Effect of polymer residues on the electrical properties of large-area graphene-hexagonal boron nitride planar heterostructures.

Polymer residue plays an important role in the performance of 2D heterostructured materials. Herein, we study the effect of polymer residual impurities on the electrical properties of graphene-boron nitride planar heterostructures. Large-area graphene (Gr) and hexagonal boron nitride (h-BN) monolayers were synthesized using chemical vapor deposition techniques. Atomic van-der-Waals heterostructure layers based on varied configurations of Gr and h-BN layers were assembled. The average interlayer resistance of the heterojunctions over a 1 cm2 area for several planar heterostructure configurations was assessed by impedance spectroscopy and modeled by equivalent electrical circuits. Conductive AFM measurements showed that the presence of polymer residues on the surface of the Gr and h-BN monolayers resulted in significant resistance deviations over nanoscale regions.

Synthesis of Half-Sphere/Half-Funnel-Shaped Silica Structures by Reagent Localization and the Role of Water in Shape Control.

Shape control of silica structures is demonstrated by localization of the reagents. A uniform dispersion of reagents provided straight silica rods, whereas localization of the reagents in the emulsion droplet periphery provided a new type of half-sphere/half-funnel structure. The effect of water concentration appeared to be related to the ease of diffusion of the silica precursor inside the emulsion droplet (i.e., the higher the water concentration, the lower the silica precursor diffusion).

Step-by-Step Growth of Complex Oxide Microstructures.

The synthesis of complex and hybrid oxide microstructures is of fundamental interest and practical applications. However, the design and synthesis of such structures is a challenging task. A solution-phase process to synthesize complex silica and silica-titania hybrid microstructures was developed by exploiting the emulsion-droplet-based step-by-step growth featuring shape control. The strategy is robust and can be extended to the preparation of complex hybrid structures consisting of two or more materials, with each having its own shape.

Sex differences in mitochondrial biogenesis determine neuronal death and survival in response to oxygen glucose deprivation and reoxygenation.

BACKGROUND: Mitochondrial dysfunction has been linked to neuronal death and a wide array of neurodegenerative diseases. Previously, we have shown sex differences in mitochondria-mediated cell death pathways following hypoxia-ischemia. However, the role of mitochondrial biogenesis in hypoxic-ischemic brain injury between male vs. female has not been studied yet. RESULTS: Primary cerebellar granule neurons (CGNs), isolated from P7 male and female mice (CD-1) segregated based on visual inspection of sex, were exposed to 2 h of oxygen glucose deprivation (OGD) followed by 6-24 h of reoxygenation (Reox). Mitochondrial membrane potential (ΔΨm) and cellular ATP levels were reduced significantly in XX CGNs as compared to XY CGNs. Mitochondrial DNA (mtDNA) content was increased (>2-fold) at 2 h OGD in XY CGNs and remained increased up to 24 h of Reox compared to XX neurons and normoxia controls. The expression of mitochondrial transcription factor A (Tfam), the nuclear respiratory factor-1 (NRF-1) and the peroxisome proliferator-activated receptor γ coactivator-1α (PGC-1α), a master regulator of mitochondrial biogenesis, were up-regulated (2-fold, ***p < 0.001) in XY CGNs but slightly reduced or remained unchanged in XX neurons. Similarly, the TFAM and PGC-1α protein levels and the mitochondrial proteins HSP60 and COXIV were increased in XY neurons only. Supportively, a balanced stimulation of fusion (Mfn 1and Mfn 2) and fission (Fis 1 and Drp 1) genes and enhanced formation of donut-shaped mitochondria were observed in XY CGNs vs. XX neurons (**p < 0.01). CONCLUSIONS: Our results demonstrate that OGD/Reox alters mitochondrial biogenesis and morphological changes in a sex-specific way, influencing neuronal injury/survival differently in both sexes.

Synthesis of segmented silica rods by regulation of the growth temperature.

The control of the diameter of colloidal structures is of fundamental interest and practical importance. We synthesized segmented silica rods by regulating the reaction temperature while the rods were growing. With higher growth temperatures, the segment diameter became smaller. Longer incubation times gave longer segments at the same temperature. Similarly, high temperature for the same incubation time gave longer segments. It appears that the correlation between temperature and diameter results from the relation between temperature and the size of the emulsion droplet, that is, the higher the temperature, the smaller the emulsion droplet.

