Efficient plasmonic water splitting by heteroepitaxial junction-induced faceting of gold nanoparticles on an anatase titanium(IV) oxide nanoplate array electrode.

Plasmonic photocatalysts represented by gold nanoparticle (NP)-loaded titanium(IV) oxide (Au/TiO2) can be promising solar-to-fuel converters by virtue of their response to visible-to-near infrared light. Hitherto, Au/rutile (R)-TiO2 has been recognized as exhibiting photocatalytic activity higher than that of Au/anatase (A)-TiO2. Herein, we demonstrate that the high potential of A-TiO2 as the Au NP support can be brought out through atomic level interface control. Faceting of Au NPs is induced by a heteroepitaxial junction on an A-TiO2(001) nanoplate array (Au/A-TiO2 NPLA). Photoexcitation towards the Au/A-TiO2 NPLA electrode generates current for the water oxidation reaction at λ < 900 nm with a maximum efficiency of 0.39% at λ = 600 nm, which is much larger than the values reported so far for the usual electrodes. The striking activity of the Au/A-TiO2 NPLA electrode was rationalized using a potential-dependent Fowler model. This study presented a novel approach for developing solar-driven electrodes for green and sustainable fuel production.

Hydrogen peroxide photo-fuel cells.

Hydrogen peroxide (H2O2) possesses both strong oxidizing and moderate reducing ability. Due to the unique chemical reactivity, one-compartmentalization of fuel cells is possible by using H2O2 as both the fuel and oxidant for fuel cells (H2O2-FC). To enhance the anode reaction (H2O2 → O2 + 2H+ + 2e-) of the H2O2-FC, a noble metal-free H2O2-photo fuel cell (PFC) has been newly developed for enhancing the conversion from chemical energy to electric energy with only emission of water and oxygen. The H2O2-photo fuel cells (PFC) take several significant advantages over the conventional hydrogen-oxygen fuel cells. With the realization of a solar-driven energy cycle with H2O2 as the key substance in mind, this Frontier article highlights the H2O2-PFCs. Firstly, the fundamentals of the H2O2-PFC are dealt with by treating the prototype using TiO2 as the photoanode. Then, recent progress in the H2O2-PFCs and an emerging application to self-powered biosensors are described. Finally, the conclusions are summarized with the future outlook.

Facile synthesis of single-crystalline MnO2 nanowire arrays with high photothermal catalytic activity.

A simple process has been developed to form single-crystalline ß-MnO2 nanowire arrays (NWAs) with a large surface area of 125 m2 g-1 on a glass plate working as a highly active three dimensional (3D) photothermal catalyst under the illumination of near infrared light due to the efficient light harvesting and heat confinement near the reaction field in addition to the large surface area.

Near Infrared Light-to-Heat Conversion for Liquid-Phase Oxidation Reactions by Antimony-Doped Tin Oxide Nanocrystals.

Effective utilization of the sunlight for chemical reactions is pivotal for dealing with the growing energy and environmental issues. So far, much effort has been focused on the development of semiconductor photocatalysts responsive to UV and visible light. However, the near infrared and infrared (NIR-IR) light occupying ∼50 % of the solar energy has usually been wasted because of the low photon energy insufficient for the band gap excitation. Antimony doping into SnO2 (ATO) induces strong absorption due to the conduction band electrons in the NIR region. The absorbed light energy is eventually converted to heat via the interaction between hot electrons and phonons. This Concept highlights the photothermal effect of ATO nanocrystals (NCs) on liquid-phase oxidation reactions through the NIR light-to-heat conversion. Under NIR illumination even at an intensity of ∼0.5 sun, the reaction field temperature on the catalyst surface is raised 20-30 K above the bulk solution temperature, while the latter is maintained near the ambient temperature. In some reactions, this photothermal local heating engenders the enhancement of not only the catalytic activity and selectivity but also the regeneration of catalytically active sites. Further, the photocatalytic activity of semiconductors can be promoted. Finally, the conclusions and possible subjects in the future are summarized.

Crystallographic interface control of the plasmonic photocatalyst consisting of gold nanoparticles and titanium(iv) oxide.

