Hard X-ray nanoprobe investigations of the subtissue metal distributions within Daphnia magna

The unique potential of nanoscale elemental imaging of major/minor and trace-level elemental distributions within thin biological tissue sections of the ecotoxicological model organism Daphnia magna is demonstrated by synchrotron radiation nano-X-ray fluorescence (nano-XRF). The applied highly specialized sample preparation method, coupled with the high spatial resolution (～180 nm) and high X-ray photon flux (6?×?10¹¹ photons/s) available at the European Synchrotron Radiation Facility (ESRF) ID22NI beamline proved to be critical for the high-quality visualization of (trace-)metal distributions on the submicron level within the target structures of interest. These include the branchial sacs on the thoracic appendages (epipodites) of D. magna, which are osmoregulatory regions where ion exchange occurs. For the main element of interest (Zn), detection limits of 0.7 ppm (3 ag) was reached in fast-scanning mode using an acquisition time of 0.3 s/pixel. As demonstrated, synchrotron radiation nano-XRF revealed the elemental distributions of Ca, Fe, and Zn within this osmoregulatory region on the submicron scale, aiding the exploration of possible detoxification mechanisms of Zn within D. magna at the subtissue level.     

Quantitative monitoring of the stripper foil degradation in the 3-GeV rapid cycling synchrotron of the Japan proton accelerator research complex

A hybrid-type boron doped carbon stripper foil of 200 μg/cm² is used for the present H^? injection beam energy of 181 MeV in the 3-GeV rapid cycling synchrotron (RCS) of the Japan Proton Accelerator Research Complex (J-PARC). A stripper foil has a certain lifetime and usually lifetime goes shorter for high power operation. Foil degradation such as foil thinning and pinhole formation caused by the radiation might be a signal of the foil breaking. As a result, one can avoid sudden foil breaking by an efficient monitoring of the foil degradation. We have succeeded measuring even a little change of the stripper foil thickness during user operation of the RCS. It is the main motivation of the present study. A single foil was irradiated with a total of 2.7 × 10²¹ particles (injected H^? itself) during 4 months continuous operation of the RCS but we did not observe any indication of the foil degradation.     

Diagnostics of Plasma Behavior and TiO<Subscript>2</Subscript> Properties Based on DBD/TiO<Subscript>2</Subscript> Hybrid System

Plasma catalysis is gaining increasing interest in environmental and energy applications, such as the destruction of gas pollutants and hydrocarbon conversion. In order to further improve the application of plasma catalysis, it is crucial to understand the fundamental mechanisms, especially the mutual interaction between plasma and catalyst. In this paper, a parallel-plate dielectric barrier discharge (DBD) reactor is developed to investigate the plasma behavior and TiO₂ properties in the plasma/catalytic hybrid system. The introduction of TiO₂ thin film coated on the dielectric improves the discharge intensity, which significantly contributes to the enhancement of reactive species and charges. The energy efficiency of generating ozone in DBD/TiO₂ system has been approximately raised by 38% compared to pure DBD when the applied voltage reaches 13 kV. It is fortunately found that the discharge does not change the crystal structure of the TiO₂, but the band gap increases from 3.13 to 3.39 eV, which has been proved to enhance the oxidizability of TiO₂ in the degradation of methyl orange experiment under UV light. The FTIR and XPS spectra also demonstrate that N element is doped into the structure of TiO₂. These results successfully illustrate the plasma behavior and catalyst properties in plasma/catalysis hybrid system and provide reference for the optimization of the plasma catalysis process.     

Synthesis of cellulose–metal nanoparticle composites: development and comparison of different protocols

Deposition of nanoparticles on the surface of a variety of materials is a subject of great interest due to their potential applications in electronic devices, sensing, catalysis and bio-medical sciences. In this context, we have explored and compared various methodologies to generate gold and silver nanoparticles on the surface of cellulose fibers. It was found that boiling of the cellulose fibers in alkaline solution of gold and silver salts led to the formation and immobilization of gold and silver nanoparticles. However, in case of lecithin treated and thiol-modified cellulose fibers, high temperature was not essentially required for the formation and deposition of nanoparticles on cellulose substrate. In both these cases, fairly uniform metal nanoparticles were obtained in good yields (~43 wt% gold loading in case of thiol modified cellulose fibers) at room temperature. Borohydride-reduction method resulted in relatively lower loading (~22 wt%) with a wide size distribution of gold and silver nanoparticles on cellulose fibers. All these nanoparticle–cellulose composites were thoroughly characterized using scanning electron microscopy, energy dispersive X-ray, Fourier transform infrared spectroscopy, UV–visible spectroscopy, and elemental analyzer. Thiol modified cellulose–gold nanoparticle composites served as active catalysts in the reduction of 4-nitrophenol into 4-aminophenol.     

