MnCO3 on Graphene Porous Framework via Diffusion-Driven Layer-by-Layer Assembly for High-Performance Pseudocapacitor.

Diffusion-driven layer-by-layer (dd-LbL) assembly is a simple yet versatile process that can be used to construct graphene oxide (GO) into a three-dimensional (3D) porous framework with good mechanical stability. In particular, the oxygen functional groups on the GO surface are well retained, providing nucleation sites for further chemical reactions to be performed upon. Therefore, such a scaffold should serve as a promising starting material for creating a wide range of 3D graphene-based composites while maintaining a high accessible surface area. Herein, we demonstrate the use of the porous GO macrostructure derived from dd-LbL assembly for the preparation of graphene-MnCO3 hybrid structures. MnCO3 is a newly reported pseudocapacitive material for supercapacitors; however, its electrochemical performance is hampered by its low electrical conductivity and poor chemical stability. Through reaction between KMnO4 and GO during a hydrothermal process, the surface of the porous scaffold was rendered with uniform MnCO3 nanoparticles. With the reduced graphene oxide (rGO) sheets serving as the conductive backbone, the resultant MnCO3 nanoparticles exhibited a capacitance of 698 F g-1 at a charge/discharge current of 0.5 mA (320 F g-1 for the combined rGO and MnCO3 composite). Furthermore, the electrode maintained 77% of its initial capacity even after 5000 cycles of charge/discharge tests at 20 mA.

Ultrafine NaTi2(PO4)3 Nanoparticles Encapsulated in N-CNFs as Ultra-Stable Electrode for Sodium Storage.

We present a feasible method for the preparation of one-dimensional N-doping carbon nanofibers encapsulated NaTi2(PO4)3 (NTP-NCNFs) through electrospinning accompanied by calcination. The poor electrical conductivity of NTP is significantly improved and the as-prepared NTP-NCNFs exhibit stable and ultrafast sodium-storage capability. The NTP-NCNFs maintains a stable specific capacity of 121 mAh g-1 at 10 C after 2,000 cycles, which only drop to 105 mAh g-1 after 20,000 cycles. Furthermore, the NTP-NCNFs show excellent rate performance from 0.2 to 20 C, whose recovery efficiency still reaches 99.43%. The superior electrochemical property is mainly attributed to the large specific surface area, high porosity, N-doping carbon coating, and one-dimensional structure of NTP-NCNFs.

In Situ Study of Li Intercalation into Highly Crystalline Graphitic Flakes of Varying Thicknesses.

An in situ Raman spectroelectrochemical study of Li intercalation into graphite flakes with different thicknesses ranging from 1.7 nm (3 graphene layers) to 61 nm (ca. 178 layers) is presented. The lithiation behavior of these flakes was compared to commercial microcrystalline graphite with a typical flake thickness of ∼100 nm. Li intercalation into the graphitic flakes was observed under potential control via in situ optical microscopy and Raman spectroscopy. As graphite flakes decreased in thickness, a Raman response indicative of increased tensile strain along the graphene sheet was observed during the early stages of intercalation. A progressively negative wavenumber shift of the interior and bounding modes of the split G band (E2g2(i) and E2g2(b)) is interpreted as a weakening of the C-C bonding. Raman spectra of Li intercalation into thin graphitic flakes are presented and discussed in the context of implications for Li ion battery applications, given that intercalation induced strain may accelerate carbon negative electrode aging and reduce long-term cycle life.

Highly Stable and Conductive Microcapsules for Enhancement of Joule Heating Performance.

Nanocarbons show great promise for establishing the next generation of Joule heating systems, but suffer from the limited maximum temperature due to precociously convective heat dissipation from electrothermal system to surrounding environment. Here we introduce a strategy to eliminate such convective heat transfer by inserting highly stable and conductive microcapsules into the electrothermal structures. The microcapsule is composed of encapsulated long-chain alkanes and graphene oxide/carbon nanotube hybrids as core and shell material, respectively. Multiform carbon nanotubes in the microspheres stabilize the capsule shell to resist volume-change-induced rupture during repeated heating/cooling process, and meanwhile enhance the thermal conductance of encapsulated alkanes which facilitates an expeditious heat exchange. The resulting microcapsules can be homogeneously incorporated in the nanocarbon-based electrothermal structures. At a dopant of 5%, the working temperature can be enhanced by 30% even at a low voltage and moderate temperature, which indicates a great value in daily household applications. Therefore, the stable and conductive microcapsule may serve as a versatile and valuable dopant for varieties of heat generation systems.

Hierarchical patterning of multifunctional conducting polymer nanoparticles as a bionic platform for topographic contact guidance.