A big question in the field of plasmonic photocatalysis is why a typical photocatalyst consisting of gold nanoparticles and rutile titanium(iv) oxide (Au/R-TiO2) usually exhibits activity much higher than that of Au/anatase TiO2 (Au/A-TiO2) under visible-light irradiation. Shedding light on the origin should present important guidelines for the material design of plasmonic photocatalysts. Au nanoparticles (NPs) were loaded on ordinary irregular-shaped TiO2 particles by the conventional deposition precipitation method. Transmission electron microscopy analyses for the Au/TiO2 particles ascertain that faceting of Au NPs is induced on R-TiO2 by using a domain-matching epitaxial junction with the orientation of (111)Au//(110)R-TiO2 , whereas non-faceted hemispherical Au NPs are exclusively formed on A-TiO2. The faceting probability of Au NPs (P f) on R-TiO2 increases with decreasing Au particle size (d Au) to reach 14% at d Au = 3.6 nm. A clear positive correlation between the photocatalytic activity and P f in several test reactions indicates that the heteroepitaxial junction-induced faceting of Au NPs is the principal factor for governing the plasmonic photocatalytic activity of Au/TiO2. In light of this finding, R-TiO2 nanorods with a high percentage (95%) of {110} facets were hydrothermally synthesized and used for the support of Au NPs. Consequently, the P f value increases to as much as 94% to enhance the photocatalytic activity with respect to that of Au/R-TiO2 with P f = 14% by factors of 2.2-4.4 depending on the type of reaction.

Photothermal Oxidation of Cinnamyl Alcohol with Hydrogen Peroxide Catalyzed by Gold Nanoparticle/Antimony-Doped Tin Oxide Nanocrystals.

Gold nanoparticles with different mean sizes were formed on antimony-doped tin oxide nanocrystals by the temperature-varied deposition-precipitation method (Au/ATO NCs). Au/ATO NCs possess strong absorption in the near-infrared region due to Drude excitation in addition to the localized surface plasmon resonance (LSPR) of AuNPs around 530 nm. Au/ATO NCs show thermally activated catalytic activity for the oxidation of cinnamyl alcohol to cinnamaldehyde by hydrogen peroxide. The catalytic activity increases with a decrease in the mean Au particle size (dAu ) at 5.3 nm≤dAu ≤8.2 nm. Light irradiation (λex >660 nm, ∼0.5 sun) of Au/ATO NCs increases the rate of reaction by more than twice with ∼95 % selectivity. Kinetic analyses indicated that the striking enhancement of the reaction stems from the rise in the temperature near the catalyst surface of ∼30 K due to the photothermal effect of the ATO NCs.

Noble Metal-Free Inorganic Photocatalyst Consisting of Antimony-Doped Tin Oxide Nanorod and Titanium oxide for Two-Electron Oxygen Reduction Reaction.

This study reports a noble metal-free robust inorganic photocatalyst for H2 O2 synthesis via two-electron oxygen reduction reaction (ORR). Antimony-doped tin oxide nanorods were heteroepitaxially grown from rutile TiO2 seed crystals with an orientation of (001)ATO //(001)TiO2 (ATO-NR//TiO2 ,//denotes heteroepitaxial junction) by a hydrothermal method. UV-light irradiation of ATO-NR//TiO2 particles stably and continuously produces H2 O2 from aerated aqueous solution of ethanol. Electrochemical measurements using rotating electrodes show that Sb-doping into SnO2 greatly enhances the electrocatalytic activity for two-electron ORR. The striking photocatalytic activity of ATO-NR//TiO2 stems from the effective charge separation, electrocatalytic activity for two-electron ORR, low catalytic activity for H2 O2 decomposition, and extraordinary robustness.

Highly Active and Renewable Catalytic Electrodes for Two-Electron Oxygen Reduction Reaction.