Nanoscale Ion Transport Enhances Conductivity in Solid Polymer-Ceramic Lithium Electrolytes.

The predictive design of flexible and solvent-free polymer electrolytes for solid-state batteries requires an understanding of the fundamental principles governing the ion transport. In this work, we establish a correlation among the composite structures, polymer segmental dynamics, and lithium ion (Li+) transport in a ceramic-polymer composite. Elucidating this structure-property relationship will allow tailoring of the Li+ conductivity by optimizing the macroscopic electrochemical stability of the electrolyte. The ion dissociation from the slow polymer segmental dynamics was found to be enhanced by controlling the morphology and functionality of the polymer/ceramic interface. The chemical structure of the Li+ salt in the composite electrolyte was correlated with the size of the ionic cluster domains, the conductivity mechanism, and the electrochemical stability of the electrolyte. Polyethylene oxide (PEO) filled with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium bis(fluorosulfonyl) imide (LiFSI) salts was used as a matrix. A garnet electrolyte, aluminum substituted lithium lanthanum zirconium oxide (Al-LLZO) with a planar geometry, was used for the ceramic nanoparticle moieties. The dynamics of the strongly bound and highly mobile Li+ were investigated using dielectric relaxation spectroscopy. The incorporation of the Al-LLZO platelets increased the number density of more mobile Li+. The structure of the nanoscale ion-agglomeration was investigated by small-angle X-ray scattering, while molecular dynamics (MD) simulation studies were conducted to obtain the fundamental mechanism of the decorrelation of the Li+ in the LiTFSI and LiFSI salts from the long PEO chain.

Enhancing the Electrochemical Performance of Aqueous Processed Li-Ion Cathodes with Silicon Oxide Coatings.

Lithium-ion battery cathode materials suffer from bulk and interfacial degradation issues, which negatively affect their electrochemical performance. Oxide coatings can mitigate some of these problems and improve electrochemical performance. However, current coating strategies have low throughput, are expensive, and have limited applicability. In this article, we describe a low-cost and scalable strategy for applying oxide coatings on cathode materials. We report synergistic effects of these oxide coatings on the performance of aqueously processed cathodes in cells. The SiO2 coating strategy developed herein improved mechanical, chemical, and electrochemical performance of aqueously processed Ni-, Mn- and Co-based cathodes. This strategy can be used on a variety of cathodes to improve the performance of aqueously processed Li-ion cells.

A fluorescence light-up Ag nanocluster probe that discriminates single-nucleotide variants by emission color.

Rapid and precise screening of small genetic variations, such as single-nucleotide polymorphisms (SNPs), among an individual's genome is still an unmet challenge at point-of-care settings. One crucial step toward this goal is the development of discrimination probes that require no enzymatic reaction and are easy to use. Here we report a new type of fluorescent molecular probe, termed a chameleon NanoCluster Beacon (cNCB), that lights up into different colors upon binding SNP targets. NanoCluster Beacons (NCBs) are collections of a small number of Ag atoms templated on single-stranded DNA that fluoresce strongly when placed in proximity to particular DNA sequences, termed enhancers. Here we show the fluorescence emission color of a NCB can change substantially (a shift of 60-70 nm in the emission maximum) depending upon the alignment between the silver nanocluster and the DNA enhancer sequence. Chameleon NCBs exploit this color shift to directly detect SNPs, based on the fact that different SNPs produce a different alignment between the Ag nanocluster and the enhancer. This SNP detection method has been validated on all single-nucleotide substitution scenarios in three synthetic DNA targets, in six disease-related SNP targets, and in two clinical samples taken from patients with ovarian serous borderline tumors. Samples with single-nucleotide variations can be easily identified by the naked eye under UV excitation, making this method a reliable and low-cost assay with a simple readout format.

A lightweight thermally insulating and moisture-stable composite made of hollow silica particles.

Thermal insulation materials are highly desirable for several applications ranging from building envelopes to thermal energy storage systems. A new type of low-cost insulation material called hollow silica particles (HSPs) was recently reported. The present work presents an HSP-based stand-alone composite that has very low thermal conductivity and is highly stable to moisture.

Ag K-edge EXAFS analysis of DNA-templated fluorescent silver nanoclusters: insight into the structural origins of emission tuning by DNA sequence variations.

