Fabricating of high-performance functional graphene fibers for micro-capacitive energy storage.

Although graphene is a typical two dimensional materials, it has converted to multi-dimensional materials with many unique properties. As an example, the one dimensional graphene fiber is fabricated by utilizing ionic liquid as coagulation and functional diamines as cross-linkers to connect graphene oxide layers. The fibers show excellent mechanical properties and superior electrical performance. The tensile strength of the resultant fibers reaches ~729 MPa after a super high temperature thermal annealing treatment at 2800 °C. Additionally, quasi-solid-state flexible micro-capacitors are fabricated with promising result on energy storage. The device show a specific volumetric capacity as high as ~225 F/cm(3) (measured at 103.5 mA cm(-3) in a three-electrode cell), as well as a long cycle life of 2000 times. The initial results indicate that these fibers will be a good candidate to replace energy storage devices for miniaturized portable electronic applications.

Chemical Vapor Deposition of an Organic Magnet, Vanadium Tetracyanoethylene.

Recent progress in the field of organic materials has yielded devices such as organic light emitting diodes (OLEDs) which have advantages not found in traditional materials, including low cost and mechanical flexibility. In a similar vein, it would be advantageous to expand the use of organics into high frequency electronics and spin-based electronics. This work presents a synthetic process for the growth of thin films of the room temperature organic ferrimagnet, vanadium tetracyanoethylene (V[TCNE]x, x~2) by low temperature chemical vapor deposition (CVD). The thin film is grown at <60 °C, and can accommodate a wide variety of substrates including, but not limited to, silicon, glass, Teflon and flexible substrates. The conformal deposition is conducive to pre-patterned and three-dimensional structures as well. Additionally this technique can yield films with thicknesses ranging from 30 nm to several microns. Recent progress in optimization of film growth creates a film whose qualities, such as higher Curie temperature (600 K), improved magnetic homogeneity, and narrow ferromagnetic resonance line-width (1.5 G) show promise for a variety of applications in spintronics and microwave electronics.

Fabrication of high-quality graphene oxide nanoscrolls and application in supercapacitor.

We reported a simple and effective way of fabricating one-dimensional (1D) graphene oxide nanoscrolls (GONS) from graphene oxide (GO) sheets through shock cooling by liquid nitrogen. The corresponding mechanism of rolling was proposed. One possibility is the formation of ice crystals during the shock cooling process in liquid nitrogen to be the driving force. The other might be due to the uneven stress of the sheets inside or outside ice during the lyophilization. After reducing, graphene nanoscrolls (GNS) exhibited good structural stability, high specific surface area, and high specific capacitance. The capacitance properties were investigated by cyclic voltammetry, galvanostatic charge-discharge, and electrical impedance spectroscopy. A specific capacity of 156 F/g for the GNS at the current density of 1.0 A/g was obtained comparing with the specific capacity of 108 F/g for graphene sheets. Those results indicated that GNS-based rolling structure could be a kind of promising electrode material for supercapacitors and batteries.

Controllable size-selective method to prepare graphene quantum dots from graphene oxide.

We demonstrated one-step method to fabricate two different sizes of graphene quantum dots (GQDs) through chemical cutting from graphene oxide (GO), which had many advantages in terms of simple process, low cost, and large scale in manufacturing with higher production yield comparing to the reported methods. Several analytical methods were employed to characterize the composition and morphology of the resultants. Bright blue luminescent GQDs were obtained with a produced yield as high as 34.8%. Moreover, how the different sizes affect fluorescence wavelength mechanism was investigated in details.

Thin-film deposition of an organic magnet based on vanadium methyl tricyanoethylenecarboxylate.

The preparation and characterization of a new thin-film organic-based magnet V[MeTCEC]x (V = vanadium; MeTCEC = methyl tricaynoethylenecarboxylate) via low-temperature chemical vapor deposition (50 °C) is reported. These thin films exhibit room-temperature magnetic ordering and semiconducting behavior, demonstrating the ability of tuning their magnetic, and potentially spintronic, functionality via chemical modification of the organic ligand.

Sulfonated polyaniline-based organic electrodes for controlled electrical stimulation of human osteosarcoma cells.

Electrically conducting polymers (CPs) were found to stimulate various cell types such as neurons, osteoblasts, and fibroblasts in both in vitro and in vivo studies. However, to our knowledge, no studies have been reported on the utility of CPs in stimulation of cancer or tumor cells in the literature. Here we report a facile fabrication method of self-doped sulfonated polyaniline (SPAN)-based interdigitated electrodes (IDEs) for controlled electrical stimulation of human osteosarcoma (HOS) cells. Increased degree of sulfonation was found to increase the SPAN conductivity, which in turn improved the cell attachment and cell growth without electrical stimulation. However, an enhanced cell growth was observed under controlled electrical (AC) stimulation at low applied voltage and frequency (≤800 mV and ≤1 kHz). The cell growth reached a maximum threshold at an applied voltage or frequency and beyond which pronounced cell death was observed. We believe that these organic electrodes may find utility in electrical stimulation of cancer or tumor cells for therapy and research and may also provide an alternative to the conventional metal-based electrodes.

