Oxidative Cleavage of Aromatic C-O Linkages by Oxoammonium Salts.

Oxidative cleavage of aromatic C(sp2)-O bond is important to the conversion of biomass and plastic wastes into value-added chemicals. Here we put forward the oxidative cleavage of para-C-O bonds in phenolic compounds in use of oxoammonium salts as oxidant and water as the oxygen source. The mechanism is that oxoammonium cation activates water to form hydroxy-oxoammonium adduct and thus realizes the ipso-substitution of 4-alkoxyphenol, which is proved by substituent effect, isotope labelling experiments, and kinetic analysis. Furthermore, this protocol is successfully applied into the depolymerization of both lignin model compounds with α-O-5 and 4-O-5 linkages and polyphenylene oxide (PPO).

Mapping the Identity of Transition Metal Doping and Surface Passivation in Indium Phosphide with Theoretical Calculation.

Understanding the electronic structure of doped InP quantum dots (QDs) is essential to optimize the material for specific optoelectronic applications. However, current synthesis approaches are often tedious and unfavorable for rational tunning. Herein, a combination of experimental and computational studies was conducted to address the doping mechanism and surface passivation of InP QDs. The successful dopant introduction requires low Cu doping concentration and heavy Mn doping, while the Ag doping amount is relatively moderate. This may correspond to the theoretical doping formation energy presented as Cu (-2.52 eV) < Ag (-1.76 eV) < Mn (-0.38 eV). As for surface passivation, inorganic ions and shell-like ZnS are unraveled through simulational investigation. Chloride ion promotes oriented growth toward tetrahedron morphology while nitrate-passivated InP QDs exhibit blurry transmission electron microscope (TEM) morphology. Correspondingly, the binding energy of chloride ion with (111) facet is -2.13 eV significantly lower than those of (110) and (100) facets. Further, the additional Zn 3d bands are more involved in the formation of conduction band, which optimized the Mn-doped InP with a 0.32 eV bandgap. These experimental and model results provide more microscopic details of doped InP, which can motivate theoretically exact control of guest ion stoichiometry with optimized characteristics for electrical devices.

Overcoming Ion Transport Barrier by Plasma Heterointerface Engineering: Epitaxial Titanium Carbonitride on Nitrogen-Doped TiO2 for High-Performance Sodium-Ion Batteries.

Anatase TiO2 is a promising anode material for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) due to its high specific capacity, low cost, and excellent cycle stability. However, low electrical conductivity and poor Na+ ion transport in TiO2 limit its practical applications. Here, substantially boosted Na+ ion transport and charge transfer kinetics are demonstrated by constructing a near-ideal non-rectifying titanium carbonitride/nitrogen-doped TiO2 (TiCx N1- x /N-TiO2 ) heterostructure. Owing to the fast plasma effects and metastable hybrid phases, the TiCx N1- x is epitaxially grown on TiO2 . Energy band engineering at the interface induces high electron densities and a strong built-in electric field, which lowers the Na+ diffusion barrier by a factor of 1.7. As a result, the TiCx N1- x /N-TiO2 electrode exhibits excellent electrochemical performance. The reversible specific capacities at rates of 0.1 and 10 C reach 312.3 and 173.7 mAh g-1 , respectively. After 600 cycles of charge and discharge at 10 C, the capacity retention rate is 98.7%. This work discovers an effective non-equilibrium plasma-enabled process to construct heterointerfaces that can enhance Na+ ion transport and provides generic guidelines for the design of heterostructures for a broader range of energy storage, separation, and other devices that rely on controlled ionic transport.

Heterostructural CsPbX3-PbS (X = Cl, Br, I) Quantum Dots with Tunable Vis-NIR Dual Emission.