The use of programmed electrical signals to influence biological events has been a widely accepted clinical methodology for neurostimulation. An optimal biocompatible platform for neural activation efficiently transfers electrical signals across the electrode-cell interface and also incorporates large-area neural guidance conduits. Inherently conducting polymers (ICPs) have emerged as frontrunners as soft biocompatible alternatives to traditionally used metal electrodes, which are highly invasive and elicit tissue damage over long-term implantation. However, fabrication techniques for the ICPs suffer a major bottleneck, which limits their usability and medical translation. Herein, we report that these limitations can be overcome using colloidal chemistry to fabricate multimodal conducting polymer nanoparticles. Furthermore, we demonstrate that these polymer nanoparticles can be precisely assembled into large-area linear conduits using surface chemistry. Finally, we validate that this platform can act as guidance conduits for neurostimulation, whereby the presence of electrical current induces remarkable dendritic axonal sprouting of cells.

Capillary force lithography: the versatility of this facile approach in developing nanoscale applications.

Since its inception as a simple, low cost alternative to more complicated lithographic techniques such as electron-beam and dip-pen lithography, capillary force lithography (CFL) has developed into a versatile tool to form sub-100 nm patterns. Utilizing the concept of a polymer melt, structures and devices generated by the technique have been used in applications varying from surfaces regulating cell growth to gas sensing. In this review, we discuss various CFL methodologies which have evolved, their application in both biological and non-biological research, and finally a brief outlook in areas of research where CFL is destined to make an enormous impact in the near future.

Diffusion driven layer-by-layer assembly of graphene oxide nanosheets into porous three-dimensional macrostructures.

Despite recent progress in preparing numerous types of nanosheets, it remains a difficult challenge to assemble the tiny building blocks into functional macroscale architectures suitable for practical applications. Here we introduce a diffusion driven layer-by-layer assembly process and demonstrate its application for the construction of graphene oxide sheets into various three-dimensional structures. This process involves complexation of the negatively charged graphene oxide sheets and positively charged branched polyethylenimine at a given interface. We find that the diffusion of branched polyethylenimine molecules allows the complex to continuously grow into foam-like frameworks with tunable porosities. Furthermore, the assembly process is quite robust and can be utilized in various configurations such as to create free-standing architectures with tailored shapes or patterned films on a substrate. With such useful features, we believe that this technique may serve as a valuable tool for the assembly of nanomaterials.

Nanofibrous gelatin substrates for long-term expansion of human pluripotent stem cells.

Nanofibrous gelatin substrates are suited for long-term expansion of human pluripotent stem cells (hPSCs) under feeder- and serum-free culture conditions. A combinatorial library with different sets of processing parameters was established to assess the culture performance of hPSCs on nanofibrous substrates in terms of cell adhesion and growth rate, using Matrigel as control. Then, the optimal conditions were applied to long-term expansion of hPSCs with several cell lines, showing a maintained pluripotency over more than 20 passages without introducing any abnormal chromosome. In addition, this approach allowed us to avoid enzymatic disassociation and mechanic cutting during passages, thereby promoting a better hPSC culture and long-term expansion.

Self-assembly of two-dimensional nanosheets induced by interfacial polyionic complexation.

Significant progress has been made during the past decade in preparing nanosheets from a wide range of materials, which are actively pursued for various applications such as energy storage, catalysis, sensing, and membranes. One of the next critical challenges is developing a robust and versatile assembly method which allows construction of the nanosheets into functional structures tailored for each specific purpose. An interesting characteristic of nanosheets is that they often behave as charged macromolecules and thus can readily interact with an oppositely charged polyelectrolyte to form a stable complex. In this report, we demonstrate how such a complexation process could be utilized for directing the self-assembly of nanosheets. By confining the nanosheet-polyelectrolyte complexation at air-liquid or liquid-liquid interfaces, the nanosheets are successfully assembled into various mesoscale architectures including fibers, capsules, and films. Furthermore, incorporation of additional components such as nanoparticles or small molecules can be easily achieved for further tailoring of material properties. This novel assembly method opens a pathway to many useful nanosheet superstructures and may be further extended to other types of nanomaterials in general.

Colloidal graphenes as heterogeneous additives to enhance protein crystal yield.

In the structural analysis of proteins via X-ray diffraction, a rate-limiting step is in favourable nucleation, a problematic obstacle in successful generation of protein crystals. Here graphene and graphene oxide were applied to protein crystallisation trials, offering improvements in crystalline output and nucleation.

Regiospecific linear assembly of Pd nanocubes for hydrogen gas sensing.