Carrier transport in the V[TCNE]x (TCNE = tetracyanoethylene; x ~ 2) organic-based magnet.

The carrier transport of chemical vapor deposition (CVD) prepared films of the room temperature organic-based magnet V[TCNE]x (TCNE = tetracyanoethylene; x ~ 2) over a broad temperature and magnetic field range is reported. Due to disorder the [TCNE](·-) sites are located in statistically different environments, and their energies vary from site-to-site, which leads to tailing the density of states into the energy gap, creating electronic traps and suppressing the electron mobility. Conversely, these variations have little effect on the valence band derived from the octahedral V(II)3d(t(2g)) levels, and, hence, on the hole mobility. Presuming a Gaussian distribution of the energies of the localized states in the gap, a model that adequately describes the experimental data is proposed. In this model the T(-1) temperature dependent term was added to the Arrhenius activation energy, Ea, which effectively describes its decrease on cooling. The linear increase of positive magnetoresistance with magnetic field, as well as its weak temperature dependence [ is proportional to (1-T/Tc)(-1/2)] is discussed in terms of a small contribution to Ea associated with the change of magnetic energy.

Photoinduced charge transfer involving a MoMo quadruply bonded complex to a perylene diimide.

Evidence, based on femtosecond transient absorption and time resolved infrared spectroscopy, is presented for photoinduced charge transfer from the Mo2δ orbital of the quadruply bonded molecule trans-Mo2(T(i)PB)2(BTh)2, where T(i)PB = 2,4,6-triisopropyl benzoate and BTh = 2,2'-bithienylcarboxylate, to di-n-octyl perylene diimide and di-n-hexylheptyl perylene diimide in thin films and solutions of the mixtures. The films show a long-lived charge separated state while slow back electron transfer, τBET ~ 500 ps, occurs in solution.

Molecular layer deposition of an organic-based magnetic semiconducting laminate.

Organic-based magnets are intriguing materials with unique magnetic and electronic properties that can be tailored by chemical methodology. By using molecular layer deposition (MLD), we demonstrate the thin film fabrication of V[TCNE: tetracyanoethylene](x), of the first known room temperature organic-based magnet. The resulting films exhibit improvement in surface morphology, larger coercivity (80 Oe), and higher Curie temperature/thermal stability (up to 400 K). Recently, the MLD method has been widely studied to implement fine control of organic film growth for various applications. This work broadens its application to magnetic and charge transfer materials and opens new opportunities for metal-organic hybrid material development and their applications in various multilayer film device structures. Finally, we demonstrate the applicability of the multilayer V[TCNE](x) as a spin injector combining LSMO, an standard inorganic magnetic semiconductor, for spintronics applications.

Synthesis and characterization of cytocompatible sulfonated polyanilines.

We report here that by good design, polyaniline (PANI) can be cytocompatible and formed into usable scaffolds for bio-medical applications. By adjusting the ratio of two monomers, aniline (AN) and metanilic acid (MA), a series of copolymers with different sulfonation degrees have been synthesized. Four-probe conductivity measurements showed that as the sulfonation degree increased, the conductivity decreased. XPS analysis was used to determine the sulfur/nitrogen ratio. In vitro cell culture study was conducted with human osteosarcoma (HOS) cells. Microscopic observation did not show abnormal cellular behavior when sulfonated polyaniline (SPAN) was put in direct contact with HOS cells. Cells growing on the non-transparent dark green SPAN films were observed with fluorescence by laser scanning cytometry (LSC). In proliferation studies more than 70% of cells were found viable on SPAN compared to 88% for poly(L-lactic acid) with the number of cells growing on glass as a control, indicating generally good biocompatibility. We expect these polymers would have great potential in biological applications of conducting polymers as we determine that a variety of physical and chemical properties can be controlled through synthesis.

A single molecule Kondo switch: multistability of tetracyanoethylene on Cu(111).

Single tetracyanoethyelene (TCNE) molecules on Cu(111) are reversibly switched among five states by applying voltage pulses with the tip of a scanning tunneling microscope. A pronounced Kondo resonance in tunneling spectroscopy indicates that one of the states is magnetic. Side bands of the Kondo resonance appear at energies which correspond to inter- and intramolecular vibrational modes. Density functional theory suggests that molecular deformation changes the occupancy in TCNE's molecular orbitals, thus producing the magnetic state.

Design and testing of a microfluidic biochip for cytokine enzyme-linked immunosorbent assay.

Enzyme-linked immunosorbent assay (ELISA) has been widely used in medical diagnostics, environmental analyses, and biochemical studies. To reduce assay time and lower consumption of reagents in cytokine ELISA analysis, a polymeric microfluidic biochip has been designed and fabricated via several new techniques: Polyaniline-based surface modification for superhydrophobic capillary valving and oxygen plasma-poly(ethyleneimine)-tyrosinase-protein A modification for high sensitivity protein detection. The proper flow sequencing was achieved using the superhydrophobic capillary valves. The burst frequency of each valve was experimentally determined and compared with two capillary force equations and the fluent finite element simulation. This fully automated microfluidic biochip with an analyzer is able to provide high fluorescence signal of ELISA with a wider linear detection range and a much shorter assay time than 96-well microtiter plates. It is applicable to a variety of nonclinic research and clinically relevant disease conditions. The modification technologies in this study can be implemented in other lab-on-a-chip systems, druggene delivery carriers, and other immunoassay biosensor applications.