DNA-templated silver nanoclusters are promising biological fluorescence probes due to their useful fluorescence properties, including tunability of emission wavelength through DNA template sequence variations. Ag K-edge EXAFS analysis of DNA-templated silver nanoclusters has been used to obtain insight into silver nanocluster bonding, size, and structural correlations to fluorescence. The results indicate the presence of small silver nanoclusters (<30 silver atoms) containing Ag-Ag bonds and Ag-N/O ligations to DNA. The DNA sequence used leads to differences in silver-DNA ligation as well as silver nanocluster size. The results support a model in which cooperative effects of both Ag-DNA ligation and variations in cluster size lead to the tuning of the fluorescence emission of DNA-templated silver nanoclusters.

A DNA--silver nanocluster probe that fluoresces upon hybridization.

DNA-templated silver nanoclusters (DNA/Ag NCs) are an emerging set of fluorophores that are smaller than semiconductor quantum dots and can have better photostability and brightness than commonly used organic dyes. Here we find the red fluorescence of DNA/Ag NCs can be enhanced 500-fold when placed in proximity to guanine-rich DNA sequences. On the basis of this new phenomenon, we have designed a DNA detection probe (NanoCluster Beacon, NCB) that "lights up" upon target binding. Since NCBs do not rely on Forster energy transfer for quenching, they can easily reach high (>100) signal-to-background ratios (S/B ratios) upon target binding. Here, in a separation-free assay, we demonstrate NCB detection of an influenza target with a S/B ratio of 175, a factor of 5 better than a conventional molecular beacon probe. Since the observed fluorescence enhancement is caused by intrinsic nucleobases, our detection technique is simple, inexpensive, and compatible with commercial DNA synthesizers.

Hollow Silica Particles: A Novel Strategy for Cost Reduction.

Thermal insulation materials are highly sought after for applications such as building envelopes, refrigerators, cryogenic fuel storage chambers, and water supply piping. However, current insulation materials either do not provide sufficient insulation or are costly. A new class of insulation materials, hollow silica particles, has attracted tremendous attention due to its potential to provide a very high degree of thermal insulation. However, current synthesis strategies provide hollow silica particles at very low yields and at high cost, thus, making the particles unsuitable for real-world applications. In the present work, a synthesis process that produces hollow silica particles at very high yields and at a lower cost is presented. The effect of an infrared heat absorber, carbon black, on the thermal conductivity of hollow silica particles is also investigated and it is inferred that a carbon black-hollow silica particle mixture can be a better insulating material than hollow silica particles alone.

Scaffolded DNA origami of a DNA tetrahedron molecular container.

We describe a strategy of scaffolded DNA origami to design and construct 3D molecular cages of tetrahedron geometry with inside volume closed by triangular faces. Each edge of the triangular face is approximately 54 nm in dimension. The estimated total external volume and the internal cavity of the triangular pyramid are about 1.8 x 10(-23) and 1.5 x 10(-23) m(3), respectively. Correct formation of the tetrahedron DNA cage was verified by gel electrophoresis, atomic force microscopy, transmission electron microscopy, and dynamic light scattering techniques.

Hollow Silica Particles: Recent Progress and Future Perspectives.

Hollow silica particles (or mesoporous hollow silica particles) are sought after for applications across several fields, including drug delivery, battery anodes, catalysis, thermal insulation, and functional coatings. Significant progress has been made in hollow silica particle synthesis and several new methods are being explored to use these particles in real-world applications. This review article presents a brief and critical discussion of synthesis strategies, characterization techniques, and current and possible future applications of these particles.

Low cost and scalable method for modifying surfaces of hollow particles from hydrophilic to hydrophobic.

Hydrophobic hollow silica particles are desirable for several applications such as hydrophobic coatings, thermal insulation, and thermally resistant insulative paints. However, converting hydrophilic particles into hydrophobic particles without compromising their structural integrity is challenging. In this work, we present a low cost strategy to modify the surface of hollow silica particles from hydrophilic to hydrophobic without compromising their structural integrity.

Hybrid hollow silica particles: synthesis and comparison of properties with pristine particles.

