Ursolic acid induces apoptosis and autophagy in oral cancer cells.

Oral squamous cell carcinoma (OSCC) is the fifth common cause of cancer mortality in Taiwan with high incidence and recurrence and needs new therapeutic strategies. In this study, ursolic acid (UA), a triterpenoid, was examined the antitumor potency in OSCC cells. Our results showed that UA inhibited the proliferation of OSCC cells in a dose- and time-dependent manner in both Ca922 and SCC2095 oral cancer cells. UA induced caspase-dependent apoptosis accompanied with the modulation of various biological biomarkers including downregulating Akt/mTOR/NF-κB signaling, ERK, and p38. In addition, UA inhibited angiogenesis as evidenced by abrogation of migration/invasion and blocking MMP-2 secretion in Ca922 cells. Interestingly, UA induced autophagy in OSCC cells, as manifested by LC3B-II conversion and increased p62 expression and accumulation of autophagosomes. Inhibition by autophagy inhibitor enhanced UA-mediated apoptosis in Ca922 cells. The experiment provides a rationale for using triterpenoid in the treatment of OSCC.

Self-Patterning of Silica/Epoxy Nanocomposite Underfill by Tailored Hydrophilic-Superhydrophobic Surfaces for 3D Integrated Circuit (IC) Stacking.

As microelectronics are trending toward smaller packages and integrated circuit (IC) stacks nowadays, underfill, the polymer composite filled in between the IC chip and the substrate, becomes increasingly important for interconnection reliability. However, traditional underfills cannot meet the requirements for low-profile and fine pitch in high density IC stacking packages. Post-applied underfills have difficulties in flowing into the small gaps between the chip and the substrate, while pre-applied underfills face filler entrapment at bond pads. In this report, we present a self-patterning underfilling technology that uses selective wetting of underfill on Cu bond pads and Si3N4 passivation via surface energy engineering. This novel process, fully compatible with the conventional underfilling process, eliminates the issue of filler entrapment in typical pre-applied underfilling process, enabling high density and fine pitch IC die bonding.

Vapor-Phase Polymerized Poly(3,4-Ethylenedioxythiophene) on a Nickel Nanowire Array Film: Aqueous Symmetrical Pseudocapacitors with Superior Performance.

Three-dimensional (3D) nanometal scaffolds have gained considerable attention recently because of their promising application in high-performance supercapacitors compared with plain metal foils. Here, a highly oriented nickel (Ni) nanowire array (NNA) film was prepared via a simple magnetic-field-driven aqueous solution deposition process and then used as the electrode scaffold for the vapor-phase polymerization of 3,4-ethylenedioxythiophene (EDOT). Benefiting from the unique 3D open porous structure of the NNA that provided a highly conductive and oriented backbone for facile electron transfer and fast ion diffusion, the as-obtained poly(3,4-ethylenedioxythiophene) (PEDOT) exhibited an ultra-long cycle life (95.7% retention of specific capacitance after 20 000 charge/discharge cycles at 5 A/g) and superior capacitive performance. Furthermore, two electrodes were fabricated into an aqueous symmetric supercapacitor, which delivered a high energy density (30.38 Wh/kg at 529.49 W/kg) and superior long-term cycle ability (13.8% loss of capacity after 20 000 cycles). Based on these results, the vapor-phase polymerization of EDOT on metal nanowire array current collectors has great potential for use in supercapacitors with enhanced performance.

An Ultralong, Highly Oriented Nickel-Nanowire-Array Electrode Scaffold for High-Performance Compressible Pseudocapacitors.

Ultralong, highly oriented Ni nanowire arrays are used as the electrode scaffold to support metal-oxide- and conductive-polymer-based electrode materials with a high mass loading; the as-obtained asymmetric supercapacitor can be compressed by fourfold and exhibits superior energy and power densities with ultrahigh cycle stability.

Conformal Pad-Printing Electrically Conductive Composites onto Thermoplastic Hemispheres: Toward Sustainable Fabrication of 3-Cents Volumetric Electrically Small Antennas.

