acquisition from Heme, Hemoglobin and Ferritin

The human opportunistic pathogen Bacillus cereus belongs to the B. cereus group that includes bacteria with a broad host spectrum. The ability of these bacteria to colonize diverse hosts is reliant on the presence of adaptation factors. Previously, an IVET strategy led to the identification of a novel B. cereus protein (IlsA, Iron-regulated leucine rich surface protein), which is specifically expressed in the insect host or under iron restrictive conditions in vitro. Here, we show that IlsA is localized on the surface of B. cereus and hence has the potential to interact with host proteins. We report that B. cereus uses hemoglobin, heme and ferritin, but not transferrin and lactoferrin. In addition, affinity tests revealed that IlsA interacts with both hemoglobin and ferritin. Furthermore, IlsA directly binds heme probably through the NEAT domain. Inactivation of ilsA drastically decreases the ability of B. cereus to grow in the presence of hemoglobin, heme and ferritin, indicating that IlsA is essential for iron acquisition from these iron sources. In addition, the ilsA mutant displays a reduction in growth and virulence in an insect model. Hence, our results indicate that IlsA is a key factor within a new iron acquisition system, playing an important role in the general virulence strategy adapted by B. cereus to colonize susceptible hosts

Single-layer graphenes functionalized with polyurea: architectural control and biomolecule reactivity

The nondestructive, covalent reactivity of single-layer graphene oxide (SLGO) and hydrazine-reduced graphene oxide (rGO) in relation to its 3-dimensional geometry has been previously considered for various chemical reactions. However, the capability of the modified system to undergo additional chemistry is now demonstrated through an in-situ polycondensation reaction resulting in various linear or hyperbranched condensed polymers [e.g., polyureas, polyurethanes, and poly(urea–urethane)-bonded graphenes]. The use of aliphatic diisocyanates as the anchor molecule initially forms star-like clusters of SLGO and rGO, and on in-situ polycondensation reaction with aliphatic diamines, the underlying graphene architecture is further modified into scroll-like domains with extensive intersheet bridging. The use of aromatic isocyanates as bridging molecules keeps the graphene structure flat and is maintained throughout the polycondensation reaction with aromatic diamines. Critical point drying of the graphene–polymer composites shows that changes to the architecture of the composite occur in the solution phase and not through surface tension effects on drying. According to TGA analysis, the aliphatic systems have higher grafted polymer weight proportions of polyurea than the aromatic counterparts and the rGO systems are found to be greater than the SLGO composites. In all experiments, the external surface of the graphene–polyurea macrostructure is demonstrated to be reactive toward biomolecules such as ferritin and is therefore useful toward a solution chemistry development of morphology-controlled graphene-based bio-nano applications

Multiwalled carbon nanotubes coated with tungsten disulfide

Novel binary-phase WS2−C nanotubes were generated by pyrolyzing WO3-coated multiwalled carbon nanotubes in an H2S/N2 atmosphere at 900 °C. The WS2 coating acts as an anti-oxidizing agent

Driving forces of conformational changes in single-layer graphene oxide

The extensive oxygen-group functionality of single-layer graphene oxide proffers useful anchor sites for chemical functionalization in the controlled formation of graphene architecture and composites. However, the physicochemical environment of graphene oxide and its single-atom thickness facilitate its ability to undergo conformational changes due to responses to its environment, whether pH, salinity, or temperature. Here, we report experimental and molecular simulations confirming the conformational changes of single-layer graphene oxide sheets from the wet or dry state. MD, PM6, and ab initio simulations of dry SLG and dry and wetted SLGO and electron microscopy imaging show marked differences in the properties of the materials that can explain variations in previously observed results for the pH dependent behavior of SLGO and electrical conductivity of chemically modified graphene-polymer composites. Understanding the physicochemical responses of graphene and graphene oxide architecture and performing selected chemistry will ultimately facilitate greater tunability of their performance

Multiwalled carbon nanotubes coated with tungsten disulfide

Novel binary-phase WS2-C nanotubes were generated by pyrolyzing WO3-coated multiwalled carbon nanotubes in an H2S/N2 atmosphere at 900 °C. The WS2 coating acts as an anti-oxidizing agent