In the past decade, interest in hollow silica particles has grown tremendously because of their applications in diverse fields such as thermal insulation, drug delivery, battery cathodes, catalysis, and functional coatings. Herein, we demonstrate a strategy to synthesize hybrid hollow silica particles having shells made of either polymer-silica or carbon-silica. Hybrid shells were characterized using electron microscopy. The effect of hybrid shell type on particle properties such as thermal and moisture absorption was also investigated.

Styrene-Based Elastomer Composites with Functionalized Graphene Oxide and Silica Nanofiber Fillers: Mechanical and Thermal Conductivity Properties.

The mechanical and thermal conductivity properties of two composite elastomers were studied. Styrene-butadiene rubber (SBR) filled with functionalized graphene oxide (GO) and silica nanofibers, and styrene-butadiene-styrene (SBS) block copolymers filled with graphene oxide. For the SBR composites, GO fillers with two different surface functionalities were synthesized (cysteamine and dodecylamine) and dispersed in the SBR using mechanical and liquid mixing techniques. The hydrophilic cysteamine-based GO fillers were dispersed in the SBR by mechanical mixing, whereas the hydrophobic dodecylamine-based GO fillers were dispersed in the SBR by liquid mixing. Silica nanofibers (SnFs) were fabricated by electrospinning a sol-gel precursor solution. The surface chemistry of the functionalized fillers was studied in detail. The properties of the composites and the synergistic improvements between the GO and SnFs are presented. For the SBS composites, GO fillers were dispersed in the SBS elastomer at several weight percent loadings using liquid mixing. Characterization of the filler material and the composite elastomers was performed using x-ray photoelectron spectroscopy, x-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, dynamic mechanical analysis, tensile testing, nanoindentation, thermal conductivity and abrasion testing.

Multilayer DNA origami packed on a square lattice.

Molecular self-assembly using DNA as a structural building block has proven to be an efficient route to the construction of nanoscale objects and arrays of increasing complexity. Using the remarkable "scaffolded DNA origami" strategy, Rothemund demonstrated that a long single-stranded DNA from a viral genome (M13) can be folded into a variety of custom two-dimensional (2D) shapes using hundreds of short synthetic DNA molecules as staple strands. More recently, we generalized a strategy to build custom-shaped, three-dimensional (3D) objects formed as pleated layers of helices constrained to a honeycomb lattice, with precisely controlled dimensions ranging from 10 to 100 nm. Here we describe a more compact design for 3D origami, with layers of helices packed on a square lattice, that can be folded successfully into structures of designed dimensions in a one-step annealing process, despite the increased density of DNA helices. A square lattice provides a more natural framework for designing rectangular structures, the option for a more densely packed architecture, and the ability to create surfaces that are more flat than is possible with the honeycomb lattice. Thus enabling the design and construction of custom 3D shapes from helices packed on a square lattice provides a general foundational advance for increasing the versatility and scope of DNA nanotechnology.

Distance-dependent interactions between gold nanoparticles and fluorescent molecules with DNA as tunable spacers.

Using stoichiometrically controlled 1:1 functionalization of gold nanoparticles with fluorescent dye molecules in which the dye molecule is held away from the particle surface by a rigid DNA spacer allows precise determination of the distance-dependent effect of the metal nanoparticles on fluorescence intensity. Two dyes were studied, Cy3 and Cy5, with two sizes of nanoparticles, 5 and 10 nm. The larger the particle, the more quenching of the photoluminescence (PL) intensity, due to increased overlap of the dye's emission spectrum with the Au surface plasmon resonance. Fluorescence is quenched significantly for distances somewhat larger than the particle diameter, in good agreement with the predictions of an electrodynamics model based on interacting dipoles. The distance dependence of surface energy transfer behavior, i.e. quenching efficiency, is proportional to 1/d(4), which involves no consideration of the size of the particle and the spectral overlap of the dye and AuNp. This surface energy transfer model is found qualitatively and agrees with the electrodynamic model, though the exponent is greater than 4 for the smaller nanoparticles (5 nm), and smaller than 4 for the larger nanoparticles (10 nm).

A novel strategy to purify conductive polymer particles.

The purification of conductive polymer (e.g., polyaniline) particles is a challenging task, especially when the particle size is small. Herein, we demonstrate a unique strategy (electrode-based) to purify polyaniline particles by exploiting the difference in surface charge between particles and surfactants, and compare the results with a commonly used purification strategy (washing).