Perovskite and chalcogenide quantum dots (QDs) are important nano semiconductors. It has been a challenge to synthesize heterostructural QDs combining perovskite and chalcogenide with tailorable photoelectronic properties. In this report, heterostructural CsPbX3-PbS (X = Cl, Br, I) QDs were successfully synthesized via a room temperature in situ transformation route. The CsPbX3-PbS QDs show a tunable dual emission feature with the visible and near-infrared (NIR) photoluminescence (PL) corresponding to CsPbX3 and PbS, respectively. Typically, the formation and evolution of the heterostructural CsPbBr3-PbS QDs with reaction time was investigated. Femtosecond transient absorption spectroscopy (TAS) was applied to illuminate the exciton dynamics in CsPbBr3-PbS QDs. The mild synthetic method and TAS proved perovskite to PbS energy transfer may pave the way toward highly efficient QD photovoltaic and optoelectronic devices.

Continuous tunable broadband emission of fluorphosphate glasses for single-component multi-chromatic phosphors.

A kind of Sn2+/Mn2+ co-doped fluorphosphate (FP) glasses that served as single-component continuous tunable broadband emitting multi-chromatic phosphors are developed for the first time. Importantly, these FP glasses have high thermal conductivity (3.25-3.70 W/m·K) and good chemical stability in water (80°C). By combining with commercially available UV-LEDs directly, the emission colors can be tuned from blue/cold-white to warm-white/red through the energy transfer from Sn2+ to Mn2+, and the broadband spectra covering the whole visible region from 380 nm to 760 nm. Notably, the FP glass can also serve as a white light phosphor by controlling the content of SnO/MnO, which has excellent optical properties. The CIE chromaticity coordinate, color rendering index, and quantum efficiency are (0.33, 0.29), 84, and 0.952, respectively. These new phosphors, possessing good optical and chemical properties, are promising for applications in solid-state lighting devices.

Method for refractive index measurement of nanoparticles.

A new method of measuring the refractive indices of nanoparticles has been proposed based on refractive index matching between nanoparticles and surrounding organic solvents. By finding the most transparent point of the transmittance spectrum, the refractive index of the nanoparticles is equal to that of the solvents at the corresponding wavelength. Utilizing a Rayleigh scattering model, the effects of refractive index mismatching (Δn) on the transmittance are investigated under different conditions. Some criteria for getting highly transparent nanoparticle dispersion and accurate refractive index measurements are suggested, which can support practical applications for nanomaterials in optical and optoelectronic applications.

Plasma-Induced 2D Electron Transport at Hetero-Phase Titanium Oxide Interface.

Interfaces of metal oxide heterojunctions display a variety of intriguing physical properties that enable novel applications in spintronics, quantum information, neuromorphic computing, and high-temperature superconductivity. One such LaAlO3 /SrTiO3 (LAO/STO) heterojunction hosts a 2D electron liquid (2DEL) presenting remarkable 2D superconductivity and magnetism. However, these remarkable properties emerge only at very low temperatures, while the heterostructure fabrication is challenging even at the laboratory scale, thus impeding practical applications. Here, a novel plasma-enabled fabrication concept is presented to develop the TiO2 /Ti3 O4 hetero-phase bilayer with a 2DEL that exhibits features of a weakly localized Fermi liquid even at room temperature. The hetero-phase bilayer is fabricated by applying a rapid plasma-induced phase transition that transforms a specific portion of anatase TiO2 thin film into vacancy-prone Ti3 O4 in seconds. The underlying mechanism relies on the screening effect of the achieved high-density electron liquid that suppresses the electron-phonon interactions. The achieved "adiabatic" electron transport in the hetero-phase bilayer offers strong potential for low-loss electric or plasmonic circuits and hot electron harvesting and utilization. These findings open new horizons for fabricating diverse multifunctional metal oxide heterostructures as an innovative platform for emerging clean energy, integrated photonics, spintronics, and quantum information technologies.

Design and Fabrication of an Ag Ultrathin Layer-Based Transparent Band Tunable Conductor and Its Thermal Stability.

