Lia Stanciu

Fabrication of high-surface-area graphene/polyaniline nanocomposites and their application in supercapacitors.

Graphene/polyaniline (PANI) nanocomposites were prepared by reducing graphene oxide with hydrazine in the presence of different amounts of polyaniline nanoparticles. In situ cryo-transmission electron microscope (TEM) images of a graphene oxide (GO)/PANI solution revealed that the PANI nanoparticles were anchored on the surface of the GO sheets. During the reduction, the as-adsorbed PANI nanoparticles were sandwiched between layers of graphene sheets. These PANI nanoparticles acted as spacers to create gaps between neighboring graphene sheets, resulting in a higher surface area compared to pure graphene. Graphene/PANI nanocomposites exhibited the high specific surface area of 891 m2/g. Utilizing this composite material, a supercapacitor with a specific capacitance of 257 F/g at a current density of 0.1 A/g has been achieved.

Structure of TRPV1 channel revealed by electron cryomicroscopy

The transient receptor potential (TRP) family of ion channels participate in many signaling pathways. TRPV1 functions as a molecular integrator of noxious stimuli, including heat, low pH, and chemical ligands. Here, we report the 3D structure of full-length rat TRPV1 channel expressed in the yeast Saccharomyces cerevisiae and purified by immunoaffinity chromatography. We demonstrate that the recombinant purified TRPV1 channel retains its structural and functional integrity and is suitable for structural analysis. The 19-Å structure of TRPV1 determined by using single-particle electron cryomicroscopy exhibits fourfold symmetry and comprises two distinct regions: a large open basket-like domain, likely corresponding to the cytoplasmic N- and C-terminal portions, and a more compact domain, corresponding to the transmembrane portion. The assignment of transmembrane and cytoplasmic regions was supported by fitting crystal structures of the structurally homologous Kv1.2 channel and isolated TRPV1 ankyrin repeats into the TRPV1 structure.

Effect of temperature and moisture on the miscibility of amorphous dispersions of felodipine and poly(vinyl pyrrolidone)

The physical stability of amorphous molecular level solid dispersions will be influenced by the miscibility of the components. The goal of this work was to understand the effects of temperature and relative humidity on the miscibility of a model amorphous solid dispersion. Infrared spectroscopy was used to evaluate drug-polymer hydrogen bonding interactions in amorphous solid dispersions of felodipine and poly(vinyl pyrrolidone) (PVP). Samples were analyzed under stressed conditions: high temperature and high relative humidity. The glass transition temperature (T(g)) of select systems was studied using differential scanning calorimetry (DSC). Atomic force microscopy (AFM) and transmission electron microscopy (TEM) were used to further investigate moisture-induced changes in solid dispersions. Felodipine-PVP solid dispersions showed evidence of adhesive hydrogen bonding interactions at all compositions studied. The drug-polymer intermolecular interactions were weakened and/or less numerous on increasing the temperature, but persisted up to the melting temperature of the drug. Changes in the hydrogen bonding interactions were found to be reversible with changes in temperature. In contrast, the introduction of water into amorphous molecular level solid dispersions at room temperature irreversibly disrupted interactions between the drug and the polymer resulting in amorphous-amorphous phase separation followed by crystallization. DSC, AFM, and TEM results provided further evidence for the occurrence of moisture induced immiscibility. In conclusion, it appears that felodipine-PVP solid dispersions are susceptible to moisture-induced immiscibility when stored at a relative humidity >or=75%. In contrast, the solid dispersions remained miscible on heating.

Natural biopolymers: Novel templates for the synthesis of nanostructures

Biological systems such as proteins, viruses, and DNA have been most often reported to be used as templates for the synthesis of functional nanomaterials, but the properties of widely available biopolymers, such as cellulose, have been much less exploited for this purpose. Here, we report for the first time that cellulose nanocrystals (CNC) have the capacity to assist in the synthesis of metallic nanoparticle chains. A cationic surfactant, cetyltrimethylammonium bromide (CTAB), was critical to nanoparticle stabilization and CNC surface modification. Silver, gold, copper, and platinum nanoparticles were synthesized on CNCs, and the nanoparticle density and particle size were controlled by varying the concentration of CTAB, the pH of the salt solution, and the reduction time.

Graphene-modified nanostructured vanadium pentoxide hybrids with extraordinary electrochemical performance for Li-ion batteries

The long-standing issues of low intrinsic electronic conductivity, slow lithium-ion diffusion and irreversible phase transitions on deep discharge prevent the high specific capacity/energy (443 mAh g(-1) and 1,550 Wh kg(-1)) vanadium pentoxide from being used as the cathode material in practical battery applications. Here we develop a method to incorporate graphene sheets into vanadium pentoxide nanoribbons via the sol-gel process. The resulting graphene-modified nanostructured vanadium pentoxide hybrids contain only 2 wt. % graphene, yet exhibits extraordinary electrochemical performance: a specific capacity of 438 mAh g(-1), approaching the theoretical value (443 mAh g(-1)), a long cyclability and significantly enhanced rate capability. Such performance is the result of the combined effects of the graphene on structural stability, electronic conduction, vanadium redox reaction and lithium-ion diffusion supported by various experimental studies. This method provides a new avenue to create nanostructured metal oxide/graphene materials for advanced battery applications.