This study has shown that antimony-doped tin oxide (ATO) works as a robust "renewable catalyst" for the electrochemical synthesis of hydrogen peroxide (H2O2) from water and oxygen. Antimony doping into SnO2 gives rise to remarkable electrocatalytic activity for two-electron oxygen reduction reaction (2e--ORR) by water with a volcano-type relation between the activity and doping levels (xSb). Density functional theory simulations highlight the importance of an isolated Sb atom of ATO inducing the high activity and selectivity for 2e--ORR due to the effects of O2 adsorption enhancement, decrease in the activation energy, and lowering the adsorptivity of H2O2. Electrolysis by a normal three-electrode cell using ATO (xSb = 10.2 mol %) at -0.22 V (vs reversible hydrogen electrode) stably and continuously produces H2O2 with a turnover frequency of 6.6 s-1. This remarkable activity can be maintained even after removing the surface layer of ATO by argon-ion sputtering.

Rational design for gold nanoparticle-based plasmonic catalysts and electrodes for water oxidation towards artificial photosynthesis.

The oxygen evolution reaction (OER) with a large overpotential is the key step common to artificial photosynthesis. In semiconductor photocatalysts, the light available to the reactions is usually limited to UV or visible with wavelengths shorter than the absorption edge of the semiconductors. On the other hand, gold nanoparticle (Au NP)-based plasmonic photocatalysts, particularly hot-electron transfer (HET)-type plasmonic photocatalysts, have the capability to utilize visible-to-near infrared light that makes up most sunlight as a driving force for the energetically uphill reactions. In recent years, experimental and theoretical studies on HET-type plasmonic photocatalysts consisting of Au NPs and a semiconductor have been intensively pursued. This perspective article highlights the fundamentals and recent progress of Au NP-based HET-type plasmonic photocatalysts for OER. After the introduction, the basics for the rational design of plasmonic photocatalysts are treated first. Secondly, the concrete design for the plasmonic photocatalysts is dealt with in the order of semiconductors, Au NPs, and their interface. Thirdly, recent advanced studies on plasmonic photocatalysts for OER are described. Finally, the conclusions are summarized with a direction for future research on plasmonic photocatalysts.

Photocatalytic Activity of Radial Rutile Titanium(IV) Oxide Microspheres for Aerobic Oxidation of Organics.

Radial rutile TiO2 nanorod homomesocrystals (TiO2 -NR HOMCs) or the so-called "sea urchin-like TiO2 microspheres" were synthesized by using a hydrothermal method. TiO2 -NR HOMCs show photocatalytic activity for aerobic oxidative degradation of 2-naphthol under irradiation of UV- and visible light. Furthermore, extremely small iron oxide clusters were formed on the surface of TiO2 -NR HOMCs (FeOx /TiO2 -NR HOMCs) by the chemisorption-calcination technique to reduce the band gap. The FeOx -surface modification gives rise to drastic enhancement of the UV- and visible-light activity. Reversed double-beam photoacoustic spectroscopy measurements were performed for TiO2 -NR HOMCs and FeOx /TiO2 -NR HOMCs to obtain the ERDT (energy-resolved distribution of electron traps)/CBB (conduction-band bottom) patterns. The ERDT/CBB pattern of TiO2 -NR HOMCs consists of two components derived from rutile (C1) and amorphous TiO2 (C2). In the pattern, the surface electron traps in C2 exist near the CBB to be removed by the FeOx -surface modification. By taking this finding into consideration, the striking surface modification effect is ascribable to the electrocatalytic activity (or the action as an electron reservoir) of the FeOx clusters for multiple ORR, the suppression of recombination, and the increase in the visible-light harvesting efficiency.

Switching of Electron Transport Direction from the Long Axis to Short Axis in a Radial SnO2(Head)-Rutile TiO2 Nanorod(Tail) Heteromesocrystal Photocatalyst.

