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Much effort has been focused on novel nanomedicine for cancer therapy. However, tumor hypoxia limits the efficacy of various cancer therapeutics. Herein, we constructed a self-sufficient hybrid enzyme-based silk fibroin hydrogel system, consisting of Pt-decorated hollow Ag-Au trimetallic nanocages (HGN@Pt) and glucose oxidase (GOx), to supply O2 continuously and consume glucose concurrently and, thereby, synergistically enhance the anti-cancer efficacy of a combined starvation and photothermal therapy operating in a hypoxic tumor microenvironment. Thanks to the cooperative effects of the active surface atoms (resulting from the island-like features of the Pt coating), the intrinsically hollow structure, and the strain effect induced by the trimetallic composition, HGN@Pt displayed efficient catalase-like activity. The enhancement in the generation of O2 through the decomposition of H2O2 mediated by the as-designed nanozyme was greater than 400% when compared with that of hollow Ag-Pt bimetallic nanospheres or tiny Pt nanoparticles. Moreover, in the presence of HGN@Pt, significant amounts of O2 could be generated within a few minutes, even in an acidic buffer solution (pH 5.8-6.5) containing a low concentration of H2O2 (100-500 μM). Because HGN@Pt exhibited a strong surface plasmon resonance peak in the near-infrared wavelength range, it could be used as a photothermal agent for hyperthermia therapy. Furthermore, GOx was released gradually from the SF hydrogel into the tumor microenvironment to mediate the depletion of glucose, leading to glucose starvation-induced cancer cell death. Finally, the O2 supplied by HGN@Pt overcame the hypoxia of the microenvironment and, thereby, promoted the starvation therapeutic effect of the GOx-mediated glucose consumption. Meanwhile, the GOx-produced H2O2 from the oxidation of glucose could be used to regenerate O2 and, thereby, construct a complementary circulatory system. Accordingly, this study presents a self-sufficient hybrid enzyme-based system that synergistically alleviates tumor hypoxia and induces an anti-cancer effect when combined with irradiation of light from a near-infrared laser.

Here, a current-accelerated phase cycling by an in situ current-induced oxidation process was demonstrated to reversibly switch the local metallic Cu and semiconducting Cu2O phases of patterned polycrystalline copper nanobelts. Once the Cu nanobelts were applied by a direct-current bias of ∼0.5 to 1 V in air with opposite polarities, the resistance between several hundred ohms and more than MΩ can be manipulated. In practice, the thickness of 60 nm with a moderate grain size inhibiting both electromigration and permanent oxidation is the optimized condition for reversible switching when the oxygen supply is sufficient. More than 40% of the copper localized beneath the positively biased electrode was oxidized assisted by the Joule heating, blocking the current flow. On the contrary, the reduction reaction of Cu2O was activated by the thermally assisted electromigration of Cu atoms penetrating the interlayer at the reverse bias. Finally, based on a high on/off ratio, the fast switching and the scalable production, reusable feasibility based on copper nanobelts such as the memristor array was demonstrated.

The morphology and metal oxidation states of atmospheric aerosols are pertinent to their formation processes and ensuing interactions with surrounding gases, vapors and other environments upon deposition, such as human respiratory tract, soil and water. Although much progress has been made in recent years through single-particle techniques, considerably less is known with respect to the three-dimensional (3D) internal morphology of single atmospheric aerosol particles due to the limited penetration depth of electron microscopy. In this study, for the first time, a novel synchrotron-based transmission X-ray microscopy (TXM) methodology has been developed to visualize the 3D internal chemical mixing state and structure of single particles. The results show that the TXM is more applicable to the imaging of solid particles containing high-density elements, e.g., iron (Fe), aluminum (Al), silicone (Si), carbon (C) and sulfur (S), and/or solid particles of sizes larger than about 100 nm. In addition, the TXM is capable to reveal the fine 3D topographic features of single particles. The derived 3D internal and external information would be difficult to discern in the 2D images from electron microscopy. The TXM 3D images illustrate that aerosol particles exhibit complex internal mixing state and structure, e.g., homogeneously-, heterogeneously-mixed, multiple inclusions, fibrous, porous, and core-shell configuration. When coupled with the synchrotron-based X-ray fluorescence spectrometry (XRF) and absorption near-edge spectroscopy (XANES) of an X-ray nanoprobe in the energy range of 4-15 keV, the 3D morphology of single particles is further supplemented with the spatial distribution and oxidation sates of selected elements, including Fe, vanadium (V), manganese (Mn), chromium (Cr) and arsenic (As). The presented cross-platform, synchrotron-based methodology shows promise in complementing existing single-particle techniques and providing new insights to the heterogeneity of single-particle micro-physicochemical states relevant to the aerosol chemistry, optical properties, and their environmental and health impacts.