Photothermal catalysis for CO2 conversion

The conversion of carbon dioxide into useful fuels or chemical feedstocks is of great importance for achieving carbon emission peak and carbon neutrality. The harvesting and conversion of solar energy will provide a sustainable and environmentally friendly energy source for human production and living. Very recently, photothermal catalysis has been proved to exhibit great advantages in reducing the reaction temperature, promoting the catalytic activity, and manipulating the reaction pathway in comparison with traditional thermal catalysis. In this review, we firstly introduced the fundamental mechanisms and categories of photothermal catalysis to understand the synergy or the difference between photochemical and thermochemical reaction pathways. Subsequently, the criteria and strategies for photothermal catalyst design are discussed in order to inspire the development of high-efficiency photothermal catalytic route by achieving intense absorption of broadband solar energy spectrum and high conversion capability of solar-to-heat. Recent progress in CO₂ reduction achieved by photothermal catalysis was summarized in terms of production types. In the end, the future challenges and perspectives of photothermal catalytic CO₂ reduction are presented. We hope that this review will not only deepen the understanding of photothermal catalysis, but also inspire the design, preparation and application of high-performance photothermal catalysts, aiming at alleviating non-renewable fossil energy consumption and carbon emissions for early carbon emission peak and carbon neutrality.     

Advances in the structure and materials of perovskite solar cells

The possible exhaustion of fossil fuels in the near future and soaring global energy demand have driven the search for new types of sustainable and renewable alternatives. Perovskite (CH₃NH₃PbX₃, X = I, Br, Cl) solar cells are a type of solar cell based on a perovskite absorber, most commonly a tin halide-based or hybrid organic–inorganic lead material, as the visible-light sensitizer layer, which produces electricity from sunlight. Recently, perovskite solar cells have received substantial worldwide attention. Compared with traditional solar cells, the perovskite solar cells can obtain high efficiency with a simple architecture and via a cost-effective process. In the latest 5 years, the efficiency of perovskite solar cells to convert power has skyrocketed from 3.8 % to more than 19.3 %. It is the fastest advancing solar technology to date. The highest efficiency demonstrated by perovskite solar cells is higher than that of dye-sensitized solar cells (DSSCs). A lager number of research groups have demonstrated that perovskite solar cells may ultimately boost efficiency as high as 25 %. The high efficiency and cheap production costs make it evident that perovskite solar cells have great potential to be commercialized soon. In this review, the history, materials, processing and architecture of solar cells are discussed to obtain a better understanding of high-performance perovskite solar cells.     

Atomic level characterization by synchrotron radiation for the design of high performance catalysts

SPring-8 is the largest third-generation synchrotron radiation facility in the world. Synchrotron radiation is the most powerful light source currently available, especially in the EUV and X-ray regions, and in the research area of catalysis synchrotron radiation offers a very useful analysis method, i.e. XAFS. This spectroscopic investigative technique enables the determination of the chemical states and local structure of the atoms in the specific elements of a sample. Here, we introduce the SPring-8 facility and report how synchrotron radiation XAFS spectroscopy is utilized for the characterization and analysis of catalysts.     