Electrically small antennas (ESAs) are becoming one of the key components in the compact wireless devices for telecommunications, defence, and aerospace systems, especially for the spherical one whose geometric layout is more closely approaching Chu's limit, thus yielding significant bandwidth improvements relative to the linear and planar counterparts. Yet broad applications of the volumetric ESAs are still hindered since the low cost fabrication has remained a tremendous challenge. Here we report a state-of-the-art technology to transfer electrically conductive composites (ECCs) from a planar mould to a volumetric thermoplastic substrate by using pad-printing technology without pattern distortion, benefit from the excellent properties of the ECCs as well as the printing-calibration method that we developed. The antenna samples prepared in this way meet the stringent requirement of an ESA (ka is as low as 0.32 and the antenna efficiency is as high as 57%), suggesting that volumetric electronic components i.e. the antennas can be produced in such a simple, green, and cost-effective way. This work can be of interest for the development of studies on green and high performance wireless communication devices.

Alternating current line-filter based on electrochemical capacitor utilizing template-patterned graphene.

Aluminum electrolytic capacitors (AECs) are widely used for alternating current (ac) line-filtering. However, their bulky size is becoming more and more incompatible with the rapid development of portable electronics. Here we report a scalable process to fabricate miniaturized graphene-based ac line-filters on flexible substrates at room temperature. In this work, graphene oxide (GO) is reduced by patterned metal interdigits at room temperature and used directly as the electrode material. The as-fabricated device shows a phase angle of -75.4° at 120 Hz with a specific capacitance of 316 µF/cm(2) and a RC time constant of 0.35 ms. In addition, it retains 97.2% of the initial capacitance after 10000 charge/discharge cycles. These outstanding performance characteristics of our device demonstrate its promising to replace the conventional AECs for ac line filtering.

Shape-Tailorable Graphene-Based Ultra-High-Rate Supercapacitor for Wearable Electronics.

With the bloom of wearable electronics, it is becoming necessary to develop energy storage units, e.g., supercapacitors that can be arbitrarily tailored at the device level. Although gel electrolytes have been applied in supercapacitors for decades, no report has studied the shape-tailorable capability of a supercapacitor, for instance, where the device still works after being cut. Here we report a tailorable gel-based supercapacitor with symmetric electrodes prepared by combining electrochemically reduced graphene oxide deposited on a nickel nanocone array current collector with a unique packaging method. This supercapacitor with good flexibility and consistency showed excellent rate performance, cycling stability, and mechanical properties. As a demonstration, these tailorable supercapacitors connected in series can be used to drive small gadgets, e.g., a light-emitting diode (LED) and a minimotor propeller. As simple as it is (electrochemical deposition, stencil printing, etc.), this technique can be used in wearable electronics and miniaturized device applications that require arbitrarily shaped energy storage units.

Electrospray-deposition of graphene electrodes: a simple technique to build high-performance supercapacitors.

Here we report an electrostatic spray deposition method to prepare three-dimensional porous graphene electrodes for supercapacitor applications. The symmetric supercapacitor exhibits excellent specific capacitance (366 F g(-1) at 1 A g(-1) in 6 M KOH) and long cycle life (108% capacitance retention up to 40 000 cycles). Moreover, the energy densities of the organic and aqueous electrolyte based supercapacitors reach 22.9 and 8.1 Wh kg(-1) when the power densities are 119.2 and 15.4 kW kg(-1), respectively. Compared with the previously reported graphene based supercapacitors, the improved properties could be attributed to the excellent three-dimensional open porous electrode structure, which is favorable for the ion diffusion and electron transport. In addition, this method provides a simple electrode-fabrication route without the involvement of conducting additives and binders. It may find vast applications in thin and miniaturized energy storage scenarios.

Low-cost high-performance solid-state asymmetric supercapacitors based on MnO2 nanowires and Fe2O3 nanotubes.

A low-cost high-performance solid-state flexible asymmetric supercapacitor (ASC) with α-MnO2 nanowires and amorphous Fe2O3 nanotubes grown on flexible carbon fabric is first designed and fabricated. The assembled novel flexible ASC device with an extended operating voltage window of 1.6 V exhibits excellent performance such as a high energy density of 0.55 mWh/cm(3) and good rate capability. The ASC devices can find numerous applications as effective power sources, such as powering color-switchable sun glasses and smart windows.

Uniform vertical trench etching on silicon with high aspect ratio by metal-assisted chemical etching using nanoporous catalysts.