Healthcare-associated infections are common causes of morbidity and mortality. Advanced nanotechnology provides a means of overcoming this problem, but it remains challenging to develop universal coating strategies for decorating antimicrobial nanomaterials onto various clinical devices. In this paper, we propose a general silane-based method for immobilizing monolayer metal nanoparticle (NP) arrays onto any type of substrate surface—especially for a diverse range of clinical implantable devices. The surface silanization was achieved simply through the adsorption of N1-(3-trimethoxysilylpropyl)diethylenetriamine (TMS), regardless of the material (polymer, metal, oxide) or morphology (flat, curved, textured) of the substrate, with no need for pretreatment or expensive instrumentation. Monolayers of various nanostructures (Ag, Au, and hollow Au NPs) were then decorated rapidly onto the TMS-treated substrates, thereby further functionalizing their surfaces. In particular, immobilization of the Ag NPs resulted in excellent anti-biofilm efficacy against three clinically life-threatening pathogens: Pseudomonas aeruginosa, Escherichia coli, and Staphylococcus aureus. Sustained release of Ag+ ions led to durable inhibition of bacterial attachment for up to 28 days. Studies with NIH3T3 fibroblasts revealed that the Ag NP arrays displayed no cytotoxicity toward mammalian cells. Overall, this universal coating process appears to be an innovative method for the surface-functionalization of diverse materials and devices employed in the fields of energy, sensing, and medicine—especially to prevent healthcare-associated infections arising from the use of clinical implantable devices in hospitals.

Much effort has been focused on novel nanomedicine for cancer therapy. However, tumor hypoxia limits the efficacy of various cancer therapeutics. Herein, we constructed a self-sufficient hybrid enzyme-based silk fibroin hydrogel system, consisting of Pt-decorated hollow Ag-Au trimetallic nanocages (HGN@Pt) and glucose oxidase (GOx), to supply O

To achieve diffraction-limited focal spot size is a goal for next-generation synchrotrons. Mirrors are increasingly important for X-ray focusing optics following recent advances in mirror fabricati...

Three-dimensional functional silver electrode on silicon with trench-like optical structure realizes both broadband light harvesting and spontaneous oxidation reaction in 1M sodium chloride solution through the silver chloride examined during hydrogen preparation. Standard electrode potential (Eo) of -0.23 V in complete electrochemical reaction benefits hydrogen preparation without external bias. Proposed no power consumption solar harvester achieves 10 to 100 times the photoresponsivity and broader solar harvesting of previous studies providing open-circuit voltage of 0.35 V under one sun (100 mW/cm2) illumination to accelerate the electrochemical reaction additionally. Actual demonstration of hydrogen preparation just relying on outdoor solar confirms suggested strategy.

A powerful, low-cost niobium oxide–niobium carbide–graphene oxide (NbO2/NbC/rGO) hybrid electrocatalyst is prepared by refluxing, hydrothermal method, followed by annealing process at the optimum temperature of 1050 °C for all vanadium redox flow battery (VRFB) application. The NbO2/NbC/rGO electrocatalyst shows the best electrochemical activity with the highest peak current densities and the lowest peak differences toward VO2+/VO2+ and V2+/V3+ redox reactions from the cyclic voltammetry compared to other samples. The rate performance of VRFB cell using NbO2/NbC/rGO modified graphite felts (NbO2/NbC/rGO/GF) shows the voltage efficiencies of 89.3%, 81.7%, 71.0%, and 59.3% by the charge-discharge current densities of 40 mA cm−2, 80 mA cm−2, 120 mA cm−2, and 160 mA cm−2, respectively, which these performances are superior to those using the pretreated GFs and the untreated GF. The charge-discharge stability test of the VRFB cell using NbO2/NbC/rGO/GF demonstrates no significant decay after 100 cycles by the current density of 80 mA cm−2. This observation is due to the synergistic effects related to the presence of excess oxygen vacancies on NbO2/NbC, the high content of oxygen functional groups, and the high electrical conductivity characteristics of the graphene sheet.