Transparent conductors (TC) have been widely applied in a wide range of optoelectronic devices. Nevertheless, different transparent spectral bands are always needed for particular applications. In this work, indium tin oxide (ITO)-free TCs with tunable transparent bands based on the film structure of TiO2/Ag/AZO (Al-doped ZnO) were designed by the transfer matrix method and deposited by magnetron sputtering. The transparent spectra and figure-of-merit (FOM) were effectively adjusted by precisely controlling the Ag layer's thickness. The fabricated as-deposited samples exhibited an average optical transmittance larger than 88.3% (400-700 nm), a sheet resistance lower than 7.7 Ω.sq-1, a low surface roughness of about 1.4 nm, and mechanical stability upon 1000 bending cycles. Moreover, the samples were able to hold optical and electrical properties after annealing at 300 °C for 60 min, but failed at 400 °C even for 30 min.

Hg(II) ion detection using thermally reduced graphene oxide decorated with functionalized gold nanoparticles.

Fast and accurate detection of aqueous contaminants is of significant importance as these contaminants raise serious risks for human health and the environment. Mercury and its compounds are highly toxic and can cause various illnesses; however, current mercury detectors suffer from several disadvantages, such as slow response, high cost, and lack of portability. Here, we report field-effect transistor (FET) sensors based on thermally reduced graphene oxide (rGO) with thioglycolic acid (TGA) functionalized gold nanoparticles (Au NPs) (or rGO/TGA-AuNP hybrid structures) for detecting mercury(II) ions in aqueous solutions. The lowest mercury(II) ion concentration detected by the sensor is 2.5 × 10(-8) M. The drain current shows rapid response within less than 10 s after the solution containing Hg(2+) ions was added to the active area of the rGO/TGA-AuNP hybrid sensors. Our work suggests that rGO/TGA-AuNP hybrid structures are promising for low-cost, portable, real-time, heavy metal ion detectors.

Ordered assembly of sorted single-walled carbon nanotubes by drying an aqueous droplet on a meshed substrate.

We report on the ordered assembly of sorted single-walled carbon nanotubes (SWCNTs) (95% semiconducting tubes) by drying aqueous droplets on meshed grids with an enhanced evaporation rate. Besides the commonly observed "coffee ring" deposit of aligned SWCNTs on the droplet contact line after water evaporation, tubes self-organized in the central area of a grid and covered up to -1/3 of the whole surface area of a grid. In addition, parallel-aligned and straightened SWCNTs were seen to span across cracks in the SWCNT-surfactant film. The evaporation-driven assembly of sorted SWCNTs has the potential to produce ordered SWCNT structures that are attractive for the fabrication of electronic devices comprising mostly semiconducting or metallic tubes.

Nanoscale discharge electrode for minimizing ozone emission from indoor corona devices.

Ground-level ozone emitted from indoor corona devices poses serious health risks to the human respiratory system and the lung function. Federal regulations call for effective techniques to minimize the indoor ozone production. In this work, stable atmospheric corona discharges from nanomaterials are demonstrated using horizontally suspended carbon nanotubes (CNTs) as the discharge electrode. Compared with the conventional discharges employing micro- or macroscale electrodes, the corona discharge from CNTs could initiate and operate at a much lower voltage due to the small electrode diameter, and is thus energy-efficient. Most importantly, the reported discharge is environmentally friendly since no ozone (below the detection limit of 0.5 ppb) was detected for area current densities up to 0.744 A/m(2) due to the significantly reduced number of electrons and plasma volume generated by CNT discharges. The resulting discharge current density depends on the CNT loading. Contrary to the conventional wisdom, negative CNT discharges should be used to enhance the current density owing to the efficient field emission of electrons from the CNT surface.

Plasma Enabled Fe2O3/Fe3O4 Nano-aggregates Anchored on Nitrogen-doped Graphene as Anode for Sodium-Ion Batteries.

Low electrical conductivity severely limits the application of Fe2O3 in lithium- and sodium-ion batteries. In respect of this, we design and fabricate Fe2O3/Fe3O4 nano-aggregates anchored on nitrogen-doped graphene as an anode for sodium-ion batteries with the assistance of microwave plasma. The highly conductive Fe3O4 in the composite can function as a highway of electron transport, and the voids and phase boundaries in the Fe2O3/Fe3O4 heterostructure facilitate Na+ ion diffusion into the nano-aggregates. Furthermore, the Fe-O-C bonds between the nano-aggregates and graphene not only stabilize the structural integrity, but also enhance the charge transfer. Consequently, the Fe2O3/Fe3O4/NG anode exhibits specific capacity up to 362 mAh g-1 at 100 mA g-1, excellent rate capability, and stable long-term cycling performance. This multi-component-based heterostructure design can be used in anode materials for lithium- and sodium-ion batteries, and potential opens a new path for energy storage electrodes.