Recently, metal-assisted chemical etching (MaCE) has been proposed as a promising wet-etching method for the fabrication of micro- and nanostructures on silicon with low cost. However, uniform vertical trench etching with high aspect ratio is still of great challenge for traditional MaCE. Here we report an innovated MaCE method, which combined the use of a nanoporous gold thin film as the catalyst and a hydrofluoric acid (HF)-hydrogen peroxide (H2O2) mixture solution with a low HF-to-H2O2 concentration ratio (ρ) as the etchant. The reported method successfully fabricated vertical trenches on silicon with a width down to 2 µm and an aspect ratio of 16. The geometry of the trenches was highly uniform throughout the 3D space. The vertical etching direction was favored on both (100)- and (111)-oriented silicon substrates. The reported method was also capable of producing multiple trenches on the same substrate with individually-tunable lateral geometry. An etching mechanism including a through-catalyst mass-transport process and an electropolishing-favored charge-transport process was identified by a comparative study. The novel method fundamentally solves the problems of distortion and random movement of isolated catalysts in MaCE. The results mark a breakthrough in high-quality silicon trench-etching technology with a cost of more than 2 orders of magnitude lower than that of the currently available methods.

Magnetic alignment of hexagonal boron nitride platelets in polymer matrix: toward high performance anisotropic polymer composites for electronic encapsulation.

We report magnetic alignment of hexagonal boron nitride (hBN) platelets and the outstanding material properties of its polymer composite. The magnetically responsive hBN is produced by surface modification of iron oxide, and their orientations can be controlled by applying an external magnetic field during polymer curing. Owing to the anisotropic properties of hBN, the epoxy composite with aligned hBN platelets shows interesting properties along the alignment direction, including significantly reduced coefficient of thermal expansion, reaching ∼28.7 ppm/°C, and enhanced thermal conductivity, 104% higher than that of unaligned counterpart, both of which are observed at a low filler loading of 20 wt %. Our modeling suggests the filler alignment is the major reason for these intriguing material properties. Finite element analysis reveals promising applications for the magnetically aligned hBN-based composites in modern microelectronic packaging.

Hydrogenated ZnO core-shell nanocables for flexible supercapacitors and self-powered systems.

Although MnO2 is a promising material for supercapacitors (SCs) due to its excellent electrochemical performance and natural abundance, its wide application is limited by poor electrical conductivity. Inspired by our results that the electrochemical activity and electrical conductivity of ZnO nanowires were greatly improved after hydrogenation, we designed and fabricated hydrogenated single-crystal ZnO@amorphous ZnO-doped MnO2 core-shell nanocables (HZM) on carbon cloth as SC electrodes, showing excellent performance such as areal capacitance of 138.7 mF/cm(2) and specific capacitance of 1260.9 F/g. Highly flexible all-solid-state SCs were subsequently assembled with these novel HZM electrodes using polyvinyl alcohol/LiCl electrolyte. The working devices achieved very high total areal capacitance of 26 mF/cm(2) and retained 87.5% of the original capacitance even after 10 000 charge/discharge cycles. An integrated power pack incorporating series-wound SCs and dye-sensitized solar cells was demonstrated for stand-alone self-powered systems.

Silicon-based hybrid energy cell for self-powered electrodegradation and personal electronics.

Silicon (Si)-based solar cell is by far the most established solar cell technology. The surface of a Si solar cell is usually covered by a layer of transparent material to protect the device from corrosion, contamination and mechanical damage. Here, we replaced this protection layer by a thin layer film of polydimethysiloxane nanowires. Based on this layer and using the conductive layer on the surface of the wavy Si, we have fabricated a triboelectric nanogenerator (TENG). The solar cell and the TENG form a hybrid energy cell for simultaneously harvesting solar and mechanical energies. The hybrid energy cell can be directly used for self-powered electrodegradation of rhodamine B, where the degradation percentage is up to 98% in 10 min. Moreover, the produced energy can also be stored in the Li-ion batteries for driving some personal electronics such as a red laser diode and a commercial cell phone.

Automated dispersion and orientation analysis for carbon nanotube reinforced polymer composites.

The properties of carbon nanotube (CNT)/polymer composites are strongly dependent on the dispersion and orientation of CNTs in the host matrix. Quantification of the dispersion and orientation of CNTs by means of microstructure observation and image analysis has been demonstrated as a useful way to understand the structure-property relationship of CNT/polymer composites. However, due to the various morphologies and large amount of CNTs in one image, automatic and accurate identification of CNTs has become the bottleneck for dispersion/orientation analysis. To solve this problem, shape identification is performed for each pixel in the filler identification step, so that individual CNTs can be extracted from images automatically. The improved filler identification enables more accurate analysis of CNT dispersion and orientation. The dispersion index and orientation index obtained for both synthetic and real images from model compounds correspond well with the observations. Moreover, these indices help to explain the electrical properties of CNT/silicone composite, which is used as a model compound. This method can also be extended to other polymer composites with high-aspect-ratio fillers.