Capillary force lithography was applied to generate large area polymer patterns. A "grafting to" approach was used on the patterns to induce linear assembly of Pd nanocubes through electrostatic interaction. Pd nanoarrays with high density were subjected to a hydrogen gas sensing test. We demonstrated a feasible method to build up a miniature hydrogen sensor using self-assembly with micrometre Pd nanoarrays.

Pd(II) conjugated chitosan nanofibre mats for application in Heck cross-coupling reactions.

Pd(II)-chitosan composite nanofibres of 62 ± 9 nm diameter are efficient catalysts for Heck cross-coupling reactions. Using a model reaction of iodo-benzene and n-butyl acrylate, we demonstrate that this material can be used as a recyclable catalytic support with a very low loading of palladium (0.17 mol% Pd).

Room temperature synthesis of upconversion fluorescent nanocrystals.

Synthesis of nanocrystals that exhibit strong upconversion (UC) luminescence upon infrared excitation has been challenging due to the stringent control needed over experimental variables. Herein, we report a method to synthesize nanocrystals demonstrating high UC at room temperature in aqueous solution on graphene.

Pd-induced ordering of 2D Pt nanoarrays on phosphonated calix[4]arenes stabilised graphenes.

p-Phosphonic acid calix[4]arenes render high stability to exfoliated graphenes in water. These calix[4]arenes modified graphenes can be used as highly effective substrates to nucleate ultra-small Pd nanoparticles, which in turn serve as galvanic reaction templates for the generation of high density 2D arrays of Pt nanoparticles.

Surface oxygen triggered size change of palladium nano-crystals impedes catalytic efficacy.

Palladium nano-crystals increase in size during the initial recycling in Heck cross coupling reactions. We demonstrate that oxygen adsorbed on the surface of palladium nano-crystals plays a pivotal role in driving the ripening. This in turn is associated with a loss in catalytic activity.

Preparation and analytical application of mimetic enzyme hemin-loading magnetic silica nanotubes.

We report here the preparation and analytical application of mimetic enzyme-loading magnetic silica nanotubes (MSNs), which were synthesized via alumina template membrane method. The nanotubes integrate the advantages of silica nanotubes and superparamagnetic characteristics. Hemin (a peroxidase mimic) was selected as a model for enzyme assays to demonstrate the applicability of these MSNs in enzyme immobilization. The immobilized hemin exhibited excellent catalytic activity and reusability. Using the immobilized hemin as the catalyst, the fluorometric measurement of thiamine has been achieved with a detection limit of 2.5 x 10(-8) mol/L. Our work herein reveals that the surface functionalized MSNs will be a promising platform as biocatalyst carriers.

Preparation of magnetic silica nanoparticle-supported iron tetra-carboxyl phthalocyanine catalyst and its photocatalytic properties.

Iron tetra-carboxyl phthalocyanine (TCFePc) was covalently immobilized to the surface of core-shell magnetite silica nanoparticles (NPs) as facilely separated supported catalyst, namely P-M SiO(2) NPs, for catalyzing the degradation of organic pollutants in aqueous solution under visible light irradiation. X-ray diffraction, transmission electron microscopy (TEM), scanning electron microscopy (SEM), superconducting quantum interference device (SQUID), and ultraviolet-visible (UV-Vis) spectroscopy were used to characterize the sample. The photocatalytic activity of P-M SiO(2) NPs was determined using rhodamine B (RhB) and methyl orange (MO) as the objective decomposition substances. The results revealed that the novel supported catalyst exhibited good catalytic activity over a wide pH range, and the degradation rate of RhB and MO is up to 90% during 120 min of reaction. Moreover, it is noteworthy that the catalyst can be easily separated using an external magnetic field and employed directly for the next round of reaction.

Preparation and fluoroimmunoassay application of new red-region fluorescent silica nanoparticles.

This is the first report on the preparation and utilization of a novel red-region fluorescent dye (tetracarboxy aluminum phthalocyanine) doped silica nanoparticles. In these nanoparticles, the tetracarboxy aluminum phthalocyanine molecules were covalently bound to silica matrix to protect the dye leaking from nanoparticles in bio-applications. The surface of the nanoparticles was modified by amino groups and easily bioconjugated with goat anti-human IgG antibody. By employing these nanoparticles as fluorescent probe, a sensitive fluoroimmunoassay method has been developed for the determination of trace level of human IgG. The calibration graph for human IgG was linear over the range of 0-500 ng mL(-1) with a detection limit of 1.6 ng mL(-1). Compared with the corresponding system using free AlC(4)Pc as a probe for determining human IgG, the sensitivity of the proposed system was notably increased. The method was applied to the analysis of human IgG in human sera with satisfactory results.