Oil-in-oil emulsions: a unique tool for the formation of polymer nanoparticles

Polymer latex particles are nanofunctional materials with widespread applications including electronics, pharmaceuticals, photonics, cosmetics, and coatings. These materials are typically prepared using waterborne heterogeneous systems such as emulsion, miniemulsion, and suspension polymerization. However, all of these processes are limited to water-stable catalysts and monomers mainly polymerizable via radical polymerization. In this Account, we describe a method to overcome this limitation: nonaqueous emulsions can serve as a versatile tool for the synthesis of new types of polymer nanoparticles. To form these emulsions, we first needed to find two nonmiscible nonpolar/polar aprotic organic solvents. We used solvent mixtures of either DMF or acetonitrile in alkanes and carefully designed amphiphilic block and statistical copolymers, such as polyisoprene- b-poly(methyl methacrylate) (PI- b-PMMA), as additives to stabilize these emulsions. Unlike aqueous emulsions, these new emulsion systems allowed the use of water-sensitive monomers and catalysts. Although polyaddition and polycondensation reactions usually lead to a large number of side products and only to oligomers in the aqueous phase, these new conditions resulted in high-molecular-weight, defect-free polymers. Furthermore, conducting nanoparticles were produced by the iron(III)-induced synthesis of poly(ethylenedioxythiophene) (PEDOT) in an emulsion of acetonitrile in cyclohexane. Because metallocenes are sensitive to nitrile and carbonyl groups, the acetonitrile and DMF emulsions were not suitable for carrying out metallocene-catalyzed olefin polymerization. Instead, we developed a second system, which consists of alkanes dispersed in perfluoroalkanes. In this case, we designed a new amphipolar polymeric emulsifier with fluorous and aliphatic side chains to stabilize the emulsions. Such heterogeneous mixtures facilitated the catalytic polymerization of ethylene or propylene to give spherical nanoparticles of high molecular weight polyolefins. These nonaqueous systems also allow for the combination of different polymerization techniques to obtain complex architectures such as core-shell structures. Previously, such structures primarily used vinylic monomers, which greatly limited the number of polymer combinations. We have demonstrated how nonaqueous emulsions allow the use of a broad variety of hydrolyzable monomers and sensitive catalysts to yield polyester, polyurethane, polyamide, conducting polymers, and polyolefin latex particles in one step under ambient reaction conditions. This nonpolar emulsion strategy dramatically increases the chemical palette of polymers that can form nanoparticles via emulsion polymerization.     

Visualization of the native shape of bodipy‐labeled DNA in Escherichia coli by correlative microscopy

The native shape and intracellular distribution of newly synthesized DNA was visualized by correlative (light and electron) microscopy in ice embedded whole cells of Escherichia coli. For that purpose, the commercially available modified nucleoside triphosphate named BODIPY® FL‐14‐dUTP was enzymatically incorporated in vivo into the genome of E. coli mutant K12 strain, which cannot synthesize thymine. The successful incorporation of this thymidine analogue was confirmed first by fluorescence microscope, where the cells were stained in the typical for bodipy green color. Later the preselected labeled E. coli were observed by Hilbert Differential Transmission Electron Microscope (HDC TEM) and the distribution of elemental boron (contained in bodipy) was visualized at high‐resolution by an electron spectroscopic imaging (ESI) technique. The practical detection limit of boron was found to be around 5 ～ 10 mmol/kg in area of 0.1 μm², which demonstrated that ESI is a suitable approach to study the cytochemistry and location of labeled nucleic fragments within the cytoplasmic chromosomal area. In addition, the fine cellular fibrous and chromosomal ultrastructures were revealed in situ by combing of phase‐plate HDC TEM and ESI. The obtained results conclude that the correlation between fluorescent microscopy with phase‐plate HDC TEM and ESI is a powerful approach to explore the structural and conformation dynamics of DNA replication machinery in frozen cells close to the living state.     

Electron microscopic visualization of complementary labeled DNA with platinum‐containing guanine derivative

The object of the present report is to provide a method for a visualization of DNA in TEM by complementary labeling of cytosine with guanine derivative, which contains platinum as contrast‐enhanced heavy element. The stretched single‐chain DNA was obtained by modifying double‐stranded DNA. The labeling method comprises the following steps: (i) stretching and adsorption of DNA on the support film of an electron microscope grid (the hydrophobic carbon film holding negative charged DNA); (ii) complementary labeling of the cytosine bases from the stretched single‐stranded DNA pieces on the support film with platinum containing guanine derivative to form base‐specific hydrogen bond; and (iii) producing a magnified image of the base‐specific labeled DNA. Stretched single‐stranded DNA on a support film is obtained by a rapid elongation of DNA pieces on the surface between air and aqueous buffer solution. The attached platinum‐containing guanine derivative serves as a high‐dense marker and it can be discriminated from the surrounding background of support carbon film and visualized by use of conventional TEM observation at 100 kV accelerated voltage. This method allows examination of specific nucleic macromolecules through atom‐by‐atom analysis and it is promising way toward future DNA‐sequencing or molecular diagnostics of nucleic acids by electron microscopic observation. Microsc. Res. Tech. 79:280–284, 2016. © 2016 Wiley Periodicals, Inc.     

SmallWorlds: Visualizing Social Recommendations

We present SmallWorlds, a visual interactive graph‐based interface that allows users to specify, refine and build item‐preference profiles in a variety of domains. The interface facilitates expressions of taste through simple graph interactions and these preferences are used to compute personalized, fully transparent item recommendations for a target user. Predictions are based on a collaborative analysis of preference data from a user's direct peer group on a social network. We find that in addition to receiving transparent and accurate item recommendations, users also learn a wealth of information about the preferences of their peers through interaction with our visualization. Such information is not easily discoverable in traditional text based interfaces. A detailed analysis of our design choices for visual layout, interaction and prediction techniques is presented. Our evaluations discuss results from a user study in which SmallWorlds was deployed as an interactive recommender system on Facebook.