Enzyme functionalized nanoparticles for electrochemical biosensors: A comparative study with applications for the detection of bisphenol A

We developed electrochemical biosensors based on enzyme functionalized nanoparticles of different compositions for the detection of bisphenol A. We utilized for the first time magnetic nickel nanoparticles as an enzyme immobilization platform and electrode material to construct screen-printing enzyme biosensors for bisphenol A. We compared the analytical performance of these sensors with those based on iron oxide (Fe(3)O(4)) and gold nanoparticles. The proposed biosensor format exhibited fast and sensitive amperometric responses to bisphenol A with a response time of less then 30s. Among the three configurations, nickel provided comparable or better characteristics in terms of detection limit and sensitivity than Fe(3)O(4) and gold nanoparticles. The biosensors were characterized by good reproducibility, stability of more than 100 assays (residual activity for nickel was 98%) and a wide linear range which spanned from 9.1 × 10(-7) to 4.8 × 10(-5)M for nickel, 2.2 × 10(-8) to 4.0 × 10(-5)M for Fe(3)O(4) and 4.2 × 10(-8) to 3.6 × 10(-5)M for gold. The highest sensitivity was obtained with nickel. The detection limits for the three types of biosensors were: 7.1 × 10(-9), 8.3 × 10(-9) and 1 × 10(-8)M for nickel, Fe(3)O(4) and gold nanoparticles in that order, respectively. These results demonstrate that nickel nanoparticles can be successfully used in the construction of electrochemical enzyme sensors for the detection of phenolic compounds.

Novel pyrolyzed polyaniline-grafted silicon nanoparticles encapsulated in graphene sheets as Li-ion battery anodes.

A simple method to fabricate graphene-encapsulated pyrolyzed polyaniline-grafted Si nanoparticles has been developed. Instead of using Si nanoparticles with a native oxide layer, HF-treated Si nanoparticles were employed in this work. The uniqueness of this method is that, first, a PANI layer over the Si nanoparticles was formed via the surface-initiated polymerization of aniline on the surface of aniline-functionalized Si nanoparticles; then, the PANI-grafted Si nanoparticles were wrapped by the GO sheets via π-π interaction and electrostatic attraction between the GO and the PANI. Finally, the GO and PANI were pyrolyzed, and this pyrolyzed PANI layer tightly binds the graphene sheets and the Si nanoparticles together in the composite. The composite materials exhibit better cycling stability and Coulombic efficiency as anodes in lithium ion batteries, as compared to pure Si nanoparticles and physically mixed graphene/Si composites. After 300 cycles at a current density of 2 A/g, the composite electrodes can still deliver a specific capacity of about 900 mAh/g, which corresponds to ∼76% capacity retention. The enhanced performance can be attributed to the absence of surface oxides, the better electronic conductivity, faster ion diffusion rate, and the strong interaction between the graphene sheets and the tightly bound carbon-coated Si nanoparticles.

AChE biosensor based on zinc oxide sol-gel for the detection of pesticides.

Zinc oxide has been used as a matrix for immobilization of acetylcholinesterase (AChE) and detection of the pesticide paraoxon. The immobilized enzyme retained its enzymatic activity up to three months when stored in phosphate buffered saline (pH 7.4) at 4 degrees C. An amperometric biosensor for the detection of paraoxon was designed. The biosensor detected paraoxon in the range 0.035-1.38 ppm and can be used to detect other AChE inhibiting organophosphate pesticides.

An aqueous media based approach for the preparation of a biosensor platform composed of graphene oxide and Pt-black.

The combination of Pt nanoparticles and graphene was more effective in enhancing biosensing than either nanomaterial alone according to previous reports. Based on the structural similarities between water soluble graphene oxide (GrO(x)) and graphene, we report the fabrication of an aqueous media based GrO(x)/Pt-black nanocomposite for biosensing enhancement. In this approach GrO(x) acted as a nanoscale molecular template for the electrodeposition of Pt-black, an amorphously nanopatterned isoform of platinum metal. Scanning electron microscopy (SEM) images and energy-dispersive X-ray spectroscopy (EDS) showed that Pt-black was growing along GrO(x). The effective surface area and electrocatalytic activity towards H(2)O(2) oxidation of GrO(x)/Pt-black microelectrodes were significantly higher than for Pt-black microelectrodes. When used to prepare a bio-nanocomposite based on protein functionalization with the enzyme glucose oxidase (GOx), the GrO(x)/Pt-black microbiosensors exhibited improved sensitivity over the Pt-black microbiosensors. This suggested that the GrO(x)/Pt-black nanocomposite facilitated an increase in electron transfer, and/or minimized mass transport limitations as compared to Pt-black used alone. Glucose microbiosensors based on GrO(x)/Pt-black exhibited high sensitivity (465.9 ± 48.0 nA/mM), a low detection limit of 1 μM, a linear response range of 1 μM-2mM, and response time of ≈ 4s. Additionally the sensor was stable and highly selective over potential interferents.

Core/shell nanoparticles as hybrid platforms for the fabrication of a hydrogen peroxide biosensor

Core/shell nanoparticles consisting of a Fe3O4 nanoparticle core and a mesoporous silica shell (Fe3O4/m-silica) were used as a matrix for immobilization of horseradish peroxidase (HRP) enzyme and subsequent design of an amperometric hydrogen peroxide biosensor. HRP enzyme was immobilized on the core/shell nanoparticles through the electrostatic interaction between oppositely charged HRP enzyme and the silica shell at neutral pH. The enzyme–core/shell nanoparticle hybrid material was deposited on screen printed electrodes and further characterized by ultraviolet–visible (UV-vis) spectroscopy and scanning electron microscopy (SEM). This set up was used as a biosensor to detect hydrogen peroxide. The hydrogen peroxide biosensor showed a detection limit of 4.3 × 10−7 M, at a signal-to-noise ratio of 3, and a sensitivity of 84.4 μA mM−1 cm2.