Cationic lipid-coated magnetic nanoparticles associated with transferrin for gene delivery.

Cationic lipid-coated magnetic nanoparticles (MPs) associated with transferrin were evaluated as gene transfer vectors in the presence of a static magnetic field. MPs were prepared by chemical precipitation and were surface-coated with cationic lipids, composed of DDAB/soy PC (60:40 mole/mole). These cationic MPs were then combined with polyethylenimine (PEI) condensed plasmid DNA, followed by transferrin. The resulting magnetic electrostatic complexes retained relatively compact particle size and showed complete DNA condensation. Their transfection activity in the presence of a static magnetic field was evaluated by luciferase and green fluorescent protein (GFP) reporter genes. The magnetic complexes exhibited up to 300-fold higher transfection activity compared to commonly used cationic liposomes or cationic polymer complexes, based on luciferase assay. The enhancement in transfection activity was maximized when the cells were exposed to the vectors for a relatively short period of time (15 min), or were treated in media containing 10% serum. Incorporation of transferrin further improved transfection efficiency of the cationic MPs. However, when cells were incubated for 4h in serum-free media, magnetic and non-magnetic vectors showed similar transfection efficiencies. In conclusion, transferrin-associated cationic MPs are excellent gene transfer vectors that can mediate very rapid and efficient gene transfer in vitro in the presence of a magnetic field.

Growth and alignment of polyaniline nanofibres with superhydrophobic, superhydrophilic and other properties.

Polyaniline nanofibres can be prepared by a number of methods based on chemical oxidative polymerization and in situ adsorption polymerization. However, the lack of alignment in these nanostructures makes them unsuitable for many applications. Here, we report a simple approach to chemical oxidative polymerization that can control the growth and simultaneous alignment of polyaniline nanofibres grown on a range of conducting and non-conducting substrates in a wide variety of sizes. The diameters of the tips of the nanofibres can be controlled within the range 10-40 nm, and the average length can be controlled within the range 70-360 nm. Moreover, the coatings display a range of properties including superhydrophilicity and superhydrophobicity. Such nanostructured coatings may be useful for applications such as anti-fog coatings, self-cleaning surfaces, DNA manipulation, transparent electrodes for low-voltage electronics, and chemical and biological sensors.

Photoinduced magnetization in the organic-based magnet Mn(TCNE)(x)* y(CH2Cl2).

Photoinduced magnetization in a magnet based on organic species is reported for the first time. Upon optical excitation in the blue region of spectrum, Mn(tetracyanoethylene)(x)*y(CH2Cl2) (x approximately 2, y is approximately 0.8) exhibits increased magnetic susceptibility at temperatures as high as 75 K, accompanied with photoinduced absorption in the visible and infrared spectral regions. These effects are partially reversible by lower energy visible light and fully reversible by thermal treatment. The results suggest trapping of the photoexcited charge in a metastable state with enhanced exchange interaction.

Weak Effect on T(c) with Increased Interchain Distances. Structure and Magnetic Properties of (meso-Tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)porphinato)manganese(III) Tetracyanoethenide, [Mn(III)TP'P](+)[TCNE](*-).

(meso-Tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)porphinato)manganese(III) tetracyanoethenide, [MnTP'P][TCNE], has been structurally and magnetically characterized. [MnTP'P][TCNE] (C(96)H(108)MnN(8)O(4)) belongs to the triclinicP&onemacr; (No. 2) space group with a = 8.597(2) Å, b = 14.756(4) Å, c = 17.573(5) Å, alpha = 101.16 (2) degrees, beta = 100.56(2) degrees, gamma = 96.37(2) degrees, and Z = 1. Due to the oxidative instability of the phenoxy groups, [Mn(III)TP'P][TCNE] was prepared from the reaction of [Mn(III)TP'P]OAc with the strong acid H(2)TCNE (pK(a) = 3.6) in the presence of TCNE to form acetic acid and the product. [MnTP'P][TCNE] is a coordination polymer with the Mn(III) sites bridged by trans-&mgr;(2)-bound [TCNE](*)(-) with relatively short (8.587 Å) intrachain and long (>/=14.756 Å) interchain Mn.Mn separations. The magnetic data above 210 K obey the Curie-Weiss expression with an effective &THETAV; value of 90.0 K, the largest yet reported for a soluble molecule-based magnet. In addition to a 15 K T(c) hysteretic behavior with a coercive field of 100 Oe is observed at 5 K. Despite the significant steric bulk leading to the substantially decreased interchain interactions that are crucial for magnetic ordering, the T(c) is unexpectedly high and suggests that other linear chain systems may be expected to exhibit magnetic ordering at higher temperatures.