Iron (Fe) speciation in xylem sap by XANES at a high brilliant synchrotron X-ray source: opportunities and limitations

The development of highly brilliant synchrotron facilities all around the world is opening the way to new research in biological sciences including speciation studies of trace elements in plants. In this paper, for the first time, iron (Fe) speciation in xylem sap has been assessed by X-ray absorption near-edge structure (XANES) spectroscopy at the highly brilliant synchrotron PETRA III, beamline P06. Both standard organic Fe-complexes and xylem sap samples of Fe-deficient tomato plants were analyzed. The high photon flux provided by this X-ray synchrotron source allows on one side to obtain good XANES spectra in a reasonable amount of time (approx. 15 min for 200 eV scan) at low Fe concentrations (sub parts-per-million), while on the other hand may cause radiation damage to the sample, despite the sample being cooled by a stream of liquid nitrogen vapor. Standard Fe-complexes such as Fe(III)-succinate, Fe(III)-α-ketoglutarate, and Fe(III)-nicotianamine are somehow degraded when irradiated with synchrotron X-rays and Fe(III) can undergo photoreduction. Degradation of the organic molecules was assessed by HPLC-UV/Vis analyses on the same samples investigated by X-ray absorption spectroscopy (XAS). Fe speciation in xylem sap samples revealed Fe(III) to be complexed by citrate and acetate. Nevertheless, artifacts created by radiation damage cannot be excluded. The use of highly brilliant synchrotrons as X-ray sources for XAS analyses can dramatically increase the sensitivity of the technique for trace elements thus allowing their speciation in xylem sap. However, great attention must be paid to radiation damage, which can lead to biased results.

A spectroscopic study on the interaction between the anticancer drug erlotinib and human serum albumin

The interaction between erlotinib and human serum albumin (HSA) in simulated physiological conditions was investigated by spectroscopic methods. The results revealed that erlotinib caused the fluorescence quenching of HSA through a static quenching procedure. The binding constants at 293, 298, 303 and 308 K were obtained as 2.53 × 10⁵, 8.13 × 10⁴, 3.59 × 10⁴ and 1.93 × 10⁴ M^?1, respectively. There may be one binding site of erlotinib on HSA at 298 K. The thermodynamic parameters indicated that the interaction between erlotinib and HSA was driven mainly by hydrogen bonding or van der Waals forces. Synchronous fluorescence spectra, UV–Vis spectra, circular dichroism and Fourier Transform infrared spectroscopy results showed erlotinib binding slightly changed the conformation of HSA with secondary structural content changes. Förster resonance energy transfer study revealed high possibility of energy transfer with erlotinib-Trp-214 distance of 3.48 nm. The results of the present study may provide valuable information for studying the distribution, toxicological and pharmacological mechanisms of erlotinib in vivo.     

Properties of surface acetylated microfibrillated cellulose relative to intra- and inter-fibril bonding

Microfibrillated cellulose (MFC) created via the micro-grinding method was heterogeneously acetylated to different substitution levels using acetic anhydride and heat rather than strong acid catalysis. The acetylated MFC was formed into thin films and characterized by infrared spectroscopy and mechanical testing. Spectral and chemical analysis confirmed controlled acetylation with increased reaction time. Due to microfibrils forming more inter-fibril bonds than whole fibers, it is generally accepted that there are more hydrogen bonds to carry the applied load. However, with increased acetylation, the initial number of possible hydrogen bonds was decreased which led to a lower tensile strength and rupture energy. At 28 % degree of substitution, the tensile index decreased to 50 % of the initial value, whereas the rupture energy was nearly completely eliminated. The acetylated fibrils, thus, created a structure that resembled the energy absorption behavior of whole fiber sheets, but behaved differently when compared in terms of tensile index.     

Investigations in annealing effects on structure and properties of β-isotactic polypropylene with X-ray synchrotron experiments

The influence of annealing on the microstructure and mechanical properties of β-form isotactic polypropylene (iPP) was investigated via in situ synchrotron small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). Transition of β-iPP to α-iPP was investigated via recrystallization at high annealing temperatures (T _a?>?120 °C). And crystallinity, crystal sizes, and long period of ordered structure increased with increasing annealing temperature. Abrupt changes were found in both mechanical properties and structural features at the same T _a range (～120 °C). The in situ synchrotron SAXS and WAXD shows that the destruction of b phase at yielding and after yielding should account for the ductility of β-iPP. The thermodynamics and kinetics of annealing were investigated with DSC and X-ray synchrotron experiments. A characteristic annealing time was investigated, which measures the rate of phase evolution in annealing of β-iPP. Eventually, a hypothesized model can be used to describe the property/structure relations during this process.     