Gastric metastasis of recurrent hepatocellular carcinoma: A case report and literature review.

Hepatocellular carcinoma (HCC) with gastric metastasis is seldom reported. It is extremely easy to misdiagnose for primary gastric cancer with liver metastasis, especially gastric hepatoid adenocarcinoma. Here, we report a case of recurrent HCC with gastric metastasis in a 22-year-old man. He had a history of left side hepatic tumor local resection due to ruptured HCC 10 years ago. Computed tomography revealed tumors in the right liver and stomach. Endoscopy identified a massive protrusion-like malignant stromal tumor at the greater curvature of gastric body. Curative resection was performed, and HCC with gastric metastasis was diagnosed by histological and immunohistochemical findings. The patient received two times of chemotherapy and remained tumor free for 15 months. Previous studies and our experience suggested that surgical resection could significantly prolong the survival and improve patients' quality of life. A brief literature review was conducted to elucidate the differential diagnosis and treatment of HCC with gastric metastasis.

Graphene/Polyaniline Aerogel with Superelasticity and High Capacitance as Highly Compression-Tolerant Supercapacitor Electrode.

Superelastic graphene aerogel with ultra-high compressibility shows promising potential for compression-tolerant supercapacitor electrode. However, its specific capacitance is too low to meet the practical application. Herein, we deposited polyaniline (PANI) into the superelastic graphene aerogel to improve the capacitance while maintaining the superelasticity. Graphene/PANI aerogel with optimized PANI mass content of 63 wt% shows the improved specific capacitance of 713 F g-1 in the three-electrode system. And the graphene/PANI aerogel presents a high recoverable compressive strain of 90% due to the strong interaction between PANI and graphene. The all-solid-state supercapacitors were assembled to demonstrate the compression-tolerant ability of graphene/PANI electrodes. The gravimetric capacitance of graphene/PANI electrodes reaches 424 F g-1 and retains 96% even at 90% compressive strain. And a volumetric capacitance of 65.5 F cm-3 is achieved, which is much higher than that of other compressible composite electrodes. Furthermore, several compressible supercapacitors can be integrated and connected in series to enhance the overall output voltage, suggesting the potential to meet the practical application.

High photon-to-heat conversion efficiency in the wavelength region of 250-1200 nm based on a thermoelectric Bi2Te3 film structure.

In this work, 4-layered SiO2/Bi2Te3/SiO2/Cu film structures were designed and fabricated and the optical properties investigated in the wavelength region of 250-1200 nm for their promising applications for direct solar-thermal-electric conversion. A typical 4-layered film sample with the structure SiO2 (66.6 nm)/Bi2Te3 (7.0 nm)/SiO2 (67.0 nm)/Cu (>100.0 nm) was deposited on a Si or K9-glass substrate by magnetron sputtering. The experimental results agree well with the simulated ones showing an average optical absorption of 96.5%, except in the shorter wavelength region, 250-500 nm, which demonstrates the superior absorption property of the 4-layered film due to the randomly rough surface of the Cu layer resulting from the higher deposition power. The high reflectance of the film structure in the long wavelength region of 2-20 µm will result in a low thermal emittance, 0.064 at 600 K. The simpler 4-layered structure with the thermoelectric Bi2Te3 used as the absorption layer may provide a straightforward way to obtain solar-thermal-electric conversion more efficiently through future study.

Synthesis of InAs nanowires via a low-temperature solvothermal route.