Time-resolved X-ray excited optical luminescence (TR-XEOL) was developed successfully for the 23A X-ray nanoprobe beamline located at the Taiwan Photon Source (TPS). The advantages of the TR-XEOL facility include (i) a nano-focused X-ray beam (

The multifunctional hard X-ray nanoprobe at Taiwan Photon Source (TPS) exhibits the excellent ability to simultaneously characterize the X-ray absorption, X-ray excited optical luminescence (XEOL) as well as the dynamics of XEOL of materials. Combining the scanning electron microscope (SEM) into the TPS 23A end-station, we can easily and quickly measure the optical properties to map out the morphology of a ZnO microrod. A special phenomenon has been observed that the oscillations in the XEOL associated with the confinement of the optical photons in the single ZnO microrod shows dramatical increase while the X-ray excitation energy is set across the Zn K-edge. Besides having the nano-scale spatial resolution, the synchrotron source also gives a good temporal domain measurement to investigate the luminescence dynamic process. The decay lifetimes of different emission wavelengths and can be simultaneously obtained from the streak image. Besides, SEM can provide the cathodoluminescence (CL) to be a complementary method to analyze the emission properties of materials, we anticipate that the X-ray nanoprobe will open new avenues with great characterization ability for developing nano/microsized optoelectronic devices.

Polarization-dependent hard X-ray excited optical luminescence (XEOL) was used to study not only the optical properties but also the crystallographic orientations of a non-polar a-plane ZnO wafer. In addition to a positive-edge jump and extra oscillations in the near-band-edge (NBE) XEOL yield, we observed a blue shift of the NBE emission peak that follows the polarization-dependent X-ray absorption near-edge structure (XANES) as the X-ray energy is tuned across the Zn K-edge. This NBE blue shift is caused by the larger X-ray absorption, generating higher free carriers to reduce the exciton-LO phonon coupling, which causes a decrease in the exciton activation energy. The extra oscillations in XANES and XEOL as the polarization is set parallel to the c-axis is attributed to simultaneous excitations of the Zn 4p - O 2pπ -bond along the c-axis and the bilayer σ-bond, whereas only the σ-bond is excited when the polarization is perpendicular to the c-axis. The polarization-dependent XEOL spectra can be used to determine the crystallographic orientations.

In this study, an eco-friendly and ultrasensitive paper substrate is developed for surface-enhanced Raman scattering (SERS) with performance approaching single molecule detection. By exploiting the laser-induced photothermal effect, paper fibrils with hybrid micro- and nanostructures can facilitate the formation of highly dense metal nanoparticles (NPs) after a single shot of laser illumination. Metal films deposited on the paper substrates feature discontinuous morphologies, with the fragments acting as multiple nucleation sites. Because thermal conductivity is low on the broken films and the underlying paper fibrils, the incident energy is absorbed efficiently. Moreover, the quasi-three-dimensional distribution of NPs on the SERS paper greatly enhances the SERS signals within the effective collection volume of a Raman microscope. As a result of the large number of highly effective hot spots and the condensation effect, the hydrophobic SERS paper provides SERS signals with stable and uniform reproducibility throughout the detection area. The limits of detection when using the paper substrates reach the attomolar (10(-18) M) level, thereby approaching single molecule detection.

The diffraction-limited Montel mirrors, equipped at the X-ray Nanoprobe (XNP) at Taiwan Photon Source (TPS), provide a 40 nm focal spot and working distance 55 mm under the total beamline length of 69 m. The underneath holder supporting for the Montel mirrors is a 12 axes flexure based manipulators in which 10 out of the 12 axes are motorized. To monitor the position and stability of individual holder motion, a monitoring system consisted of three optical encoders and three- axes laser interferometers for angle movement is implemented. The gap width between the two mirrors and their orthogonality can be adjusted by a tilting sensor and a high magnification optical microscope. The focusing properties, phase and amplitude, after the Montel mirrors will be investigated by means of coherent Ptychography, as well as by zone plate imaging. An SEM in close cooperation with laser interferometers is equipped to precisely position the samples and conduct the on-the-fly scan. A high speed FPGA based circuit is developed to address signal from XRF, XAS, XEOL and XRD. Data is in tag with position and time information and been processed by computers to allow 5nm precision stage scanning free from mechanical feedback. The XNP at TPS is under commissioning since February 2017. The commissioning result, particularly the performance of the Montel mirrors will be reported in this presentation.