KOH direct treatment of kombucha and in situ activation to prepare hierarchical porous carbon for high-performance supercapacitor electrodes

Kombucha, a renewable biomass, has been successfully utilized as an accessible carbon source to fabricate kombucha-derived hierarchical porous carbon (KHPC) by KOH direct treatment and in situ activation. The prepared KHPC shows an interconnected hierarchical porous structure, a pore volume of 0.41 cm³ g^?1, and a specific surface area of 917 m² g^?1. Due to the multiple synergistic effects of these advantages, the KHPC-3 exhibits a high specific capacitance of 326 F g^?1 at a current density of 1 A g^?1 in 6 M KOH, good rate capability of 82% retention from 1 to 20 A g^?1, and cycling performance with 91.3% retention over 5000 cycles. Moreover, the KHPC-3 symmetric supercapacitor reveals a good energy density of 20.97 Wh kg^?1 at a power density of 871.2 W kg^?1 and retains 8.08 Wh kg^?1 at 6330 W kg^?1 in 1 M Na₂SO₄ electrolyte. Therefore, the KHPC obtained via the simple synthesis process shows great promise as an electrode material in energy storage devices.     

Thermogravimetric and kinetic analysis of energy crop Jerusalem artichoke using the distributed activation energy model

Jerusalem artichoke has great potential as future feedstock for bioenergy production because of its high tuber yield (up to 90 t ha^?1), appropriate biomass characteristics, low input demand, and positive environmental impact. The pyrolytic and kinetic characteristics of Jerusalem artichoke tubers were analyzed at heating rates of 5, 10, 20 and 30 °C min^?1. TG and DTG curves in an inert (nitrogen) atmosphere suggested that there were three distinct stages of mass loss and the major loss occurs between about 190–380 °C. Heating rate brought a lateral shift toward right in the temperature. And, it not only affects the temperature at which the highest mass loss rate reached, but also affect the maximum rate of mass loss. The distributed activation energy model (DAEM) was used to study the pyrolysis kinetics and provided reasonable fits to the experimental data. The activation energy (E) of tubers ranged from 146.40 to 232.45 kJ mol^?1, and the frequency factor (A) changed greatly corresponding to E values at different mass conversion.     

Size Reduction of Bulk Alumina for Mass Production of Fluorescent Nanoalumina by Fungus <Emphasis Type="Italic">Humicola</Emphasis> sp.

In recent years, nanomaterials have made their way into hundreds of biomedical, life-sciences and technological applications. One such nanomaterial of extreme importance is nanoalumina (Al₂O₃ nanoparticles). This nanomaterial is an epitome of diversity with applications exhibited in the fields of catalysis, cosmetics, theranostics, energy generation, biosensors, drug-delivery, tumor-regression, etc. However, problems persist in terms of biocompatibility, cost-effectiveness, reproducibility and mass-production of nanoalumina by the presently existent physical, chemical and biological methodologies. Herein, we for the first time are presenting a top-down biofabrication method by which size reduction of commercial bulk alumina/aluminum oxide (5 µm) into nanoalumina (5–25 nm) is carried out by a thermophilic fungus Humicola sp. within 96 h of reaction at just 50 °C. The so-formed nanoalumina is highly stable, water dispersible, fluorescent and natural protein capped; characterization engaged standard techniques. These nanoparticles exhibit anti-bacterial properties against Gram-positive Bacillus subtilis strain and may serve as broad spectrum bactericidal agents. We believe that our novel top-down approach may be extensively used in the facile, inexpensive, eco-friendly and reliable fabrication of abundant quantities of nanomaterials of different chemical compositions, sizes and shapes with better control and predictability over the properties as derived from their substrates. The mechanistic aspect of said protocol is underway.     

On-line product analysis of pine wood pyrolysis using synchrotron vacuum ultraviolet photoionization mass spectrometry

The pyrolysis process of pine wood, a promising biofuel feedstock, has been studied with tunable synchrotron vacuum ultraviolet photoionization mass spectrometry. The mass spectra at different photon energies and temperatures as well as time-dependent profiles of several selected species during pine wood pyrolysis process were measured. Based on the relative contents of three lignin subunits, the data indicate that pine wood is typical of softwood. As pyrolysis temperature increased from 300 to 700 °C, some more details of pyrolysis chemistry were observed, including the decrease of oxygen content in high molecular weight species, the observation of high molecular weight products from cellulose chain and lignin polymer, and potential pyrolysis mechanisms for some key species. The formation of polycyclic aromatic hydrocarbons (PAHs) was also observed, as well as three series of pyrolysis products derived from PAHs with mass difference of 14 amu. The time-dependent profiles show that the earliest products are formed from lignin, followed by hemicellulose products, and then species from cellulose.