Heteroepitaxial growth of rutile TiO2 nanorods from SnO2 seeds yielded radial heteromesocrystals consisting of SnO2(head) and rutile TiO2 nanorod(tail) with the SnO2(head) oriented toward the center (TiO2-NR//SnO2 HEMCs). Iron oxide clusters were formed on the surface by the chemisorption-calcination technique. The FeOx-surface modification gives rise to drastic increases in the photocatalytic activity for aerobic oxidation of 2-naphthol under irradiation of UV and visible light. As a 2D-model for 3D-TiO2-NR//SnO2 HEMC, electrochemical measurements were performed for the rutile TiO2-NR array formed on a fluorine-doped tin oxide (SnO2:F) electrode. The results showed that the FeOx clusters possess electrocatalytic activity for a multielectron oxygen reduction reaction, and the high photocurrent of the electrode is remarkably reduced by the FeOx-surface modification. Consequently, the striking photocatalytic activity of FeOx/TiO2-NR//SnO2 HEMCs was ascribable to the switching of the electron transport direction necessary for the charge separation from the long axis of the TiO2 NR to the short axis.

Bottom-up formation of gold truncated pyramids smaller than 10 nm on SrTiO3 nanocubes: an application for plasmonic water oxidation.

An atomically commensurate interface gives rise to Au truncated pyramids < 10 nm on single-crystalline SrTiO3 nanocubes (NCs) in a simple deposition-precipitation process without a surface modifier, and the resulting hybrid nanocrystals exhibit a high level of photocatalytic activity for a plasmonic oxygen evolution reaction at light wavelengths (λex) ≤ 1200 nm.

Hereditary spherocytosis diagnosed with extremely low glycated hemoglobin compared to plasma glucose levels.

Glycated hemoglobin (HbA1c) is an important indicator of glycemic control in patients with diabetes. High-performance liquid chromatography (HPLC) is the most commonly used method for measuring HbA1c levels; as HPLC measures all hemoglobin types, the values can be influenced by hemoglobin variants. Moreover, as HPLC-HbA1c levels are low in some diseases, including hemolytic anemia, it may be difficult to differentiate hemoglobin variants from these diseases based on HPLC-HbA1c levels alone. Similar HbA1c values using both HPLC and immunoassays (IAs) are noted for these diseases, while discrepancies are noted in the case of hemoglobin variants. Herein, we describe our process of differential diagnosis for hereditary spherocytosis, the most common inherited hemolytic anemia, in a 56-year-old man presenting with a low HPLC-HbA1c level compared to the glucose concentration, concomitant with anemia, jaundice, hyperbilirubinemia, cholelithiasis, and splenomegaly. There was a discrepancy between HbA1c levels measured with HPLC and IAs and glycated albumin levels. The possibility of hemoglobin variants was unlikely, based on the chromatography and isoelectric focusing results. The haptoglobin levels and reticulocyte counts were low and high, respectively. The direct and indirect Coomb's tests were negative. The presence of spherocytes on blood smears and flow cytometric analysis of the eosin-5-maleimide binding test supported a diagnosis of hereditary spherocytosis. We recommend that when a discrepancy between HPLC-HbA1c levels and glucose concentrations is noted, clinicians should consider hemolysis or hemoglobin variants as the diagnosis. It should be considered that a discrepancy between HbA1c levels measured with HPLC and IAs does not specifically exclude hemolysis.

Splenic abscess diagnosed following relapsing sterile peritonitis in a peritoneal dialysis patient: A case report with literature review.

Peritoneal dialysis (PD)-related peritonitis is sometimes complicated with other infections; however, few cases of splenic abscess have been reported. We present the case of a 64-year-old PD patient with complicated splenic abscesses diagnosed following relapsing sterile peritonitis. After PD induction, he presented with turbid peritoneal fluid and was diagnosed with PD-related peritonitis. A plain abdominal computed tomography (CT) did not reveal any intra-abdominal focus of infection. After empiric intravenous antibiotics, the peritoneal dialysate was initially cleared, with a decrease in dialysate white blood cells (WBC) to 20/µL. However, WBC and C-reactive protein (CRP) levels remained elevated. A contrast-enhanced abdominal CT showed two areas of low-density fluid with no enhancement in a mildly enlarged spleen, making it difficult to distinguish abscesses from cysts. Due to relapsing sterile peritonitis, we performed an abdominal ultrasonography, and suspected splenic abscesses due to rapid increase in size. Repeated imaging tests were useful in establishing a diagnosis of splenic abscesses. Considering the persistent elevation of WBC and CRP levels, imaging findings, and episodes of relapsing peritonitis, we comprehensively formed the diagnosis, and performed a splenectomy as a rescue therapy. We should consider the possibility of other infectious foci with persistent inflammation after resolving PD-related peritonitis.