This on-the-fly scanning control system is for the x-ray nanoprobe endstation at Taiwan Photon Source(TPS) and built base-on the high speed Hardware (H/W), high throughput data stream and multi-channel control interfaces. The main idea is to tag each data with information of time and position, which generates by circuit and laser interferometer. The data is then processed by a computer to be analyzed and visualized. By using high speed FPGA with embedded processer to process the input and output data which includes the DAC, ADC, Gigabit Ethernet (GbE), X-ray fluorescence (XRF) and laser interferometer control interfaces. Three DAC control the X,Y and Z axes of the flexure stage, four ADCs and sensor interfaces gather the data and packet it into data packet. GbE send data back to computer to do image processing then reconstruct the scanning image. The numerous data not only for rebuild the image but also good for information analysis. Including the vibration, time slide analysis. Our demo system is built by an e-beam source, flexure stage and laser interferometer. The current maximum scanning speed is up to 5 lines/sec which is limited by the mechanical, the sample rate can be as high as 20M samples/sec which limited by laser interferometer, and the maximum data rate is close to 100M bytes/sec which is limited by the GbE. Interferometer information combine with position data in data packet, makes easy for data analysis and also for image stitching. The system is going to commission on beamline at March, 2017. The commission result for this system will be presented.

The hard X-ray nanoprobe facility at Taiwan Photon Source (TPS) provides versatile X-ray analysis techniques, with tens of nanometer resolution, including XRF, XAS, XEOL, projection microscope, CDI, etc. Resulting from the large numerical aperture obtained by utilizing Montel KB mirrors, the beamline with a moderate length 75 meters can conduct similar performance with those beamlines longer than 100 meters. The two silica-made Montel mirrors are 45 degree cut and placed in a V-shape to eliminate the gap loss and the deformation caused by gravity. The slope error of the KB mirror pair is less than 0.04 µrad accomplished by elastic emission machining (EEM) method. For the beamline, a horizontal DCM and two-stage focusing in horizontal direction is applied. For the endstation, a combination of SEM for quickly positioning the sample, a fly scanning system with laser interferometers, a precise temperature control system, and a load lock transfer system will be implemented. In this presentation, the design and...

The hard X-ray nanoprobe facility at Taiwan Photon Source (TPS) provides multimodal X-ray detections, including XRF, XAS, XEOL, projection microscope, CDI, etc. Resulting from the large numerical aperture obtained by utilizing nested Montel mirrors, the beamline with a moderate length 75 meters can conduct similar performance with those beamlines longer than 100 meters. The mirrors are symmetrically placed with a 45 degrees cut. The beamline optics is thus designed to take the advantage of the symmetry of mirrors such that a round focal spot is accomplished. The size and the divergence of the focus spot are simulated around 40 nm and 6.29 mrad, respectively. The whole facility including the beamline and the stations will be operated under vacuum to preserve the photon coherence as well as to prevent the system from unnecessary environmental interference. A SEM in close cooperation with laser interferometers is equipped to precisely locate the position of the sample. This endstation is scheduled to be commissioned in the fall of 2016.

The hard X-ray nanoprobe at Taiwan Photon Source (TPS) makes use of the large numerical aperture obtained by nested Montel mirrors. To fully uptake the focusing power and flux, these mirrors requires the surface slope error no less than 0.05 μrad and are symmetrically placed with a 45 degrees cut for perfect surface matching. The beamline optics is designed to take the advantage of the symmetry of mirrors such that a round focal spot is accomplished. The final size of the focus spot are simulated below 40 nm at 9-15 keV. The whole facility including the beamline and the stations will be operated under vacuum to preserve photon coherence as well as to prevent the system from unnecessary environmental interference. The station equips with multimodal x-ray probes, including XRF, XAS, XEOL, projection microscope, CDI, etc. A SEM in close cooperation with laser interferometers is equipped to precisely locate the position of the sample. The beamline and the station are scheduled to be in commissioning phase in 2016.

The temperature-dependent hard X-ray excited optical luminescence (XEOL) spectroscopy was used to study the optical properties of O and Zn polarity of a c-plane single crystal ZnO wafer. By analyzing the XEOL and XRD, we found an unprecedented blue shift of the free exciton transition with increasing the excited carrier density as tuning the X-ray energy across the Zn K-edge, and the O-polar face possesses better crystal structure than the Zn-polar one. This spectral blue shift is attributed to the Coulomb screening of the spontaneous polarization by the excited free carriers that result in decreasing the exciton-phonon Frohlich interaction to reduce exciton binding energy.