InAs nanowires with diameters of 7-70 nm and lengths of up to several micrometres were synthesized by a new modified solvothermal method. The x-ray diffraction pattern showed that the InAs nanowires that were prepared had zinc blende and wurtzite structures. A combination of concentration-driven and ligand-aided solution-solid (LSS) growth mechanisms was used to explain the morphology evolution of the InAs nanowires. The preparation method features a low temperature (120-180 degrees C) and economical mass-production and is free of catalyst nanoparticles. It was believed that we have explored a promising path towards the synthesis of other morphology-controllable one-dimensional (1D) III-V group nano-materials. The structural stability of InAs nanowires during annealing was also studied.

Endometrial stromal sarcoma arising in vagina.

Endometrial stromal sarcoma (ESS) arising in the vagina is an extremely rare extrauterine endometrial stroma sarcoma, with only 4 cases reported in the literature up to date. Here we report a case of neoplasm originating from vagina. A 32-year-old woman complained of intermittent vaginal bleeding especially after intercourse. A mass with a diameter of 1.0 cm was found in the middle and upper segments of the right posterior vaginal wall. Biopsy showed ESS. Total abdominal hysterectomy, unilateral salpingo-oophorectomy (right) and partial vaginectomy were performed. No ESS lesion was found in endometrium. The patient received six courses of platinum-containing combination chemotherapy after surgery and was free of tumor 18 months after the diagnosis of ESS. The diagnosis of ESS relies on pathologic examination. CD10 is the most useful immunohistochemical marker for the diagnosis of this tumor. The mainstay treatment of ESS is surgery. Local excision and ovarian retaining may be considered in premenopausal women.

Semiconducting graphene: converting graphene from semimetal to semiconductor.

Interest in graphene has grown extensively in the last decade or so, because of its extraordinary physical properties, chemical tunability, and potential for various applications. However, graphene is intrinsically a semimetal with a zero bandgap, which considerably impedes its use in many applications where a suitable bandgap is required. The transformation of graphene into a semiconductor has attracted significant attention, because the presence of a sizable bandgap in graphene can vastly promote its already-fascinating potential in an even wider range of applications. Here we review major advances in the pursuit of semiconducting graphene materials. We first briefly discuss the electronic properties of graphene and some theoretical background for manipulating the band structure of graphene. We then summarize many experimental approaches proposed in recent years for producing semiconducting graphene. Despite the relatively short history of research in semiconducting graphene, the progress has been remarkable and many significant developments are highly anticipated.

Direct growth of vertically-oriented graphene for field-effect transistor biosensor.

A sensitive and selective field-effect transistor (FET) biosensor is demonstrated using vertically-oriented graphene (VG) sheets labeled with gold nanoparticle (NP)-antibody conjugates. VG sheets are directly grown on the sensor electrode using a plasma-enhanced chemical vapor deposition (PECVD) method and function as the sensing channel. The protein detection is accomplished through measuring changes in the electrical signal from the FET sensor upon the antibody-antigen binding. The novel biosensor with unique graphene morphology shows high sensitivity (down to ~2 ng/ml or 13 pM) and selectivity towards specific proteins. The PECVD growth of VG presents a one-step and reliable approach to prepare graphene-based electronic biosensors.

Plasma-enhanced chemical vapor deposition synthesis of vertically oriented graphene nanosheets.

Vertically oriented graphene (VG) nanosheets have attracted growing interest for a wide range of applications, from energy storage, catalysis and field emission to gas sensing, due to their unique orientation, exposed sharp edges, non-stacking morphology, and huge surface-to-volume ratio. Plasma-enhanced chemical vapor deposition (PECVD) has emerged as a key method for VG synthesis; however, controllable growth of VG with desirable characteristics for specific applications remains a challenge. This paper attempts to summarize the state-of-the-art research on PECVD growth of VG nanosheets to provide guidelines on the design of plasma sources and operation parameters, and to offer a perspective on outstanding challenges that need to be overcome to enable commercial applications of VG. The review starts with an overview of various types of existing PECVD processes for VG growth, and then moves on to research on the influences of feedstock gas, temperature, and pressure on VG growth, substrate pretreatment, the growth of VG patterns on planar substrates, and VG growth on cylindrical and carbon nanotube (CNT) substrates. The review ends with a discussion on challenges and future directions for PECVD growth of VG.