Ammonium ion-promoted electrochemical production of synthetic gas from water and carbon dioxide on a fluorine-doped tin oxide electrode.

In situ generated Sn nanoparticles on fluorine-doped tin oxide act as an electrocatalyst for the CO2 reduction reaction to efficiently and stably produce synthetic gas from water and carbon dioxide with the reaction rate drastically enhanced by the addition of ammonium ions.

Optical Hot Spot Generation by the Plasmonic Coupling of Au Nanoparticles in the Nanospaces of Mesoporous Titanium(IV) Oxide.

An in situ reduction technique consisting of chemisorption of 1,3,5,7-tetramethylcyclotetrasiloxane (TMCTS) and subsequent reaction with HAuCl4 has been developed for depositing Au nanoparticles (NPs) uniformly in the depth direction of a mesoporous TiO2 nanocrystalline film (Au/TMCTS/mp-TiO2). The TMCTS monolayer is further converted into silicon oxide by heating in the air (Au/SiOx/mp-TiO2). In the absorption spectra of Au/SiOx/mp-TiO2 prepared at varying HAuCl4 concentrations (C), the localized surface plasmon resonance (LSPR) band of Au NPs significantly broadens C ≈ 1.22 mM at 546 nm to be split into two peaks around 500 and 700 nm at C ≥ 2.43 mM, whereas such a phenomenon is not observed for the usual Au NP-loaded TiO2 particles. Three-dimensional-finite difference time domain simulations showed that the unique optical property of Au/SiOx/mp-TiO2 stems from the effective LSPR coupling of very close Au NPs and partial fusions in the nanospaces of mp-TiO2. Further, the optical hot spots in Au/TMCTS/mp-TiO2 as well as Au/SiOx/mp-TiO2 generate an intense local electric field giving increase to a great enhancement of the absorption in the infrared spectrum of the TMCTS monolayer on mp-TiO2.

Pain sensitivity after low-level clenching is influenced by preloading eccentric exercise.

PURPOSE: To examine the effect of preloading eccentric exercise on pain sensitivity in healthy volunteers. METHODS: In 20 healthy volunteers, pain-related sensations (6 items: pain, unpleasantness, fatigue, stiffness, tension, and soreness during maximum biting), and pain intensities induced by repeated electrical stimuli on the masseter and the hand palm were evaluated using a visual analog scale (VAS) of 0-100 mm. Eccentric exercise (6 min-test) or gum chewing (6 min-control) was used as preloading exercise to evaluate the effect on pain sensitivities before and after low-level clenching (15 min) performed 2 days after the preloading exercise. RESULTS: Eccentric exercise induced only low levels of pain-related sensations 2 days later. However, the time course of temporal summation induced by four repeated electrical stimuli on the masseter was influenced by the type of preloading exercise, i.e., temporal summation increased after the low-level clenching (P = 0.016) when preloading was done by the eccentric exercise, while no significant change was observed when preloading was done by the gum chewing. CONCLUSIONS: Eccentric exercise may facilitate pain sensitivity induced by subsequent low-level clenching via the central nervous system. In addition, it was demonstrated that pain sensitivity after the low-level clenching could be influenced by the type of preloading exercise. These experimental results may suggest that eccentric exercise could act as one of the triggering factors in the mechanism by which tooth clenching leads to a chronic pain condition in susceptible individuals.

Clinical Characteristics and Risk Factors for Mortality due to Bloodstream Infection of Unknown Origin in Hemodialysis Patients: A Single-Center, Retrospective Study.