Reversible superhydrophobic-superhydrophilic transition of ZnO nanorod/epoxy composite films.

Tuning the surface wettability is of great interest for both scientific research and practical applications. We demonstrated reversible transition between superhydrophobicity and superhydrophilicity on a ZnO nanorod/epoxy composite film. The epoxy resin serves as an adhesion and stress relief layer. The ZnO nanorods were exposed after oxygen reactive ion etching of the epoxy matrix. A subsequent chemcial treatment with fluoroalkyl and alkyl silanes resulted in a superhydrophobic surface with a water contact angle up to 158.4° and a hysteresis as low as 1.3°. Under UV irradiation, the water contact angle decreased gradually, and the surface eventually became superhydrophilic because of UV induced decomposition of alkyl silanes and hydroxyl absorption on ZnO surfaces. A reversible transition of surface wettability was realized by alternation of UV illumination and surface treatment. Such ZnO nanocomposite surface also showed improved mechanical robustness.

A combined etching process toward robust superhydrophobic SiC surfaces.

Large-scale porous SiC was fabricated by a combination of Pt-assisted etching and reactive ion etching. It was found that the surface roughness of combined etchings increased dramatically in comparison with metal-assisted etching or reactive ion etching only. To reduce the surface energy, the porous SiC surface was functionalized with perfluorooctyl trichlorosilane, resulting in a superhydrophobic SiC surface with a contact angle of 169.2° and a hysteresis of 2.4°. The superhydrophobicity of the SiC surface showed a good long-term stability in an 85 °C/85% humidity chamber. Such superhydrophobicity was also stable in acidic or basic solutions, and the pH values showed little or no effect on the SiC surface status. In addition, enhancement of porosity-induced photoluminescence intensity was found in the superhydrophobic SiC samples. The robust superhydrophobic SiC surfaces may have a great potential for microfluid device, thermal ground plane, and biosensor applications.

Facile preparation of nitrogen-doped graphene as a metal-free catalyst for oxygen reduction reaction.

Nitrogen-doped graphene (nG) is a promising metal-free catalyst for oxygen reduction reaction (ORR) on the cathode of fuel cells. Here we report a facile preparation of nG via pyrolysis of graphene oxide with melamine. The morphology of the nG is revealed using scanning electron microscopy and transmission electron microscopy while the successful N doping is confirmed by electron energy loss spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. The resulting nG shows high electrocatalytic activity toward ORR in an alkaline solution with an onset potential of -0.10 V vs. Ag/AgCl reference electrode. The nG catalyzed oxygen reduction exhibits a favorable formation of water via a four-electron pathway. Good stability and anti-crossover property are also observed, which are advantageous over the Pt/C catalyst. Furthermore, the effect of pyrolysis temperature on the structure and activity of nG is systematically studied to gain some insights into the chemical reactions during pyrolysis.

Facile fabrication of superhydrophobic octadecylamine-functionalized graphite oxide film.

We demonstrated a facile strategy of producing superhydrophobic octadecylamine (ODA)-functionalized graphite oxide (GO) films. ODA was chemically grafted on GO sheets by the nucleophilic substitution reaction of amine groups with epoxy groups. The long hydrocarbon chain in ODA reduces the surface energy of the GO sheet. The fabricated ODA-functionalized GO film exhibited a high contact angle (163.2°) and low hysteresis (3.1°). This method is promising in terms of low-cost and large-scale superhydrophobic coatings and has potential applications for surface modification of GO paper or other GO-based composite materials.

Rational preparation of faceted platinum nanocrystals supported on carbon nanotubes with remarkably enhanced catalytic performance.

Faceted platinum nanocrystals supported on carbon nanotubes were prepared using NO2- as a crucial shape-controlling agent. The composites exhibit high electrochemical catalytic activity for oxygen reduction facilitated by the cooperation between the Pt{111} facets and atomic steps, and extremely high selectivity for the oxidation of glycerol to glyceraldehyde.