One-pot synthesis of tetrahydroindoles via a copper catalyzed N-alkynation/[4+2] cycloaddition cascade

4,7-Dihydroindolines are prepared from alkyne bromides and 2-dienyl sulfonamides via a CuSO₄ catalyzed cascade in a one-pot fashion.     

In situ synthesis of crosslinked-polyaniline nano-pillar arrays/reduced graphene oxide nanocomposites for supercapacitors

Crosslinked-polyaniline (CPA) nano-pillar arrays adsorbed on the surface of reduced graphene oxide (RGO) sheets were synthesized by in situ solution polymerization through two steps of reduction. The electrochemical analyses demonstrated that the befittingly reduced CPA/RGO composite exhibited high performance as electrode materials for supercapacitors. The CPA/RGO composite showed very high specific capacitance of 1532 F g^?1 at a scan rate of 10 mV s^?1 or 694 F g^?1 at a current density of 2 A g^?1 in 1 M H₂SO₄ electrolyte, as well as great energy density of 61.4 W h kg^?1 at a current density of 2 A g^?1. The electrode material also had decent power density of 4 kW kg^?1 at a current density of 10 A g^?1, and good cycling stability of 92.5 % capacitance retained after 500 cycles of cyclic voltammetry at 500 mV s^?1. The neat microstructures and super electrochemical properties suggest the potential use of the composites in supercapacitors.     

An Array of Micro-hollow Surface Dielectric Barrier Discharges for Large-Area Atmospheric-Pressure Surface Treatments

A robust, commercial micro-hollow plasma source was used to generate atmospheric-pressure plasma, of surface area 18 × 18 mm, in ambient air, nitrogen and argon. An electrode system consisting of 105 micro-hollow surface dielectric barrier discharges was powered by sinusoidal high-voltage at a frequency of 26.7 kHz. The influence of the plasmas on the polycarbonate surface was investigated by means of surface energy measurements and X-ray photoelectron spectroscopy. It emerged that short plasma exposures led to significant increases in surface energy. It is suggested that this may arise out of incorporation of polar groups on the polycarbonate surface. A thermal camera was used to monitor the plasma source surface temperatures for the gases at flow rates ranging from 0 to 5 L/min. It was found that the temperature of the micro-hollow ceramic when operated upon in ambient air decreased significantly from 147 °C at 0 L/min to 49 °C at 5 L/min. In order to investigate further the thermal properties of the plasma, optical emission spectroscopy was employed to monitor the vibrational and rotational temperatures of the plasma generated in ambient air. CCD camera spectroscopic measurements estimated plasma thickness and temperature distribution at high spatial resolution.     

High-performance Pt-NiO nanosheet-based counter electrodes for dye-sensitized solar cells

High-performance counter electrodes for dye-sensitized solar cells (DSSCs) are fabricated with platinum-nickel oxide (Pt-NiO) nanosheets as catalytic materials. Firstly, the Pt-Ni nanosheets are synthesized via galvanic replacement reaction between pre-synthesized Ni nanosheets and an aqueous H₂PtCl₆ solution. Secondly, after thermal treatment in air, the Pt-Ni alloys are turned to Pt-NiO nanosheets. The related data of cyclic voltammetry, electrochemical impedance spectroscopy, and Tafel polarization reveal that Pt-NiO counter electrodes show highly catalytic activity and low charge transfer resistance. The DSSC with Pt-NiO counter electrode exhibits power conversion efficiency (PCE) of 8.40 %, which is lower than that of the DSSC containing commercial available Pt counter electrode (9.15 %) under full sunlight illumination (100 mW cm^?2, AM1.5G). However, owing to the extremely high transparency of Pt-NiO counter electrode, when putting an Ag mirror behind the back side of the DSSC, the reflected light can bring great enhanced PCE (11.27 %).