INTRODUCTION: Hemodialysis patients are at a high risk of bloodstream infection (BSI). The risk factors for BSI-associated mortality, especially of unknown origin, remain uncertain. BSI of unknown origin is highly prevalent and related to high mortality. The present study aimed to investigate the clinical and microbiological characteristics of BSI and risk factors for BSI-associated mortality, including BSI of unknown origin, in hemodialysis patients. METHODS: This study was a single-center, retrospective study conducted from August 2012 to July 2019 in hemodialysis patients with BSI at Kawashima Hospital. Data related to demographics, clinical parameters, BSI sources, causative microorganisms, and initial treatments were collected from the medical records. The predictors for mortality associated with BSI were evaluated by logistic regression. RESULTS: Among 174 patients, 55 (30.9%) had the infection from unknown origin. The most frequent bacterium was Staphylococcus aureus. Low serum albumin level was an independent predictor of mortality due to BSI (odds ratio [OR]: 0.28, 95% confidence interval [CI]: 0.13-0.59). A lower serum albumin level (≤2.5 g/dL) was associated with poorer mortality. Methicillin-resistant Staphylococcus aureus (MRSA) was independently associated with mortality due to BSI of unknown origin (OR: 6.20, 95% CI: 1.04-37.1); 87.5% cases with BSI of unknown origin due to MRSA were not initially administrated anti-MRSA antibiotics, and in such patients, the mortality rate was 85.7%. CONCLUSIONS: Serum albumin level of 2.5 g/dL is a cutoff value, which could predict the mortality due to BSI in hemodialysis patients. Considering the high mortality rate of MRSA-associated BSI of unknown origin, wherein no focus of infection was identified in the present study, initial empiric treatment should be considered for MRSA-associated BSI of unknown origin.

Parathyroidectomy for tertiary hyperparathyroidism after second kidney transplantation: a case report.

Successful kidney transplantation usually resolves secondary hyperparathyroidism (SHPT). However, some patients fail to normalize, and their condition is often referred to as tertiary hyperparathyroidism (THPT). Surgical consensus on the timing of post-transplant parathyroidectomy (PTX) for THPT has not been reached. Herein, we report a case of a 58-year-old post-transplant woman, considering the concrete timing of PTX for both SHPT and THPT. She initiated hemodialysis with end-stage renal disease at the age of 24, and underwent first kidney transplantation at the age of 28. When peritoneal dialysis (PD) was induced due to the worsening kidney function at the age of 50, the serum intact parathyroid hormone (iPTH) level remarkably increased (2332 pg/mL). Although cinacalcet was administered, the patient's iPTH levels were not sufficiently suppressed for seven years. Diagnostic images including ultrasound, computed tomography, and 99mTc-methoxyisobutylisonitrile scintigraphy indicated THPT as the reason for prolonged post-transplant hypercalcemia. Therefore, PTX was performed 14 months after the second transplantation. Histology showed nodular hyperplasia of all parathyroid glands, indicating autonomous secretion of parathyroid hormone. In general, patients with more severe THPT are recognized with more severe SHPT prior to transplantation during the dialysis period. We should consider a referral for surgery based on the individual risk factors. We recommend to perform parathyroidectomy earlier, before the kidney transplantation in the clinical suspicion of severe SHPT.

Au-Ag alloy nanoparticle-incorporated AgBr plasmonic photocatalyst.

A solid-phase photochemical method produces Au-Ag alloy nanoparticles (NPs) with a sharp size distribution and varying composition in AgBr crystals (Au-Ag@AgBr). These features render Au-Ag@AgBr promising as a material for the plasmonic photocatalyst further to provide a possibility of elucidating the action mechanism due to the optical tunability. This study shows that the visible-light activity of Au-Ag@AgBr for degradation of model water pollutant is very sensitive to the alloy composition with a maximum at the mole percent of Au to all Ag in AgBr (y) = 0.012 mol%. Clear positive correlation is observed between the photocatalytic activity and the quality factor defined as the ratio of the peak energy to the full width at half maximum of the localized surface plasmon resonance band. This finding indicates that Au-Ag@AgBr works as a local electromagnetic field enhancement-type plasmonic photocatalyst in which the Au-Ag NPs mainly promotes the charge separation. This conclusion was further supported by the kinetic analysis of the light intensity-dependence of external quantum yield.